JPH0489884A - Antistatic polymer dispersion - Google Patents
Antistatic polymer dispersionInfo
- Publication number
- JPH0489884A JPH0489884A JP20632490A JP20632490A JPH0489884A JP H0489884 A JPH0489884 A JP H0489884A JP 20632490 A JP20632490 A JP 20632490A JP 20632490 A JP20632490 A JP 20632490A JP H0489884 A JPH0489884 A JP H0489884A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- water
- polymer dispersion
- polymerizable
- antistatic
- 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
- 239000004815 dispersion polymer Substances 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- -1 alkali metal salts Chemical class 0.000 claims abstract description 9
- 238000007127 saponification reaction Methods 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims abstract description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 5
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000002216 antistatic agent Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229920001187 thermosetting polymer Polymers 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100049042 Arabidopsis thaliana PVA11 gene Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- JRHRGDYSAMZWQE-UHFFFAOYSA-N C(C)OCC=C(C(=O)N)C Chemical compound C(C)OCC=C(C(=O)N)C JRHRGDYSAMZWQE-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はフィルム用帯電防止剤として使用可能な素材を
与えるものであり、透明性に優れかつ、耐水性に優れる
ところから、例えばフィルム感材の支持体表面に塗布し
た場合、感光材料の特性に悪影響を与えることなく、現
像処理前後において良好な帯電防止性能を与え、一般の
銀塩を利用したフィルム感光材料その他に好適に使用出
来るものである。Detailed Description of the Invention (Field of Industrial Application) The present invention provides a material that can be used as an antistatic agent for films. When applied to the surface of a support, it provides good antistatic properties before and after development without adversely affecting the properties of the photosensitive material, and can be suitably used for film photosensitive materials using general silver salts. be.
（従来技術およびその問題点）
従来から、種々の帯電防止剤が入手可能であり、それら
の内には例えば感光材料を構成するゼラチン中に導入す
ることで、現像処理以前の段階においては、ある程度の
帯電防止性能を示すものも存在するが、いずれも耐水性
に乏しく、単にゼラチンに混合し塗布、乾燥するのみで
は現像処理を経た後には感光材料から脱落するのが通常
である。(Prior art and its problems) Various antistatic agents have been available to date, and some of them, for example, can be incorporated into gelatin, which constitutes a photosensitive material, to some extent to prevent static electricity at a stage prior to development processing. Although there are some materials that exhibit antistatic properties, they all have poor water resistance, and if they are simply mixed with gelatin, coated, and dried, they usually fall off from the photosensitive material after development.
感光材料における帯電防止剤の重要性については、現像
以前の段階においては、例えばスタチックマークの発生
防止、静電吸着による搬送トラブルの防止あるいは、静
電的に付着するゴミの防止等種々挙げられるが、同様に
現像処理を経たフィルムにおいても帯電防止作用か存在
しない場合には、例えば製版用フィルムの場合、ＰＳ版
への密着焼付けの際にゴミの付着により画像欠陥を生じ
るなど重大な問題を引き起こしうる。Regarding the importance of antistatic agents in photosensitive materials, there are various reasons for the importance of antistatic agents at the stage before development, such as preventing the generation of static marks, preventing transport problems due to electrostatic adsorption, and preventing dust from electrostatically adhering. However, if the developed film does not have an antistatic effect, for example, in the case of film for plate making, serious problems such as image defects due to adhesion of dust may occur when printing in close contact with the PS plate. It can cause
このような問題を解決するために、耐水性を有する帯電
防止層を形成する手段として例えば、特開昭５５−８４
６５８号、同５６−９２５３５号、同６１−１７４５４
２号、同６１−１７４５４３号公報に記載されているよ
うに、カルボキシル基を導入した帯電防止性ポリマーに
多官能性アジリジンを添加し架橋させることで帯電防止
皮膜の耐水性を高める方法があるが、アジリジン化合物
が不安定であり、塗液中に添加した場合、塗液の液性が
経時変化する問題や、毒性の問題等が生じ、製造現場で
の使用には問題が多々あった。In order to solve such problems, as a means for forming a water-resistant antistatic layer, for example, Japanese Patent Laid-Open No. 55-84
No. 658, No. 56-92535, No. 61-17454
As described in No. 2, No. 61-174543, there is a method of increasing the water resistance of an antistatic coating by adding polyfunctional aziridine to an antistatic polymer into which a carboxyl group has been introduced and crosslinking it. The aziridine compound is unstable, and when added to a coating solution, there are problems such as changes in the liquid properties of the coating solution over time, toxicity, etc., and there are many problems when using it at a manufacturing site.
