JP3662230B2 - Support composed of aromatic polyester film and photographic light-sensitive material using the same - Google Patents

Description

【００２４】
【表２】

【００２５】
（２−１）コロナ処理
塗布に先立ち両面にコロナ処理（ピラー社製ソリッドステートコロナ処理機６ＫＶＡモデルを用い、支持体の両面を室温下において２０ｍ／分で処理）を実施した。この時の電流、電圧の読み取り値から、支持体には０．３７５ｋＶ・Ａ・分／ｍ^２の処理がなされている。この時の処理周波数は９．６ｋＨｚ、電極と誘電体ロールのギャップクリアランスは１．６ｍｍであった。この上に下記層を塗設した。
（２−２）下塗第１層
下記組成の水分散ラテックスをワイヤーバーを用いて乾燥膜厚が０．３μｍとなるよう塗布し１２０℃で２分間乾燥した。
ブタジエン−スチレン共重合ラテックス １３ｍｌ
（固形分４３％、ブタジエン／スチレン重量比＝３２／６８）
２，４−ジクロロ−６−ヒドロキシ−Ｓ−トリアジンナトリウ ７ｍｌ
ム塩 ８％水溶液
ラウリルベンゼンスルホン酸ナトリウム １％水溶液 １．６ｍｌ
コロイダルシリカ 粒径と量は表１に記載
蒸留水 ８０ｍｌ
【００２６】
（２−３）下塗第２層
下記組成の水溶液をワイヤーバーを用いて乾燥膜厚が０．１４μｍとなるように塗布した。塗布の有無および乾燥条件は表１に示した。
ゼラチン ０．９ｇ
メチルセルロース（メトローズＳＭ１５ 置換度１．７９〜 ０．１ｇ１．８３）
酢酸（濃度９９％） ０．０２ｍｌ
蒸留水 ９９ｍｌ
【００２７】
（２−４）バック第１層（導電性層）
下記組成の導電性素材を含むアクリルラテックス水分散液を、乾燥膜厚が表１の値になるように塗布し１８０℃で３０秒乾燥し、表面電気抵抗が１０^６Ωの支持体を作成した。
アクリル樹脂水分散液 ２．０重量部
（ジュリマ−ＥＴ４１０、固形分２０重量％、日本純薬（株) 製）
酸化スズ−酸化アンチモン水分散物 １８．１重量部
（平均粒径０．１μｍ、１７重量％）
ポリオキシエチレンフェニルエーテル ０．１重量部
コロイダルシリカ サイズ・添加量は表１に記載
これに蒸留水を加えて１００重量部となるように調製した。
【００２８】
（２−５）ポリオレフィン層（すべり層）
下記組成のポリオレフィンラテックス水分散液を、乾燥膜厚が表１の値になるように塗布した。塗布の有無および乾燥条件は表１に記載した。
ポリオレフィン ３．０重量部
（ケミパールＳ−１２０、２７重量％、三井石油化学（株) 製）
コロイダルシリカ ２．０重量部
（スノーテックスＣ、日産化学（株) 製）
エポキシ化合物 ０．３重量部
（デナコールＥＸ−６１４Ｂ、ナガセ化成（株) 製）
蒸留水を加えて合計が１００重量部になるように調製
（３）熱処理
熱処理に先だって上記の方法に従って下記の評価を実施し、結果を表１に示した。
▲１▼１５０℃熱収縮
▲２▼Ｒ_ａ、Ｒ_ｔ
表１に示した条件で熱処理を実施した。
【００２９】
（４）評価
熱処理後の熱可塑性フィルムに対し上記の方法に従って下記の評価を実施し、結果を表１に示した。
▲１▼縦皺
▲２▼１２０℃熱収縮
（５）感材の作成
上記下塗、バック層を塗設し熱処理を施した熱可塑性フィルムの下塗側に表１に示した感光層を塗設した。これを発光時間１０^−４SECのキセノンフラッシュ光でテストパターンを焼き付けた後特表平７−５０５４８８号に記載の熱現像機を用いて１２０℃で３０秒現像を行った。これをＰＳ版に焼き付けたところ、本発明では良好な平面性と寸法安定性を達成し良好な焼き付けを実現した。一方比較例では焼き付け時に縦皺に起因するボケと寸法変化に起因する焼き付けズレを発生した。
【００３０】
【発明の効果】
本発明の熱可塑性フィルムは平面性が良好であり熱寸法安定性にすぐれ写真用支持体として用いた時に熱現像による寸法変化によるボケや焼き付けズレなどの故障を惹起しない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aromatic polyester film support and a photographic light-sensitive material using the same.
