JPH0283066A - Simultaneous multilayer coating - Google Patents
Simultaneous multilayer coatingInfo
- Publication number
- JPH0283066A JPH0283066A JP23671988A JP23671988A JPH0283066A JP H0283066 A JPH0283066 A JP H0283066A JP 23671988 A JP23671988 A JP 23671988A JP 23671988 A JP23671988 A JP 23671988A JP H0283066 A JPH0283066 A JP H0283066A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- viscosity
- layer
- bottom layer
- solid content
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 87
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000010409 thin film Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 71
- 239000000839 emulsion Substances 0.000 description 39
- 108010010803 Gelatin Proteins 0.000 description 29
- 239000008273 gelatin Substances 0.000 description 29
- 229920000159 gelatin Polymers 0.000 description 29
- 235000019322 gelatine Nutrition 0.000 description 29
- 235000011852 gelatine desserts Nutrition 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000011241 protective layer Substances 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 16
- 239000002562 thickening agent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- -1 silver halide Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- 238000007796 conventional method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 210000003205 muscle Anatomy 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 5
- 229910021612 Silver iodide Inorganic materials 0.000 description 5
- 229940045105 silver iodide Drugs 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 241000195940 Bryophyta Species 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229960000633 dextran sulfate Drugs 0.000 description 3
- 235000011929 mousse Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- RZCXRDBYLLLRKH-UHFFFAOYSA-N 2-(2-ethylhexyl)-2-sulfobutanedioic acid Chemical compound CCCCC(CC)CC(S(O)(=O)=O)(C(O)=O)CC(O)=O RZCXRDBYLLLRKH-UHFFFAOYSA-N 0.000 description 1
- XFSMEWPSXDHRNU-UHFFFAOYSA-N 4-(2-ethylhexoxy)-4-oxo-3-sulfobutanoic acid Chemical compound CCCCC(CC)COC(=O)C(S(O)(=O)=O)CC(O)=O XFSMEWPSXDHRNU-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960002086 dextran Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000009753 muscle formation Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- XAATWVAYTRHTQX-UHFFFAOYSA-M sodium;2,3,4-tri(propan-2-yl)benzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C(C(C)C)=C1C(C)C XAATWVAYTRHTQX-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はスライドホッパー装置による多層同時塗布方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a multilayer simultaneous coating method using a slide hopper device.
ウェブと通常体している長尺可撓性支持体上にスライド
ホッパー装置を用いて多数の層を同時に塗布する例とし
ては写真感光材料塗布の例が挙げられる。この方法はス
ライド面上を複数の層が重畳して同時に流れ、スライド
端において移動するウェブと出会う点にビードを形成し
、このビードを介して該多数の塗布層をウェブ上に同時
に塗布す、る。この塗布方法においてはビードの安定が
非常に重要であって、ビードの状態が不安定であると筋
状の故障が発生したり、液切れを起こして塗布不能にな
る場合すらあり、製品収率の低下、品質保証の問題等が
起こる。この対策として、例えばビードの上下に空気圧
力差を設は下側を負圧にすることにより、ビードの安定
をはかる方法等の技術がよく使用されている。このよう
な塗布方法において特に多層同時塗布の場合、各塗布層
の塗布液物性、ならびに相互の関係が安定な塗布を行う
為に非常に重要である。An example of coating a plurality of layers simultaneously using a slide hopper apparatus onto a long flexible support, which is usually a web, is in the case of coating photosensitive materials. In this method, a plurality of layers flow simultaneously on a slide surface in a superimposed manner, a bead is formed at the point where it meets the moving web at the end of the slide, and the multiple coating layers are simultaneously applied onto the web via this bead. Ru. Bead stability is very important in this coating method, and if the bead is unstable, streaks may occur, or the liquid may run out, making it impossible to coat, resulting in reduced product yield. This may lead to a decline in quality and quality assurance problems. As a countermeasure against this problem, techniques are often used, such as a method of stabilizing the bead by, for example, creating an air pressure difference between the upper and lower sides of the bead and creating a negative pressure on the lower side. In such a coating method, especially in the case of simultaneous multi-layer coating, the physical properties of the coating liquid of each coating layer and their mutual relationships are very important for stable coating.
近時、写真感光材料は薄膜化し、しかも高速塗布の要請
が強く、このような場合、安定な塗布を行う事が益々困
難になっている。In recent years, photographic materials have become thinner and there is a strong demand for high-speed coating, and in such cases it has become increasingly difficult to perform stable coating.
従来、このような対策として最下層の低粘度化が行なわ
れてきた。例えば特公昭56−20534号においては
、最下層2〜12μmの湿潤膜厚(以下hwと記す)で
粘度1〜8cpとし、次の層はhv15〜20μIで粘
度10= 100cpとする方法が開示されている。こ
の場合、最下層の粘度が低いためビード部が不安定とな
り、最下層と次層の間で層間混合が起こる。Conventionally, as a countermeasure to this, the viscosity of the bottom layer has been lowered. For example, Japanese Patent Publication No. 56-20534 discloses a method in which the lowest layer has a wet film thickness of 2 to 12 μm (hereinafter referred to as hw) and a viscosity of 1 to 8 cp, and the next layer has a wet film thickness of 2 to 12 μm and a viscosity of 10=100 cp. ing. In this case, since the viscosity of the bottom layer is low, the bead portion becomes unstable and interlayer mixing occurs between the bottom layer and the next layer.
特公昭60−12107号では、最下層の粘度が低剪断
速度(10”5ec−’)の時、20〜200cp、高
剪断速度(LO’5ec−’)の時、1Ocp以下とす
る方法が開示されているが、最下層のみの設定では層間
混合を起こしてしまう事がある。Japanese Patent Publication No. 60-12107 discloses a method in which the viscosity of the bottom layer is 20 to 200 cp at low shear rate (10''5ec-') and 1Ocp or less at high shear rate (LO'5ec-'). However, setting only the bottom layer may cause interlayer mixing.
特開昭56−108566号では、低剪断速度の時は最
下層と隣接層の粘度差を±10cpとし高剪断速度の時
は最下層がその隣接層より低粘度になる方法を開示して
いる。JP-A-56-108566 discloses a method in which the viscosity difference between the bottom layer and the adjacent layer is ±10 cp at low shear rates, and the bottom layer has a lower viscosity than its adjacent layer at high shear rates. .