さらには、こうした帯電防止剤の感光材料の特性に与え
る影響も重大であり、感光層中に直接導入することで感
度低下や地被りの原因となることもしばしば経験すると
ころであった。Furthermore, the influence of such antistatic agents on the properties of photosensitive materials is significant, and it has often been experienced that direct introduction into the photosensitive layer causes a decrease in sensitivity and background fog.
（発明の目的）
本発明は前述した種々の問題に鑑み、耐水性に優れ、特
に通常の写真現像処理を施した後にも良好な帯電防止作
用を有する帯電防止剤を与え、これらを含有する層をフ
ィルム感材に設けることで、感光材料の特性に影響を与
えることなく現像処理前後において静電気の発生による
種々のトラブルを解消することを目的とし、さらにはか
かる帯電防止剤自体の安定性を向上させることで製造時
の塗液の性質を安定化させることを目的とするものであ
る。(Object of the Invention) In view of the various problems mentioned above, the present invention provides an antistatic agent that is excellent in water resistance and has a good antistatic effect even after ordinary photographic processing, and provides a layer containing the antistatic agent. By providing antistatic agents in film-sensitive materials, the purpose is to eliminate various troubles caused by the generation of static electricity before and after development processing without affecting the properties of the photosensitive materials, and further improve the stability of the antistatic agent itself. The purpose of this is to stabilize the properties of the coating liquid during manufacture.
（発明の構成）
単独もしくはゼラチンその他の水溶性ポリマーとの併用
により帯電防止作用を有する化合物を帯電防止層として
導入する場合、それらの帯電防止剤そのものの耐水性を
高めない限り、本発明の目指すような現像処理前後にお
いて帯電防止性能を実現することは困難である。いわゆ
る帯電防止剤はそれらの化学的骨格から明らかなように
親水性構造をとっているため、特に低分子化合物におい
ては水溶性が高く、耐水性に乏しいのが通常であるが、
高分子化合物においては、同様な親水性構造を有する成
分をポリマー骨格中に含み、かつ耐水性を高めるために
熱硬化性置換基を共重合成分として導入することで帯電
防止性能と耐水性のバランスをとることが可能であるこ
とを見いだし、本発明に至った。本発明では、高い帯電
防止作用を有する官能基をポリマー骨格中の置換基とし
て導入し、さらにポリマー中に熱硬化性基を、重合中に
熱硬化させることなしに安定に導入することを見いだし
たことで、優れた帯電防止作用を示すとともに、皮膜形
成時に熱硬化することで良好な耐水性を示す、安定な帯
電防止剤を与えることに成功した。(Structure of the Invention) When a compound having an antistatic effect is introduced as an antistatic layer either alone or in combination with gelatin or other water-soluble polymer, the aim of the present invention cannot be achieved unless the water resistance of the antistatic agent itself is increased. It is difficult to achieve antistatic performance before and after such development processing. So-called antistatic agents have a hydrophilic structure as is clear from their chemical skeletons, so they are usually highly water soluble, especially in low molecular weight compounds, and have poor water resistance.
In polymer compounds, a balance between antistatic performance and water resistance can be achieved by containing components with similar hydrophilic structures in the polymer skeleton and introducing thermosetting substituents as copolymerization components to increase water resistance. We have found that it is possible to take the following steps, and have arrived at the present invention. In the present invention, it has been discovered that a functional group having a high antistatic effect can be introduced as a substituent in the polymer skeleton, and a thermosetting group can be stably introduced into the polymer without thermosetting during polymerization. As a result, they succeeded in providing a stable antistatic agent that not only exhibits an excellent antistatic effect but also exhibits good water resistance by being thermally cured during film formation.
即ち、本発明は水と水混和性有機溶剤の混合溶媒中にお
いて鹸化度９５％以上のポリビニルアルコールの存在下
で少なくとも下記のモノマー（１）および（ｎ）を共重
合させることで本発明の目的を達成したものである。That is, the present invention achieves the object of the present invention by copolymerizing at least the following monomers (1) and (n) in a mixed solvent of water and a water-miscible organic solvent in the presence of polyvinyl alcohol with a degree of saponification of 95% or more. has been achieved.