[0002]
[Prior art]
Conventional photographic light-sensitive materials are subjected to wet development using a developer after photographing. However, this method has the following problems, and improvement of this point has been desired.
(1) Since development, bleaching, fixing, and drying are performed, time is required for development processing.
(2) Since a plurality of tanks containing developer are required, the developing machine cannot be reduced in size and weight.
(3) Replenishment of developer, disposal, and cleaning of the developing tank are required.
In order to improve this, 80-150 ° C. as described in US Pat. No. 3,152,904, US Pat. No. 3,457,075, Japanese Examined Patent Publication No. 43-4921, Japanese Examined Patent Publication No. 43-4924, etc. A photographic material is proposed which is processed by a heat developing method (hereinafter sometimes abbreviated as heat development). As an example of this, there is a method in which a precursor of a developer is previously contained in the photosensitive layer, which is decomposed by heat to form a developer, and then developed. In such a thermal development system, the development process can be performed in a short time only by applying heat, and the developing machine can be downsized. Furthermore, there is no need to worry about replenishment or disposal of the developer.
However, when this type of photosensitive material is used as a printing photosensitive material, color shift occurs when four plates (blue, green, red, black) are stacked due to dimensional changes that occur during thermal development. There is a difficulty. In order to solve this, conventional methods for heat-treating a photographic support under low tension are known (for example, JP-A-60-22616, JP-A-64-64883, JP-A-54). -158470, U.S. Pat. No. 2,796,684). By applying these low-tensile heat treatments, the dimensional change before and after heat development could be reduced, but with this, poor flatness (vertical failure: vertical piles in the longitudinal direction of the support, The wrinkles generated at a pitch of 10 to 20 cm in the width direction are generated, which is a serious problem for a photographic support that requires high flatness. As a countermeasure against this, there is known a method of extending a ridge on a roll by passing between a large number of rolls as described in US Pat. No. 3,663,683. However, in this method, the tension loss generated in the pass roll is large, and it is difficult to convey with low tension, so that sufficient dimensional stability cannot be achieved.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a silver halide photographic support comprising an aromatic polyester film having good flatness and excellent thermal dimensional stability, and a silver halide photographic light-sensitive material using the same.
[0004]
[Means for Solving the Problems]
  These problems have been achieved by the following means.
  That is, the present invention
(1)An aromatic polyester film having a thermal shrinkage at 150 ° C. of 0.01% or more and 0.4% or less is heat-treated while being transported under the conditions simultaneously satisfying the following formulas (1) to (3);Silver halide photographic light-sensitive material comprising an aromatic polyester film characterized by having a vertical gutter height of 0 μm to 200 μm and a longitudinal heat shrinkage at 120 ° C. of 0.001% to 0.05%. Support.
          0.001 ≦ F ≦ 0.05 (1)
          120 ≦ T ≦ 220 (2)
          1 ≦ (T × L) / (F × 1000) ≦ 800 (3)
    F = Conveyance tension per unit cross-sectional area applied to the thermoplastic film
    Force (kg / mm ² )
    T = heat treatment temperature (° C)
    L = longest non-contact transport length in heat treatment zone (m)
(2) An aromatic polyester film having a ten-point average roughness (Rz) of 0.18 μm to 8.0 μm and a maximum point height (Rt) of 0.3 μm to 10 μm.SaidA support for a silver halide photographic light-sensitive material comprising the aromatic polyester film according to (1) obtained by heat treatment.
(3)An aromatic polyester film having an undercoat layer containing a matting agent and a backing layer,Silver halide photographic light-sensitive material comprising an aromatic polyester film characterized by having a vertical gutter height of 0 μm to 200 μm and a longitudinal heat shrinkage at 120 ° C. of 0.001% to 0.05%. Support.