尚特開昭61−174970号では上記と同様の方法を
最上層とその隣接層にも適用する方法を開示している。Furthermore, Japanese Patent Laid-Open No. 174970/1983 discloses a method in which the same method as above is applied to the uppermost layer and its adjacent layer.
特開昭59〜100434号には、比較的高粘度の層の
下側に加速層、上側に伸展層を設けることとし、この加
速層はhw2〜30μmの時、粘度1〜20cpとし、
伸展層はhw5〜20μmで1〜100pとする方法を
開示している。In JP-A-59-100434, an acceleration layer is provided below a relatively high viscosity layer, and an extension layer is provided above the layer, and this acceleration layer has a viscosity of 1 to 20 cp when hw is 2 to 30 μm,
A method is disclosed in which the extension layer has a hw of 5 to 20 μm and a thickness of 1 to 100 p.
以上の特許は、いずれも基本的には最下層の粘度を次層
の粘度より低くする方法であるが、薄膜塗、布条件で低
粘度化することはビード形成には有利であるが、筋の発
生に対しては劣化する傾向にある。このI;め特願昭6
3−30180号にはむしろ最下層粘度を高くする方法
が開示されており、筋の発生の完全な対策は未だ確立さ
れていないのが現状である。All of the above patents basically involve making the viscosity of the bottom layer lower than the viscosity of the next layer, but lowering the viscosity through thin film coating and cloth conditions is advantageous for bead formation, but It tends to deteriorate in response to the occurrence of. This I;me special request 1976
No. 3-30180 discloses a method of increasing the viscosity of the bottom layer, and the current situation is that a complete countermeasure against the occurrence of streaks has not yet been established.
上記問題点に対し本発明の目的は、スライドホッパー装
置を用いて多層同時塗布を行う場合、高速、薄膜条件に
おいても筋故障の出難い安定な塗布方法を提供すること
である。In view of the above-mentioned problems, an object of the present invention is to provide a stable coating method in which streak failure is unlikely to occur even under high-speed, thin-film conditions when performing multilayer simultaneous coating using a slide hopper device.
本発明の上記目的は、スライドホッパー装置を用いて、
多数の塗布液を移動しているウェブに同時に塗布する多
層同時塗布方法において、支持体に接する最下層を形成
する塗布液に含有する水に不溶性の固形分含量が2〜1
5W/V%である場合、該最下層の粘度を上記固形分含
量に応じて調節することを特徴とする多層同時塗布方法
により達成される。The above object of the present invention is to use a slide hopper device to
In a multilayer simultaneous coating method in which a large number of coating solutions are simultaneously applied to a moving web, the water-insoluble solid content contained in the coating solution forming the bottom layer in contact with the support is 2 to 1.
5 W/V% is achieved by a multilayer simultaneous coating method characterized in that the viscosity of the bottom layer is adjusted according to the solid content.
また、支持体側より第1層に塗布すべき液を2分し、1
方を上記の条件に適合する粘度及び固形分濃度条件とし
て、最下層塗布液とし、他方を第2層とすることを特徴
とする多層同時塗布方法も適用することができる。In addition, the liquid to be applied to the first layer from the support side was divided into two parts, and one
It is also possible to apply a multilayer simultaneous coating method characterized in that one layer is used as the bottom layer coating liquid and the other layer is used as the second layer, with the viscosity and solid content concentration conditions meeting the above conditions.
以下、本発明の詳細について説明する。The details of the present invention will be explained below.
前記のごとく、スライドホッパーによる多層同時塗布方
法における安定性に対しては各層の物性が非常に重要で
ある。特に最下層の粘度の設定は重要であるが、従来は
層間の関係のみに注意がはられれており、本発明のごと
く層を構成する固形含量と粘度の関係が塗布安定性に及
ぼす影響について着目し、解明した例はない。As mentioned above, the physical properties of each layer are very important for stability in the multilayer simultaneous coating method using a slide hopper. Setting the viscosity of the bottom layer is particularly important, but conventionally attention has been paid only to the relationship between layers, but as in the present invention, attention has been focused on the influence of the relationship between the solid content and viscosity of the layers on coating stability. However, there are no cases where this has been solved.
本発明者等は鋭意研究の結果、筋故障が出ない塗布安定
性を有する最下層の粘度は、該最下層塗布液中の固形含
量と2次式で表される関係があることを見いだした。し
かし、多層同時塗布する塗布液あるいは塗布条件により
上記粘度の絶対値としては若干の変動があるが、−例と
して固形含量による最下層の粘度の設定は下記式で算出
される値、(cps)以上であり、好ましくは該値〜該
値+IOである。ただし、塗布限界以上の高粘度に適用
出来ないことは言うまでもない。As a result of intensive research, the present inventors have discovered that the viscosity of the bottom layer, which has coating stability without streak failure, has a relationship expressed by a quadratic equation with the solid content in the bottom layer coating liquid. . However, the absolute value of the above viscosity may vary slightly depending on the coating solution or coating conditions used for simultaneous multi-layer coating; for example, the viscosity of the bottom layer based on the solids content can be calculated using the following formula: (cps) The value is above, and preferably the value is from the value to the value +IO. However, it goes without saying that it cannot be applied to high viscosities exceeding the coating limit.
2≦C≦8.8
r(C)=0.7C”−12,33c+61.47゜8
.8≦C≦14
f(C)=2.0C2−35,24C+162.4〔式
中、Cは固形分濃度(w /V%)であり、f (C)
は該固形分より上式で算出される粘度(c p s)を
表す。〕
尚、最下層の粘度調整に増粘剤を用いることできる。2≦C≦8.8 r(C)=0.7C”-12,33c+61.47°8
.. 8≦C≦14 f (C) = 2.0C2-35, 24C + 162.4 [In the formula, C is the solid content concentration (w / V%), f (C)
represents the viscosity (c p s) calculated from the solid content using the above formula. ] Note that a thickener can be used to adjust the viscosity of the bottom layer.