(4)  The support for a silver halide photographic light-sensitive material comprising the aromatic polyester film according to (3), wherein the matting agent has a particle size of 0.1 to 15 μm.
(5)  Any one of (1) to (4)A silver halide photographic light-sensitive material, which is used as a support for the aromatic polyester film described in 1.
(6)  It is a heat-developable photographic photosensitive material (5)The silver halide photographic light-sensitive material described.
[0005]
The present invention has been made clear that the downside failure occurs as a result of the thermoplastic film shrinking between rolls during the heat treatment process. That is, when heat treatment is performed at a high temperature with low tension, the support tends to shrink. However, shrinkage is suppressed on the pass roll by the frictional force between the film and the roll. On the other hand, since it can shrink freely between rolls, the width of the film is reduced. In order to eliminate such a difference in width between the roll and the roll, undulation occurs in the vicinity of the roll. Creeping is easy at high temperatures, and such deformation becomes permanent. Therefore, such vertical warp tends to occur when transporting at high temperature and low tension.
Therefore, warp is more likely to occur as the length between the pass rolls in the heat treatment zone, that is, the non-contact conveyance length is longer, and is likely to occur as the temperature is higher and the tension is smaller. In the method of the present invention, this heat treatment is performed without the occurrence of vertical lines.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
  The manufacturing method of the aromatic polyester film used as a thermoplastic film in the present invention is as follows.
(A) It can be manufactured by heat-treating while being transported under the conditions satisfying the following formulas (1) to (3).
0.001 ≦ F ≦ 0.05 (1)
120 ≦ T ≦ 220 (2)
1 ≦ (T × L) / (F × 1000) ≦ 800 (3)
F = Conveying tension per unit cross-sectional area applied to the thermoplastic film (kg / mm 2)
T = heat treatment temperature (° C)
L = longest non-contact transport length in heat treatment zone (m)
(B) 150 ° C. heat shrinkage before heat treatment of the thermoplastic film is 0.01% or more and 0.4% or less, and the heat treatment described in (a) is performed and manufactured.
(C) The difference between the maximum value and the minimum value of the width direction distribution of heat shrinkage at 150 ° C. before heat treatment of the thermoplastic film is 0% or more and 0.1% or less. The described thermoplastic film is produced.
(D) The ten-point average roughness (Rz) of the thermoplastic film before heat treatment is 0.18 μm or more and 8.0 μm or less, and the maximum point height (Rt) is 0.3 μm or more and 10 μm or less. ) ~ (B)The heat treatment method described is performed and manufactured. If the conveying tension F exceeds the range of the present invention, thermal shrinkage tends to increase, which is not preferable. On the other hand, if it is less than the range of the present invention, it is not preferable because a trouble such as meandering is likely to occur. Transport tension is usually 0.001kg / mm²0.05 kg / mm²Or less, preferably 0.003 kg / mm²0.03 kg / mm²Or less, more preferably 0.007 kg / mm²0.02 kg / mm or more²It is as follows. Such tension can be achieved by adjusting a motor installed on at least one of the winding side and the feeding side. At this time, it is preferable to adjust the tension pickup while monitoring the tension. However, since it is easy to collapse when it is wound with such a low tension, it is preferable to wind with a high tension after the tension cut in front of the winding portion.
[0007]
The heat treatment temperature is usually 120 ° C. or higher and 220 ° C. or lower, preferably 135 ° C. or higher and 200 ° C. or lower, and more preferably 145 ° C. or higher and 180 ° C. or lower. If this temperature range is exceeded, oligomers contained in the thermoplastic film are deposited on the surface and haze is likely to increase, which is not desirable. Below this temperature range, thermal shrinkage tends to increase and the object of the invention cannot be achieved. Such temperature control may be achieved by blowing hot air into a heat treatment zone using a heat insulating material, or the plastic film may be heated by heat transfer in contact with a high-temperature heat medium such as a heat roll. The temperature may be raised by radiant heat using an infrared heater or the like. Any method may be used, but it is preferable to reduce the temperature distribution in the width direction in order to reduce the width direction distribution of heat shrinkage. This can be achieved by installing fins at the hot air outlet and adjusting the direction of the air to eliminate the accumulation of the air, or by dividing and controlling the heat roll and infrared heater so that the temperature at both ends tends to be high. Can be achieved. Here, the heat treatment temperature T is higher than the glass transition temperature Tg.
[0008]
The maximum length between pass rolls is usually in the range of 1 ≦ (T × L) / (F × 1000) ≦ 800 shown in the above equation (3) as a function of tension (F) and heat treatment temperature (T), Preferably, it is set to satisfy 2 ≦ (T × L) / (F × 1000) ≦ 200, more preferably 4 ≦ (T × L) / (F × 1000) ≦ 80. Below this range, it is necessary to install a large number of pass rolls with a short roll interval, and it is necessary to set a large conveying tension due to the tension loss occurring here, and the dimensional stability tends to deteriorate. On the other hand, if it exceeds this range, shrinkage of the base width tends to be large, and vertical wrinkles tend to occur, which is not desirable. The length between pass rolls here refers to the maximum length existing in the heat treatment zone. This is because if a single point exceeds the range of the present invention, vertical lines occur there, so the maximum length needs to be within the above range. This is important because downspout once generated between pass rolls is hard to disappear.
[0009]
  Furthermore, the present invention can further reduce the problem of downpipe by improving the thermoplastic film used. The 1st makes 150 degreeC heat shrink of the thermoplastic film before heat processing 0.01% or more and 0.4% or less.. GoodPreferably, 0.05% or more and 0.3% or less, more preferably 0.1% or more and 0.25% or less is used. That is, by using a thermoplastic film having a small heat shrinkage, there is an effect of reducing the shrinkage between the pass rolls generated during the heat treatment and suppressing the occurrence of warp. If the heat shrinkage exceeds 0.4%, the dimensional stability of the photographic image is deteriorated. On the other hand, a thermoplastic film having a 150 ° C. heat shrinkage lower than the above range has sufficiently high thermal dimensional stability, and there is no need to carry out the heat treatment of the present invention. Such a support isa.Improved stretching conditions,b.There is a method of pre-heat treatmentbThe method is more preferable.bIn this method, the heat treatment is performed at 120 to 220 ° C., more preferably 130 to 200 ° C., further preferably 150 to 190 ° C. before the heat treatment of the present invention. Thus, heat shrinkage is performed to some extent in advance to reduce the amount of heat shrinkage generated by the heat treatment of the present invention. Therefore, since this pre-heat treatment does not require high dimensional stability like the above heat treatment, it is preferable to prevent the occurrence of warp by increasing the tension accordingly. Such a heat treatment may be performed alone, but when there is a coating process, it is efficient to perform it in the subsequent drying process. When used as a photographic support, it is preferably carried out in this drying step in order to coat a primer and a backing layer.
  on the other handMethod aCan be achieved by decreasing the draw ratio and increasing the heat setting temperature, both of which are in the direction of decreasing the elastic modulus of the thermoplastic film, and are not so preferred.
[0010]
Next, the second improvement of the thermoplastic film is that the difference between the maximum value and the minimum value of the 150 ° C. heat shrinkage width direction distribution before heat treatment is 0% or more and 0.10 or less, more preferably 0% or more and 0.07%. Hereinafter, it is more preferable to use a thermoplastic film of 0% or more and 0.05% or less. That is, it is preferable to use a thermoplastic film having uniform heat shrinkage in the width direction. This is because if there is unevenness in the amount of heat shrinkage, it will shrink greatly locally and tend to cause downfall. Such a thermoplastic film can be achieved by (1) improvement of film forming conditions and (2) pre-heat treatment. {Circle around (1)} can be achieved by raising the heat setting temperature for the end portion where heat shrinkage tends to increase. {Circle around (2)} is the same as described above, and attempts to reduce the difference between the maximum value and the minimum value by reducing the absolute value of heat shrinkage.