また、支持体側から第1層に予定される塗布液層が前記
条件に適合しない場合、必ずしも該塗布液層全部を希釈
または増粘して前記条件範囲にする必要はなく、その1
部を前記条件範囲に固形分濃度及び粘度を調整して最下
層とすることができる。すなわち全部を希釈または増粘
することによる、乾燥負荷や塗布液供給系への負荷の増
大を防ぎつつ、筋故障の発生を防止することができる。In addition, if the coating liquid layer scheduled as the first layer from the support side does not meet the above conditions, it is not necessarily necessary to dilute or increase the viscosity of the entire coating liquid layer to bring it into the above condition range.
The bottom layer can be formed by adjusting the solid content concentration and viscosity within the above condition range. In other words, it is possible to prevent the occurrence of streak failure while preventing an increase in the drying load and the load on the coating liquid supply system due to dilution or thickening of the entire composition.
本発明でいう固形分とは、例えばハロゲン化銀写真感光
材料に適用した場合では、塗布液中のハロゲン化銀結晶
、マット剤等水に不溶の固形分を意味する。濃度C%は
塗布液100cc中の固形分の重量(9)で表す。In the present invention, the solid content refers to solid content insoluble in water, such as silver halide crystals and matting agents in the coating solution, when applied to silver halide photographic materials, for example. The concentration C% is expressed as the weight (9) of solid content in 100 cc of the coating liquid.
粘度はブルックフィールド型粘度計で測定した値を採用
した。The viscosity was measured using a Brookfield viscometer.
本発明においてはスライドホッパー塗布方式によるもの
であれば、特に塗布液等に限定はないが、ハロゲン化銀
写真感光材料の多層同時塗布に対しては特に有効に適用
することができる。In the present invention, there are no particular limitations on the coating liquid as long as the slide hopper coating method is used, but it can be particularly effectively applied to simultaneous multilayer coating of silver halide photographic light-sensitive materials.
本発明に適用するハロゲン化銀写真感光材料には限定は
なく、該業界公知の各種材料、技術を適用することがで
きる。There is no limitation to the silver halide photographic material applicable to the present invention, and various materials and techniques known in the industry can be applied.
本発明の感光材料に用いるハロゲン化銀乳剤には、ハロ
ゲン化銀としで、臭化銀、塩化銀、沃臭化銀、塩臭化銀
、塩沃臭化銀等の通常の/10ゲン化銀乳剤に使用され
る任意のものを用いる事ができ、ハロゲン化銀粒子は、
酸性法、中性法及びアンモニア法のいずれで得られたも
のでもよい。The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any grains used in silver emulsions can be used, and the silver halide grains are
It may be obtained by any of the acidic method, neutral method and ammonia method.
、本発明のハロゲン化銀写真感光材料には各種添加剤を
含んでもよく、増粘剤又は可塑剤として例えば米国特許
2,960.404号、特公昭43−4939号、***
国出願公告1,904,604号、特開昭48−637
15号、ベルギー国特許762.833号、米国特許3
,767.410号、ベルギー国特許588.143号
の各明細書に記載されている物質、例えばスチレン−マ
レイン酸ソーダ共重合体、デキストランサルフェート等
を用いることが出来、更に、塗布助剤、乳化剤、処理液
等に対する浸透性の改良剤、消泡剤或いは感光材料の種
々の物理的性質をコントロールするために用いられる界
面活性剤としては英国特許548,532号、同1,2
16.389号、米国特許2,026.202号、同3
,514゜293号、特公昭44−26580号、同4
3−17922号、同43−17926号、同43−3
166号、同48−20785号、仏画特許202.5
88号、ベルギー国特許773.459号、特開昭48
−101118号等に記載されているアニオン性、カチ
オン性、非イオン性或いは両性の化合物を使用すること
ができるが、これらのうち特にスルホン基を有するアニ
オン界面活性剤、例えばコハク酸エステルスルホン化物
、アルキルベンゼンスルホン化物等が好ましい。また構
成層にはマット化剤、例えばスイス特許330.158
号に記載のシリカ、仏閣特許1,296,995号に記
載のガラス粉、英国特許1,173.181号に記載の
アルカリ土類金属又はカドミウム、亜鉛などの炭酸塩な
どの無機物粒子;米国特許2,322.037号に記載
の澱粉、ベルギー特許625.451号或いは英国特許
981,198号に記載された澱粉誘導体、特公昭44
−3643号に記載のポリビニルアルコール、スイス特
許330.158号に記載されたポリスチレン或いはポ
リメチルメタアクリレート、米国特許3,079,25
7号に記載のポリアクリロニトリル、米国特許3,02
2,169号に記載のポリカーボネートのような有機物
粒子を含むことができる。The silver halide photographic material of the present invention may contain various additives, such as thickeners or plasticizers, such as those described in U.S. Pat. No. 904,604, JP-A-48-637
No. 15, Belgian Patent No. 762.833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc., and coating aids and emulsifiers. As surfactants used for improving permeability to processing liquids, antifoaming agents, and controlling various physical properties of photosensitive materials, British Patent Nos. 548,532 and 1, 2 are used as surfactants.
No. 16.389, U.S. Patent No. 2,026.202, No. 3
, No. 514゜293, Special Publication No. 44-26580, No. 4
No. 3-17922, No. 43-17926, No. 43-3
No. 166, No. 48-20785, French painting patent 202.5
No. 88, Belgian Patent No. 773.459, Japanese Unexamined Patent Publication No. 1973
Anionic, cationic, nonionic or amphoteric compounds described in No. 101118, etc. can be used, and among these, anionic surfactants having a sulfonic group, such as succinic acid ester sulfonated compounds, Alkylbenzene sulfonated compounds and the like are preferred. The constituent layers may also contain matting agents, such as Swiss Patent No. 330.158.
silica described in No. 1,296,995; glass powder described in British Patent No. 1,173.181; inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc described in British Patent No. 1,173.181; Starch described in No. 2,322.037, starch derivatives described in Belgian patent No. 625.451 or British patent No. 981,198, Japanese Patent Publication No. 1973
-3643, polystyrene or polymethyl methacrylate as described in Swiss Patent No. 330.158, U.S. Pat. No. 3,079,25
Polyacrylonitrile as described in No. 7, U.S. Pat. No. 3,02
Organic particles such as polycarbonate described in US Pat. No. 2,169 may be included.