[0011]
  Third, the ten-point average roughness (Rz) of the thermoplastic film is preferably 0.18 μm or more and 8.0 μm or less, more preferably 0.20 μm or more and 6.0 μm or less, and even more preferably 0.3 μm or more. It is 4.5 μm or less. Rz refers to the difference between the average value of 10 points from the highest of the peaks present in the reference length and the average value of 10 points from the deepest valley. That is, when the height of the protrusion larger than the average unevenness (average roughness; Ra) is within the range of the present invention, the friction between the roll and the thermoplastic film can be effectively lowered. For the same reason, the maximum point height (Rt) Between 0.3 μm and 10.0 μm, more preferably between 0.4 μm and 8.0 μm, and even more preferably between 0.6 μm and 6.0 μm. Rt indicates the difference between the highest protrusion and the deepest valley present in the reference length. If both Rz and Rt are less than the range of the present invention, the flatness tends to be lowered, and if it exceeds, the added fine particles are peeled off to cause roll contamination, which is not preferable.
[0012]
Such a thermoplastic film adjusts the friction with the pass roll by imparting irregularities to the surface of the thermoplastic film, and makes it easy to heat shrink even on the pass roll. Since it can shrink | contract similarly to the thermoplastic film between the pass rolls which are not receiving the restraining force by this, generation | occurrence | production of a vertical wrinkle can be reduced. Exceeding the scope of the present invention is not preferable because the fine particles added to achieve the surface roughness peel off and contaminate the process. On the other hand, if it falls below, the effect cannot be obtained and the vertical warp tends to occur. Such a thermoplastic film can be supported by (1) providing a fine particle layer on the outermost surface, and (2) increasing the amount of fine particles (filler) added to the thermoplastic film.
[0013]
The method of (1) is an inorganic material such as silica, alumina, barium sulfate, calcium carbonate, titania, tin oxide, indium oxide, talc, or organic materials such as polystyrene, polymethyl methacrylate, polymethacrylate, polyacrylonitrile, cellulose, gelatin and the like. A method of coating fine particles together with a binder is mentioned. The shape of these fine particles is not particularly limited, and can be used in a needle shape, a spherical shape, a plate shape, or a crushed shape. A preferable size is 0.1 to 15 μm, more preferably 0.2 to 10 μm, and still more preferably 0.3 to 7 μm. The amount of matting agent added is 1m on one side²It is 0.1 to 50 mg per unit, more preferably 0.2 to 30 mg, and still more preferably 0.3 to 20 mg. Among these fine particles, ZnO and TiO are particularly preferable.₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃, V₂O₅At least one crystalline metal oxide selected from the group consisting of fine particles of these composite oxides. Further preferred is SnO₂Is a conductive material containing about 5 to 20% of antimony oxide and / or further containing other components (for example, silicon oxide, boron, phosphorus, etc.). When these conductive fine particles are used, it is possible to suppress a dusty failure due to static electricity generated during the heat treatment. These conductive inorganic fine particles have a volume resistivity of 10⁷Ωcm or less, more preferably 10⁶Ωcm or less, more preferably 10⁵Ωcm or less. The binder for dispersing these fine particles is not particularly limited, and gelatin, water-soluble polyester, polyurethane, styrene-butadiene rubber, polyvinylidene chloride, polyvinyl chloride, polyurethane, polyacrylic ester, polymethacrylic ester, polyamide, etc. should be used. Can do.
[0014]
Prior to these coatings, it is also preferable to carry out glow discharge treatment, corona treatment, ultraviolet treatment, and flame treatment to improve adhesion. Moreover, these coating methods can use a well-known method. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper described in US Pat. No. 2,681,294, or US Pat. No. 2,761,418 Multi-layer simultaneous coating methods described in US Pat. Nos. 3,508,947 and 2,761791 can be used.
[0015]
The method (2) is a method in which a filler such as an inorganic substance such as silica, alumina, barium sulfate, calcium carbonate, titania, tin oxide, indium oxide and talc is kneaded into the thermoplastic film. There is no restriction | limiting in particular in the shape of these fillers, A needle shape, a spherical shape, a plate shape, and a crushed shape can be used. A preferable size is 0.01 to 10 μm, more preferably 0.05 to 5 μm, and still more preferably 0.1 to 3 μm. The amount of filler added is 10 to 1000 ppm, more preferably 20 to 500 ppm, and still more preferably 30 to 300 ppm.
[0016]
The thermoplastic film that can be produced by applying the heat treatment method of the present invention is made of an aromatic polyester. The aromatic polyester as used herein refers to a compound in which 50 mol% or more of the dicarboxylic acid forming the polyester is composed of an aromatic dicarboxylic acid. More specifically, a polyethylene terephthalate polymer (PET), a polyethylene naphthalate polymer, a polybutylene terephthalate polymer, and a polybutylene naphthalate polymer can be mentioned. More preferred are polyethylene terephthalate and polyethylene naphthalate. Their average molecular weight (M_w ) Is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 300,000.
[0017]
This thermoplastic film is preferably formed into two or more axes. For example, the melting point (T_m) ~ T_mAfter melting between + 50 ° C, the glass transition temperature (T_g-50 ° C ~ T_gExtruded into a + 20 ° C. cooling drum to form an unstretched sheet. At this time, electrostatic application to the cooling drum is also preferable. This unstretched sheet is T_g~ T_gStretched vertically between 2 and 4 times between + 60 ° C and T_g~ T_gStretch laterally between 2 and 5 times between + 60 ° C. T_m-60 ° C to T_mAnd heat-fix for 5 seconds to 1 minute. After this T_m-60 ° C to T_mIt is also preferable to relax by 0 to 10% in at least one of horizontal / vertical. It is also preferable that the film is stretched again in the vertical / horizontal direction. The thickness of the thermoplastic film thus obtained is preferably 50 to 500 μm, more preferably 70 to 300 μm, still more preferably 90 to 200 μm.
[0018]
By carrying out the present invention described above, the height of the vertical hook is 0 μm or more and 200 μm or less, more preferably 0 μm or more and 150 μm or less, and further preferably 0 μm or more and 100 μm or less, and the longitudinal direction at 120 ° C. Excellent thermal dimensional stability with high thermal shrinkage of 0.001% to 0.05%, more preferably 0.001% to 0.04%, and even more preferably 0.001% to 0.03% Thermoplastic film can be made. As a result, when used as a photographic support, particularly when used as a photographic material support with thermal development, high-quality images that do not cause image displacement or blurring when overprinted on a printing original plate (PS plate) are used. A support can be provided.
The photographic light-sensitive material of the present invention can be formed by coating a photographic light-sensitive layer on the support thus obtained. As preferred photographic light-sensitive materials, those described in Japanese Patent Application No. 9-226699, Japanese Patent Application No. 8-158652, and the like can be used.
[0019]
The measurement method used in the present invention will be described below.
(1) Vertical support height After cutting, the support is cut into a width of 50 cm and a length of 30 cm. This is floated on water so that bubbles do not enter, and this is scanned with a laser focus displacement meter (for example, LC2210 manufactured by Keyence Corporation) in the width direction at 50 cm / min. The maximum value-minimum value (excluding both ends) obtained in this way was defined as the vertical height in the width direction of the support.
(2) The thermoplastic film before heat shrinkage heat treatment at 150 ° C. is cut into a longitudinal direction (longitudinal direction; MD) of 25 cm × width direction (TD) of 5 cm. Two holes are made at intervals of 20 cm in this, and the sample is measured with a pin gauge after humidity adjustment for 12 hours or more at 25 ° C. and 60% RH (this length is L₁And). After that, it is left for 30 minutes without applying tension to an air constant temperature bath at 150 ° C. After that, after adjusting the humidity at 25 ° C. and 60% RH for 12 hours or more, measure the length again using a pin gauge (this length is L₂And). The thermal dimensional change rate is obtained based on the following formula.
150° C heat shrink (%) = {100 × (L₁-L₂) / L₁} Absolute value Measured at points obtained by dividing this measurement into 5 in the width direction, and an average value, maximum value, and minimum value are obtained.
[0020]
(3) 120 ° C heat shrinkage
The thermoplastic film after the heat treatment is cut into a longitudinal direction (MD) 25 cm × width direction (TD) 5 cm. Two holes are made at intervals of 20 cm in this, and the sample is measured with a pin gauge after humidity adjustment for 12 hours or more at 25 ° C. and 60% RH (this length is L₁And). Thereafter, it is pressed against a smooth stainless steel plate having a thickness of 10 mm heated to 120 ° C. for 30 seconds. After that, after adjusting the humidity at 25 ° C. and 60% RH for 12 hours or more, measure the length again using a pin gauge (this length is L₂And). The thermal dimensional change rate is obtained based on the following formula.