多層同時塗布方法はカラー感光材料において特に有用で
あるが、カラー感光材料にはカプラー紫外線吸収剤、抗
酸化剤等の油溶性化合物が含まれる。感光材料には、更
に目的に応じて種々の添加剤を用いることができる。こ
れらの添加剤は、より詳しくは、リサーチディスクロー
ジャー第176巻1 tem17643 (1978年
12月)及び同187巻1 te1118716(19
79年11月)に記載されている。The multilayer simultaneous coating method is particularly useful for color light-sensitive materials, which contain oil-soluble compounds such as couplers, ultraviolet absorbers, and antioxidants. The photosensitive material may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem 17643 (December 1978) and Research Disclosure, Vol.
(November 1979).
また感光材料に用いられるバインダー(又は保護コロイ
ド)としては、ゼラチンを用いるのが有利であるが、ゼ
ラチン誘導体、ゼラチンと他の高分子のグラフトポリマ
ー それ以外の蛋白質、糖誘導体、セルロース誘導体、
単一或は共重合体のごとき合成親水性高分子物質等の親
水性コロイドも用いることが出来る。Furthermore, as a binder (or protective colloid) used in photosensitive materials, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used.
実施例1
常法により、沃化銀2モル%を含み、緑感性を有する沃
臭化銀乳剤を調製した。該乳剤はゼラチンをバインダー
とし、該乳剤35(2中には沃臭化銀6.65に9、ゼ
ラチン1.75に9を含有し、延展剤として、界面活性
剤ソヂウムージー(2−エチルヘキシル)−スルホサク
シネートの1%水溶液、増粘剤としてはスチレン−マレ
イン酸共重合体の4%水溶液を使用した。保護層として
は、8%のゼラチン水溶液20Qに前記界面活性剤を1
.212、硬膜剤としてホルマリンの4%水溶液1.6
+2.更に増粘剤としては前記の共重合体を加え、保護
層塗布粘度を35゛Cにおいて20cpに調節した。Example 1 A silver iodobromide emulsion containing 2 mol % of silver iodide and having green sensitivity was prepared by a conventional method. The emulsion uses gelatin as a binder, emulsion 35 (2 contains 6.65 to 9 silver iodobromide and 1.75 to 9 gelatin), and the surfactant sodium mousse (2-ethylhexyl) as a spreading agent. A 1% aqueous solution of sulfosuccinate was used, and a 4% aqueous solution of styrene-maleic acid copolymer was used as a thickener.As a protective layer, 1% of the above surfactant was added to 8% gelatin aqueous solution 20Q.
.. 212, 4% aqueous solution of formalin as hardening agent 1.6
+2. Further, the above copolymer was added as a thickener, and the coating viscosity of the protective layer was adjusted to 20 cp at 35°C.
乳剤層塗布液は表1に示すゼラチン、界面活性剤を加え
、種々の固形分濃度を有する液を調製した。上記塗布液
をポリエチレンテレフタレートベース上に塗布速度60
m/minで支持体側から乳剤層、保護層の順にスライ
ドホッパー装置を用いて2層同時塗布した。その際のコ
ーター間隙は150μm1表1
表1に使用した乳剤量は総て各35Qであり、各試料は
表2に示すごとく増粘剤を添加して35゛Cにおいて各
種の粘度を有する塗布液を調製した。The gelatin and surfactant shown in Table 1 were added to the emulsion layer coating solution to prepare solutions having various solid content concentrations. Coating the above coating solution onto the polyethylene terephthalate base at a speed of 60
Two layers were simultaneously coated using a slide hopper device in the order of the emulsion layer and the protective layer from the support side at m/min. The coater gap at that time was 150 μm1 Table 1 The amount of emulsion used in Table 1 was all 35Q, and each sample was coated with a coating solution having various viscosities at 35°C by adding a thickener as shown in Table 2. was prepared.
これらの各種条件の塗布液を前記のごとく保護層と2層
同時塗布した。塗布時の液温は35°Cである。塗布乾
燥後、常法により現像し、得られた現像ずみ試料を検討
し、単位幅当たりの筋発生本数を調べた。Coating liquids under these various conditions were simultaneously coated in two layers, including the protective layer, as described above. The liquid temperature during application was 35°C. After coating and drying, development was performed by a conventional method, and the developed sample obtained was examined to determine the number of streaks generated per unit width.
この結果をグラフlに示す。The results are shown in graph 1.
同グラフにおいて筋発生本数は
○・・0本、△・・1〜5本、X・・6〜12本、××
・・20本以上を示す。In the same graph, the number of muscles generated is ○...0, △...1 to 5, X...6 to 12, ××
...Indicates 20 or more pieces.
単位 c p s (35℃)
グラフlの結果より筋故障の出ない粘度は固形分含量と
2次関数関係がみられ、固形分含量から導かれる粘度以
上であれば筋故障の発生が抑制されることがわかる。た
だし、ある粘度以上では当然ビード破壊がおこる。本実
施例ではその限界は約50c p sである。Units: c p s (35°C) From the results in graph 1, it can be seen that the viscosity at which muscle failure does not occur has a quadratic relationship with the solids content, and if the viscosity is higher than the viscosity derived from the solid content, the occurrence of muscle failure will be suppressed. I understand that. However, above a certain viscosity, bead breakage naturally occurs. In this example, the limit is approximately 50 cps.
実施例2
Emlの調製
常法により、沃化銀7モル%を含み、青感性を有する沃
臭化銀乳剤を調製した。該乳剤はゼラチンをバインダー
とし、該乳剤30ff中には沃臭化銀6゜73に9、ゼ
ラチン1.5Kgを含有し、延展剤として、界面活性剤
ソヂウムージー(2−エチルヘキシル)−スルホサクシ
ネートの1%水溶液、増粘剤としてはカルボキシアルキ
ルデキストラン
ルの4%水溶液を使用した。また、下記黄色カプラー溶
液を添加してEmlとした。Example 2 Preparation of Eml A silver iodobromide emulsion containing 7 mol % of silver iodide and having blue sensitivity was prepared by a conventional method. The emulsion uses gelatin as a binder, and 30 ff of the emulsion contains 6.73 to 9 silver iodobromide and 1.5 kg of gelatin, and the surfactant sodium mousse (2-ethylhexyl)-sulfosuccinate is used as a spreading agent. A 1% aqueous solution was used, and a 4% aqueous solution of carboxyalkyl dextran was used as the thickener. Further, the following yellow coupler solution was added to prepare Eml.
Emlは表3に示すように乳剤304に下記カプラー溶
液40Qを加え、ゼラチン量及び仕上げ量をかえてA−
Dの4種類の乳剤を作成し、さらにこれら各乳剤を表4
に示すように上記増粘剤量のコントロールにより粘度(
38°C)をかえた試料を作成した。As shown in Table 3, Eml was prepared by adding the following coupler solution 40Q to emulsion 304 and changing the amount of gelatin and finishing amount.
Four types of emulsions D were prepared, and each of these emulsions was shown in Table 4.
As shown in the figure, the viscosity (
Samples were prepared at different temperatures (38°C).
黄色カプラー溶液
下記構造のカプラー1.8Kgをジブチル7タレート1
.8Kgと酢酸エチル3.6Q.に溶解し、ラウリルス
ルホコハク酸ナトリウム1009を含む5%ゼラチン溶
液3012に加え、APVゴーリン社製ホモジナイザー
タイプM3で乳化分散を行い4Hに仕上げ、黄色形成
カプラー
表 3
表3に使用した乳剤量は各30Q1カプラー量は40a
である。Yellow coupler solution 1.8 kg of coupler with the following structure is mixed with 7 dibutyl talates and 1 part
.. 8Kg and ethyl acetate 3.6Q. The amount of emulsion used in Table 3 is 30Q1 for each yellow forming coupler. Coupler amount is 40a
It is.
表4
単位 cps(38℃)
Em2の調製
常法により、沃化銀4モル%を含み、緑感性を有する沃
臭化銀乳剤を調製した。該乳剤はゼラチンをバインダー
とし、該乳剤3512中には沃臭化銀6゜68に9、ゼ
ラチン1.75Kgを含有し、延展剤として、界面活性
剤ソヂウムージ−(2−エチルヘキシル)スルホサクシ
ネートの1%水溶液、さらに上記カプラー液を40Q加
え、増粘剤としてはカルボキシ、アルキルデキストラン
硫酸エステルの4%水溶液を使用し、液粘度20c p
s (38°C)になるように133.6ffに仕上
げ、Em2とした。Table 4 Unit cps (38°C) A silver iodobromide emulsion containing 4 mol % of silver iodide and having green sensitivity was prepared by a conventional method for preparing Em2. The emulsion uses gelatin as a binder, and emulsion 3512 contains 6.68 to 9 silver iodobromide and 1.75 kg of gelatin, and contains the surfactant sodium mousse (2-ethylhexyl) sulfosuccinate as a spreading agent. A 1% aqueous solution and 40Q of the above coupler liquid were added, a 4% aqueous solution of carboxy and alkyl dextran sulfate was used as a thickener, and the liquid viscosity was 20cp.
It was finished to 133.6ff so that the temperature was 38°C (38°C), and it was named Em2.
保護層の調製
保護層としては、5%のゼラチン水溶液中20Q中にラ
ウリルベンゼンスルホン酸ナトリウムを0.2%の濃度
で含み、硬膜剤としてホルマリンの4%水溶液1.61
2.更に増粘剤としては前記の共重合体を加え、保護層
塗布粘度を20cp(38℃)に調節し に 。Preparation of the protective layer The protective layer contained sodium laurylbenzenesulfonate at a concentration of 0.2% in 20Q in a 5% aqueous gelatin solution, and a 4% aqueous formalin solution 1.61% as a hardening agent.
2. Furthermore, the above copolymer was added as a thickener to adjust the coating viscosity of the protective layer to 20 cp (38°C).
上記のように調製した各塗布液を支持体側からEml、
Em2、保護層の順にスライドホッパー装置によりトリ
アセテートペース上に同時塗布した。その条件は塗布時
湿潤膜厚はEmlが40μm。Eml each coating solution prepared as above from the support side,
Em2 and the protective layer were simultaneously coated on the triacetate paste in this order using a slide hopper device. The conditions were that the wet film thickness at the time of coating was 40 μm.
Em2は30μm1保護膜は20μmとし、塗布速度8
0m/min、コーター間隙150.um、コーター減
圧度は一30mmaq、塗布液温度38°Cで塗布した
。Em2 is 30 μm, protective film is 20 μm, coating speed is 8
0m/min, coater gap 150. The coater was coated at a vacuum of -30 mmaq and a coating solution temperature of 38°C.
これらの各種条件の試料を塗布乾燥後、常法により現像
し、得られた現像ずみ試料を検討し、単位幅当たりの筋
発生本数を調べた。After coating and drying samples under these various conditions, they were developed by a conventional method, and the developed samples obtained were examined to determine the number of streaks generated per unit width.
この結果をグラフ2に示す。The results are shown in Graph 2.
グラフ2から明らかなように本実施例の結果でも実施例
1と同様に筋故障の出ない粘度は固形分含量と相関が認
められる。As is clear from Graph 2, in the results of this example, as in Example 1, the viscosity at which muscle failure does not occur is correlated with the solid content.
実施例3
常法により、塩化銀90モル%、臭化銀10モル%を含
む塩臭化銀乳剤を調製した。該乳・剤はゼラチンをバイ
ンダーとし、該乳剤35Q中には塩臭化銀5゜2LKg
、ゼラチン1.75Kgを含有し、延展剤として、界面
活性剤ソヂウムーイソアミルーN−デシル−スルホサク
シネートの2%水溶液、増粘剤としてはポリスチレンス
ルホン酸ナトリウムの4%水溶液を使用した。保護層と
しては、8%のゼラチン水溶液1012に前記界面活性
剤をo、aQ、硬膜剤としてホルマリンの4%水溶液0
.8L グリオキザールの4%水溶液O,a12、更に
増粘剤としては前記のものを加え、保護層塗布粘度を2
0cp(38°C)に調節しtこ。Example 3 A silver chlorobromide emulsion containing 90 mol % of silver chloride and 10 mol % of silver bromide was prepared by a conventional method. The emulsion uses gelatin as a binder, and the emulsion 35Q contains 5°2 LKg of silver chlorobromide.