120 ° C. thermal shrinkage (%) = {100 × (L₁-L₂) / L₁} Absolute value
This is measured at both ends and the center of the thermoplastic film to determine the average value.
(4) Ten-point average roughness (R_z), Maximum roughness (R_t)
Using a universal surface shape measuring instrument SE-3C manufactured by Kosaka Laboratory Ltd., measurement is performed under the following conditions at 25 ° C. and 60% RH.
Measurement length: 2.5mm
Cut-off: 0.25mm
The measurement is performed on both sides of the sample film, and the surface with the larger value is displayed.
(5) Tension
A differential transformer type tension tester (for example, LX-TC-100 manufactured by Mitsubishi Electric Corporation) was installed on the roll immediately before and after the heat treatment zone, and the tension at 25 ° C. was measured to obtain an average value thereof.
[0021]
【Example】
Examples are shown below, but the present invention is not limited thereto.
Example-1
(1) Production of support
(1-1) Preparation of polyethylene terephthalate (PET) support
Using terephthalic acid and ethylene glycol, PET of IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) was obtained according to a conventional method. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and then rapidly cooled to prepare an unstretched film having a thickness such that the film thickness after heat setting was 120 μm. .
This was longitudinally stretched 3.3 times using rolls with different peripheral speeds, and then stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, and knurling was applied to both ends with a width of 1 cm.
[0022]
(1-2) Preparation of polyethylene-2,6-naphthalate (PEN) support
Using dimethyl naphthalene-2,6-dicarboxylate and ethylene glycol, PEN of IV = 0.58 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) was obtained according to a conventional method. This was pelletized, dried at 150 ° C. for 4 hours, melted at 320 ° C., extruded from a T-die, and then rapidly cooled to prepare an unstretched film having a thickness such that the film thickness after heat setting was 120 μm. .
This was longitudinally stretched 2.8 times using rolls having different peripheral speeds, and then laterally stretched 3.7 times with a tenter. The temperatures at this time were 140 ° C. and 150 ° C., respectively. Thereafter, the film was heat-fixed at 250 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, and knurling was applied to both ends with a width of 1 cm.
(2) Creation of coating layer
The following undercoat and back coat layers were provided on the support as shown in Table 1.
[0023]
[Table 1]

[0024]
[Table 2]

[0025]
(2-1) Corona treatment
Prior to coating, corona treatment was performed on both sides (using a solid-state corona treatment machine 6KVA model manufactured by Pillar, treating both sides of the support at 20 m / min at room temperature). From the current and voltage readings at this time, the support is 0.375 kV · A · min / m.²Is being processed. The treatment frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The following layers were coated on this.
(2-2) Undercoat first layer
A water-dispersed latex having the following composition was applied using a wire bar to a dry film thickness of 0.3 μm and dried at 120 ° C. for 2 minutes.
Butadiene-styrene copolymer latex 13ml
(Solid content 43%, butadiene / styrene weight ratio = 32/68)
2,4-dichloro-6-hydroxy-S-triazine sodium 7 ml
Mu salt 8% aqueous solution
1.6% sodium laurylbenzenesulfonate 1% aqueous solution
Colloidal silica Particle size and amount are listed in Table 1.
80ml of distilled water
[0026]
(2-3) Undercoat second layer
An aqueous solution having the following composition was applied using a wire bar so that the dry film thickness was 0.14 μm. The presence / absence of coating and drying conditions are shown in Table 1.
Gelatin 0.9g
Methyl cellulose (Metroise SM15, substitution degree: 1.79 to 0.1 g 1.83)
Acetic acid (concentration 99%) 0.02ml
99ml of distilled water
[0027]
(2-4) Back first layer (conductive layer)
An acrylic latex aqueous dispersion containing a conductive material having the following composition was applied so that the dry film thickness was the value shown in Table 1, dried at 180 ° C. for 30 seconds, and the surface electrical resistance was 10⁶An Ω support was prepared.
Acrylic resin aqueous dispersion 2.0 parts by weight
(Jurima-ET410, solid content 20% by weight, manufactured by Nippon Pure Chemicals Co., Ltd.)