, 1.75 kg of gelatin was used, a 2% aqueous solution of surfactant sodium isoamyl N-decyl-sulfosuccinate was used as a spreading agent, and a 4% aqueous solution of sodium polystyrene sulfonate was used as a thickener. As a protective layer, the above surfactant was added to 8% gelatin aqueous solution 1012, aQ, and 4% formalin aqueous solution 0 was used as a hardening agent.
.. 8L 4% aqueous solution of glyoxal O, a12, and further add the above-mentioned thickener to reduce the coating viscosity of the protective layer to 2.
Adjust to 0cp (38°C).
乳剤層塗布液は表5に示すようにゼラチン、界面活性剤
を加え、種々の固形分濃度を有する液を調・製した。Emulsion layer coating solutions were prepared by adding gelatin and surfactants as shown in Table 5, and having various solid content concentrations.
上記塗布液をポリエチレンテレフタレートペース上に塗
布速度90m/minで支持体側から乳剤層、保護層の
順にスライドホッパー装置を用いて2層間時塗布した。The above coating solution was coated onto a polyethylene terephthalate paste at a coating speed of 90 m/min in two layers from the support side in the order of the emulsion layer and the protective layer using a slide hopper device.
その際のコーター間隙は150μm。The coater gap at that time was 150 μm.
減圧度−3Qmmaq、塗布液温度35℃とした。The degree of vacuum was -3Qmmaq, and the coating liquid temperature was 35°C.
表 5
表5に使用した乳剤量は総て各35Qであり、各試料は
表6に示すごとく増粘剤を添加して35°Cにおいて各
種の粘度を有する塗布液を調製した。Table 5 The amounts of emulsions used in Table 5 were all 35Q, and as shown in Table 6, thickeners were added to each sample to prepare coating solutions having various viscosities at 35°C.
これらの各種条件の塗布液を前記のごとく保護!と2層
間時塗布した。塗布乾燥後、常法により現像し、得られ
た現像ずみ試料を検討し、単位幅当たりの筋発生本数を
調べた。Protect the coating liquid under these various conditions as described above! The two layers were coated for one hour. After coating and drying, development was performed by a conventional method, and the developed sample obtained was examined to determine the number of streaks generated per unit width.
この結果をグラフ3に示す。The results are shown in Graph 3.
同グラフにおいて筋発生本数の表示は実施例1と同じで
ある。In the same graph, the display of the number of muscle formations is the same as in Example 1.
表6
単位 el)S(35°C)
グラフ3の結果より筋故障の出ない粘度は固形分含量と
2次関数関係がみられ、固形分含量から導かれる粘度以
上であれば筋故障の発生が抑制されることがわかる。Table 6 Unit: el) S (35°C) From the results of Graph 3, the viscosity at which muscle failure does not occur has a quadratic relationship with the solid content, and if the viscosity is higher than the viscosity derived from the solid content, muscle failure will occur. can be seen to be suppressed.
さらに、実施例1〜3において筋の発生しない最低の粘
度値をプロットしたのがグラフ4である。Further, Graph 4 is a plot of the lowest viscosity values at which streaks do not occur in Examples 1 to 3.
グラフ4から実験系が異なっているにも拘わらずこのグ
ラフは驚くべき連続性をしめしていることがわかる。本
発明者等は他の数多くの実験の結果、支持体に接する最
下層塗布液の固形分濃度に対し下記実験式で表現される
数値以上の値を粘度値として採用すれば、筋の発生が極
めてよく抑制される。ことを見いだした。またこの関係
をグラフ5に示す。From graph 4, it can be seen that this graph shows surprising continuity despite the different experimental systems. As a result of numerous other experiments, the present inventors have found that if a value greater than the value expressed by the following empirical formula is adopted as the viscosity value for the solid content concentration of the bottom layer coating liquid in contact with the support, streaks will not occur. Very well suppressed. I found out. This relationship is also shown in graph 5.
2≦C≦8.8
f(C)=0.7C”−12,33c+61.47゜8
.8≦C≦14
f(C)=2−QC’−35,24C+162.4〔式
中、Cは固形分濃度(W/v%)であり、f (C)は
該固形分より上式で算出される粘度(c p s)を表
す。〕
実施例4
常法により、沃化銀2モル%、を含む沃臭化銀乳剤を調
製した。該乳剤はゼラチンをバインダーとし、該乳剤3
5g中には沃臭化銀6.65に9、ゼラチン1.575
に9を含有し、延展剤として、界面活性剤ソヂウムージ
(−2−エチルヘキシル)−スルホサクシネートの1%
水溶液、増粘剤としてはスチレン−マレイン酸共重合体
の4%水溶液を使用した。2≦C≦8.8 f(C)=0.7C”-12,33c+61.47°8
.. 8≦C≦14 f(C)=2-QC'-35,24C+162.4 [wherein, C is the solid content concentration (W/v%), and f (C) is It represents the calculated viscosity (c p s). Example 4 A silver iodobromide emulsion containing 2 mol % of silver iodide was prepared by a conventional method. The emulsion uses gelatin as a binder, and the emulsion 3
5 g contains 6.65 to 9 silver iodobromide and 1.575 to 9 gelatin.
9 and 1% of the surfactant sodium sulfosuccinate (-2-ethylhexyl)-sulfosuccinate as a spreading agent.
A 4% aqueous solution of styrene-maleic acid copolymer was used as the aqueous solution and thickener.
E m 3の調製
上記乳剤35g中にゼラチン2493g、上記界面活性
剤51.2ccを添加し、51.2Qに仕上げた。Preparation of E m 3 2493 g of gelatin and 51.2 cc of the above surfactant were added to 35 g of the above emulsion to give an emulsion of 51.2Q.
Em4の調製
上記乳剤356中にゼラチン2493g、上記界面活性
剤73.8ccを添加し、73.8Qに仕上げた。Preparation of Em4 2493 g of gelatin and 73.8 cc of the above surfactant were added to the above emulsion 356 to give an emulsion of 73.8Q.
上記E m 3.4は共に12c p s (38℃)
に粘度調整した。The above E m 3.4 is both 12c ps (38℃)
The viscosity was adjusted to
保護層の調製
堡−裏層としては、8%のゼラチン水溶液10ffiに
前記界面活性剤を0.82.硬膜剤としてホルマリンの
4%水溶液0.8ρ、グリオキザールの4%水溶液0.
812.更に増粘剤としては前記のものを加え、保護層
塗布粘度を20cp(38℃戸こ調節した。Preparation of protective layer - For the back layer, 0.82% of the above surfactant was added to 10ffi of an 8% aqueous gelatin solution. As a hardening agent, a 4% aqueous solution of formalin 0.8ρ and a 4% aqueous solution of glyoxal 0.8ρ.
812. Furthermore, the above-mentioned thickener was added, and the coating viscosity of the protective layer was adjusted to 20 cp (38° C.).
塗布試料lとして支持体側最下層にE m 3を湿潤膜
厚50μm1その上に保護層を同じ<20μmで同時2
層塗布した。As a coating sample 1, E m 3 was applied as the lowest layer on the support side at a wet film thickness of 50 μm 1 and a protective layer was placed on top of it at the same <20 μm 2 at the same time.
A layer was applied.
塗布試料2としては支持体側最下層にEm4を湿潤膜厚
14.4/7 m 、その上にEm3を40μm、さら
にその上層に保護膜を同じ<20μmで同時3層塗布し
I;。For coating sample 2, Em4 was applied as the lowest layer on the support side to a wet film thickness of 14.4/7 m, Em3 was applied on top of that to a thickness of 40 μm, and a protective film was applied on top of that in three layers simultaneously at the same thickness of <20 μm.
支持体は180μmのポリエチレンテレフタレートベー
スを用い、塗布速度60m/winでスライドホッパー
装置を用い、コーター間隙は1502m1減圧度−39
cmaq、液温度38℃とした。A 180 μm polyethylene terephthalate base was used as the support, a slide hopper device was used at a coating speed of 60 m/win, and the coater gap was 1502 m1 and the degree of vacuum was -39.
cmaq, and the liquid temperature was 38°C.
実施例1と同様の方法で評価した結果、単位幅当たりの
筋本数は塗布試料lが30本、塗布試料2は発生がなか
った。As a result of evaluation in the same manner as in Example 1, the number of streaks per unit width was 30 for coated sample 1, and no streaks for coated sample 2.
本実施例のごとく2、固形分12%を含む乳剤層塗布液
を粘度12cpsとし、そのまま塗布した系では筋が多
発したにも拘わらず、その1部を希釈し、これを新たな
最下層として塗布した系では筋は発生しなかった。As in Example 2, the emulsion layer coating solution containing 12% solid content was made to have a viscosity of 12 cps, and even though many streaks occurred when the system was applied as is, a part of it was diluted and used as a new bottom layer. No streaks occurred in the applied system.
塗布試料l及び2は乾燥後においては全く同じ銀付量、
ゼラチン付量であり、性能上は全く同一の品質であった
。Coated samples 1 and 2 have exactly the same amount of silver coating after drying,
The amount of gelatin applied was the same, and the quality was exactly the same in terms of performance.
本実施例の別の実施態様として塗布液の粘度を上昇させ
ることなく、最下層に塗布すべき液の一部を分割し、所
望の固形分濃度とした上でこれを新たな最下層として用
い、残りはそのまま第2層目以上に適用することにより
、筋のない良好な塗布品質を得ることが出来る。As another embodiment of this example, without increasing the viscosity of the coating liquid, a part of the liquid to be applied to the bottom layer is divided, the desired solid content concentration is achieved, and this is used as a new bottom layer. By applying the rest as is to the second layer or higher, good coating quality without streaks can be obtained.
実施例5
常法により、沃化銀5モル%を含み、緑感性を有する沃
臭化銀乳剤を調製した。該乳剤はゼラチンをバインダー
とし、該乳剤30Q中には沃臭化銀6゜697Kg、ゼ
ラチン1.2に9を含有し、延展剤として、界面活性剤
ソヂウムージ−(2−エチルヘキシル)−スルホサクシ
ネートの1%水溶液、増粘剤としてはカルボキシアルキ
ルデキストラン硫酸エステルの4%水溶液を使用した。Example 5 A silver iodobromide emulsion containing 5 mol % of silver iodide and having green sensitivity was prepared by a conventional method. The emulsion uses gelatin as a binder, and emulsion 30Q contains 6.697 kg of silver iodobromide, 9 to 1.2 kg of gelatin, and the surfactant sodium mousse-(2-ethylhexyl)-sulfosuccinate as a spreading agent. A 1% aqueous solution of carboxyalkyl dextran sulfate was used as the thickener.
また、下記マゼンタカプラー溶液を添加した。Additionally, the following magenta coupler solution was added.
さらに上記乳剤30ffに下記カブラ−溶液3512を
加えた。Furthermore, the following fogler solution 3512 was added to 30ff of the above emulsion.
下記構造のカプラー1.8Kgを酢酸エチル4.0Qと
ジブチル7タレート1.8Kgに溶解し、トリイソプロ
ピルベンゼンスルホン酸ナトリウム100gを含む5%
ゼラチン溶液30Qに加え、APVゴーリン社製ホモジ
ナイザー タイプM3で乳化分散を行い水を加えて35
Qに仕上げ、乳剤に添加した。Dissolve 1.8 kg of a coupler with the following structure in 4.0 Q of ethyl acetate and 1.8 kg of dibutyl 7-talate, and prepare a 5% solution containing 100 g of sodium triisopropylbenzenesulfonate.
In addition to gelatin solution 30Q, emulsify and disperse with APV Gorlin homogenizer type M3 and add water.
Q was finished and added to the emulsion.