Tin oxide-antimony oxide aqueous dispersion 18.1 parts by weight
(Average particle size 0.1 μm, 17% by weight)
0.1 parts by weight of polyoxyethylene phenyl ether
Colloidal silica Size and amount added are listed in Table 1.
Distilled water was added thereto to prepare 100 parts by weight.
[0028]
(2-5) Polyolefin layer (slip layer)
A polyolefin latex aqueous dispersion having the following composition was applied so that the dry film thickness was as shown in Table 1. The presence / absence of application and drying conditions are shown in Table 1.
3.0 parts by weight of polyolefin
(Kemipearl S-120, 27% by weight, manufactured by Mitsui Petrochemical Co., Ltd.)
Colloidal silica 2.0 parts by weight
(Snowtex C, manufactured by Nissan Chemical Co., Ltd.)
Epoxy compound 0.3 parts by weight
(Denacol EX-614B, manufactured by Nagase Kasei Co., Ltd.)
Prepared to add 100 parts by weight with distilled water
(3) Heat treatment
Prior to the heat treatment, the following evaluation was performed according to the above method, and the results are shown in Table 1.
(1) 150 ° C heat shrinkage
▲ 2 ▼ R_a, R_t
Heat treatment was performed under the conditions shown in Table 1.
[0029]
(4) Evaluation
The following evaluation was performed on the thermoplastic film after the heat treatment according to the above method, and the results are shown in Table 1.
▲ 1 ▼ downspout
(2) 120 ° C heat shrinkage
(5) Creation of photosensitive material
The photosensitive layer shown in Table 1 was applied to the undercoat side of the thermoplastic film on which the above-mentioned undercoat and back layers had been applied and heat-treated. This is the light emission time 10^-4After printing the test pattern with SEC xenon flash light, development was performed at 120 ° C. for 30 seconds using a heat developing machine described in JP 7-505488. When this was baked on a PS plate, in the present invention, good flatness and dimensional stability were achieved, and good baking was realized. On the other hand, in the comparative example, blurring caused by vertical flaws and burning deviation caused by dimensional change occurred during baking.
[0030]
【The invention's effect】
The thermoplastic film of the present invention has good flatness and excellent thermal dimensional stability, and when used as a photographic support, it does not cause failures such as blurring and printing misalignment due to dimensional changes due to thermal development.

Claims (6)

An aromatic polyester film having a thermal shrinkage at 150 ° C. of 0.01% or more and 0.4% or less is heat-treated while being transported under the conditions satisfying the following formulas (1) to (3) at the same time, and has a vertical height. A support for a silver halide photographic light-sensitive material comprising an aromatic polyester film, wherein the heat shrinkage in the longitudinal direction at 120 ° C. is from 0.001% to 0.05%.
0.001 ≦ F ≦ 0.05 (1)
120 ≦ T ≦ 220 (2)
1 ≦ (T × L) / (F × 1000) ≦ 800 (3)
F = Conveyance tension per unit cross-sectional area applied to the thermoplastic film
Force (kg / mm ² )
T = heat treatment temperature (° C)
L = longest non-contact transport length in heat treatment zone (m) Ten-point average roughness (Rz) is 0.18μm or 8.0μm or less, according to claim 1, the maximum height point (Rt) was obtained by the heat treatment of the aromatic polyester film is 0.3μm or more 10μm or less A support for a silver halide photographic material comprising the aromatic polyester film described in 1. An aromatic polyester film having an undercoat layer and a backing layer containing a matting agent, having a vertical gutter height of 0 μm to 200 μm, and a longitudinal heat shrinkage at 120 ° C. of 0.001% to 0.05% A support for a silver halide photographic light-sensitive material, comprising an aromatic polyester film. 4. A support for a silver halide photographic light-sensitive material comprising an aromatic polyester film according to claim 3, wherein the matting agent has a particle size of 0.1 to 15 [mu] m. A silver halide photographic light-sensitive material, which is used as a support for an aromatic polyester film according to any one of claims 1 to 4 . 6. The silver halide photographic light-sensitive material according to claim 5, which is a heat-developable photographic light-sensitive material.