上記乳剤30ffとカプラー35Qの中にゼラチン62
30り、上記界面活性剤22.3ccを添加し、223
Qに仕上げた。粘度は15cps (38℃)に調整し
た。Gelatin 62 in the above emulsion 30ff and coupler 35Q
30, add 22.3 cc of the above surfactant,
I finished it in Q. The viscosity was adjusted to 15 cps (38°C).
Em6の調製
Em5の111.612を大川原製作所製遠心薄膜濃縮
機CEP−Is型を用いて67ffまで濃縮した。この
結果、塗布液粘度は20cps(33℃)となった。Preparation of Em6 111.612 of Em5 was concentrated to 67ff using a centrifugal thin film concentrator model CEP-Is manufactured by Okawara Seisakusho. As a result, the viscosity of the coating liquid was 20 cps (33° C.).
保護層としては、5%のゼラチン水溶液中20ff中に
ラウリルベンゼンスルホン酸ナトリウムを0.2%の濃
度で含み、硬膜剤としてホルマリンの4%水溶液1.6
ff、更に増粘剤としては前記の共重合体を加え、保護
層塗布粘度を20cp(38℃)に調節した。The protective layer contained sodium laurylbenzenesulfonate at a concentration of 0.2% in 20ff of a 5% aqueous gelatin solution, and the hardening agent was a 4% aqueous formalin solution (1.6%).
ff, and the above-mentioned copolymer was added as a thickener, and the coating viscosity of the protective layer was adjusted to 20 cp (38° C.).
塗布試料3として支持体側最下層にEm5を湿潤膜厚4
0μm1その上に実施例2で用いたE m 2を35μ
m1さらに保護層を同じ<20μmで同時3層塗布した
。As coating sample 3, Em5 was applied as the lowest layer on the support side at a wet film thickness of 4.
0 μm 1 On top of that, 35 μm of E m 2 used in Example 2
ml and three protective layers with the same <20 μm thickness were simultaneously applied.
塗布試料4としては支持体側最下層にE m 6を湿潤
膜厚12μm1その上にEm5を20 p m sさら
にその上層に上記Em2を35μm1次に保護膜を同じ
<20μmで同時4層塗布した。For coating sample 4, the lowest layer on the support side was coated with E m 6 at a wet film thickness of 12 μm, on top of which Em5 was coated at 20 pm, and the above Em2 was coated on top with a wet film thickness of 35 μm, and then a protective film was coated in 4 layers at the same thickness of <20 μm.
支持体は120μmのトリアセテートベースを用い、塗
布速度80a+/winでスライドホッパー装置ヲ用い
、コーター間隙は150I4m1減圧度−30mmaq
1塗布液温度38℃とした。A 120μm triacetate base was used as the support, a slide hopper device was used at a coating speed of 80a+/win, and the coater gap was 150I4m1 and the degree of vacuum was -30mmaq.
1 Coating solution temperature was 38°C.
実施例1と同様の方法で評価した結果、単位幅光たりの
筋本数は塗布試料3が36本、塗布試料4は発生がなか
った。As a result of evaluation in the same manner as in Example 1, the number of streaks per unit width of light was 36 for coated sample 3, and no streaks for coated sample 4.
固形分3%を含むEm5を粘度15cps (38°C
)とし、そのまま塗布した系では、筋が多発した(こも
拘わらず、その1部を濃縮し、これを新たな最下層とし
て塗布した系んでは筋の発生はなかった。Em5 containing 3% solids with a viscosity of 15 cps (38°C
), and in the system where it was applied as it was, many streaks occurred (However, in the system where a part of it was concentrated and applied as a new bottom layer, no streaks occurred.
塗布試料5.6は乾燥後においては全く同じ銀付量、同
じゼラチン付量であり、性能上全べ同じ品質であった。Coated samples 5.6 had exactly the same amount of silver and gelatin after drying, and had the same quality in terms of performance.
本発明により、多層同時塗布において、高速薄膜条件に
おいても筋故障の出難い安定な塗布方法を提供すること
ができた。According to the present invention, it was possible to provide a stable coating method in which streak failure is unlikely to occur even under high-speed thin film conditions in multilayer simultaneous coating.
グラフ1〜グラフ5はそれぞれ多層同時塗布の際の、最
下層の固形分含量と粘度の関係における筋故障発生状況
を示すグラフである。Graphs 1 to 5 are graphs showing the occurrence of streak failure in the relationship between the solid content and viscosity of the bottom layer during simultaneous multilayer coating.
Claims (2)
、移動しているウェブに同時に塗布する多層同時塗布方
法において、支持体に接する最下層を形成する塗布液が
水に不溶性の固形分含量を2〜15W/V%含有する場
合、該最下層の粘度を上記固形分含量に応じて調節する
ことを特徴とする多層同時塗布方法。(1) In a multilayer simultaneous coating method in which multiple coating solutions are simultaneously applied to a moving web using a slide hopper device, the water-insoluble solid content of the coating solution that forms the bottom layer in contact with the support. 2 to 15 W/V%, the viscosity of the bottom layer is adjusted according to the solid content.
方を上記請求項1の条件に適合する粘度及び固形分濃度
条件として、最下層塗布液とし、他方を第2層とするこ
とを特徴とする多層同時塗布方法。(2) Divide the liquid to be applied to the first layer from the support side into two parts, and
A multi-layer simultaneous coating method, characterized in that one of the coating liquids is used as the bottom layer coating liquid, and the other layer is used as the second layer, with the viscosity and solid content concentration conditions meeting the conditions of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23671988A JPH0283066A (en) | 1988-09-20 | 1988-09-20 | Simultaneous multilayer coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23671988A JPH0283066A (en) | 1988-09-20 | 1988-09-20 | Simultaneous multilayer coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0283066A true JPH0283066A (en) | 1990-03-23 |
Family
ID=17004763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23671988A Pending JPH0283066A (en) | 1988-09-20 | 1988-09-20 | Simultaneous multilayer coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0283066A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8695788B2 (en) | 2007-06-18 | 2014-04-15 | Interroll Holding Ag | Conveyor roller mounted via bearing pots |
-
1988
- 1988-09-20 JP JP23671988A patent/JPH0283066A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8695788B2 (en) | 2007-06-18 | 2014-04-15 | Interroll Holding Ag | Conveyor roller mounted via bearing pots |
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