（Ｉ）スルホン酸基もしくはその塩を置換基として有す
る重合性ビニルモノマー
（ＩＩ）一般式
％式％
（一般式においてＲ１およびＲ２は水素原子又はメチル
基、Ｒ３は水素原子又は炭素数１から８個のアルキル基
である。）
上記モノマー（Ｉ）の具体例としてはｐ−スチレンスル
ホン酸もしくはそのアルカリ金属塩もしくはアンモニウ
ム塩、２−アクリルアミド−２メチルプロパンスルホン
酸もしくはそのアルカリ金属塩もしくはアンモニウム塩
もしくは有機アミンによる中和塩、あるいは２−スルホ
エチル（メタ）アクリル酸ナトリウム等が挙げられる。(I) Polymerizable vinyl monomer having a sulfonic acid group or its salt as a substituent (II) General formula % Formula % (In the general formula, R1 and R2 are hydrogen atoms or methyl groups, R3 is a hydrogen atom or has 1 to 8 carbon atoms. ) Specific examples of the monomer (I) include p-styrenesulfonic acid or its alkali metal salt or ammonium salt, 2-acrylamido-2methylpropanesulfonic acid or its alkali metal salt or ammonium salt, or Examples include neutralized salts with organic amines, sodium 2-sulfoethyl (meth)acrylate, and the like.
モノマー（ｎ）としては、例えばヒドロキシメチル（メ
タ）メタアクリルアミド、エトキシメチル（メタ）アク
リルアミド、ブトキシメチル（メタ）アクリルアミド等
の種々のモノマーが挙げられる。これらのうち、熱硬化
性の観点からは特にヒドロキシメチル（メタ）アクリル
アミドが、比較的穏和な条件で良好な架橋皮膜を与える
ことから好ましい。Examples of the monomer (n) include various monomers such as hydroxymethyl (meth)methacrylamide, ethoxymethyl (meth)acrylamide, and butoxymethyl (meth)acrylamide. Among these, from the viewpoint of thermosetting properties, hydroxymethyl (meth)acrylamide is particularly preferred because it provides a good crosslinked film under relatively mild conditions.
上記モノマー（１）および（ＩＩ）の全重合性モノマー
に対する比率は、得られる皮膜の帯電防止性能および耐
水性の観点から、（１）を少なくとも４０重量％以上、
特に４０重量％以上９０重量％以下、（ｎ）を少なくと
も１０重量％以上、特に１０重量％以上６０重量％以下
含むことが好ましい。The ratio of the above monomers (1) and (II) to the total polymerizable monomers is such that (1) is at least 40% by weight or more, from the viewpoint of antistatic performance and water resistance of the resulting film.
It is particularly preferable that the content of (n) is 40% by weight or more and 90% by weight or less, and at least 10% by weight or more, especially 10% by weight or more and 60% by weight or less.
上記モノマー（Ｉ）および（ＩＩ）以外に第３の共重合
成分として種々のモノマーが導入可能である。この場合
の第３のモノマーとして特に制約はなく、（１）あるい
は（ＩＩ）のモノマーのいずれかと共重合するようなモ
ノマーであれば特に問題はない。例えば、スチレンおよ
びその誘導体、（メタ）アクリル酸およびそれらの種々
のエステル誘導体、（メタ）アクリルアミドおよびそれ
らの誘導体、アクリロニトリル、クロトン酸、マレイン
酸、ジビニルベンゼン、エチレングリコールジ（メタ）
アクリレート、メチレンビスアクリルアミドその他多種
のモノマーが使用可能である。In addition to the above monomers (I) and (II), various monomers can be introduced as the third copolymerization component. There are no particular restrictions on the third monomer in this case, and there are no particular problems as long as it is a monomer that copolymerizes with either monomer (1) or (II). For example, styrene and its derivatives, (meth)acrylic acid and their various ester derivatives, (meth)acrylamide and their derivatives, acrylonitrile, crotonic acid, maleic acid, divinylbenzene, ethylene glycol di(meth)
Acrylates, methylenebisacrylamide, and many other monomers can be used.
上記モノマー（１）及び（ＩＩ）以外の第３のモノマー
として分子内に酸性基と重合性二重結合を有するような
モノマーを使用した場合、特に生成したポリマーの熱硬
化性が向上することを見いだした。具体的には（メタ）
アクリル酸、クロトン酸、マレイン酸のようなカルボン
酸基を有するモノマーや、２−アクリルアミド−２−メ
チルプロパンスルホン酸、ビニルスルホン酸のようにス
ルホン酸基を有するモノマー等が好ましく、こうしたモ
ノマーは共重合体中に１−３０重量％の範囲で導入する
のが良い。When a monomer having an acidic group and a polymerizable double bond in the molecule is used as the third monomer other than monomers (1) and (II) above, it is known that the thermosetting properties of the resulting polymer are particularly improved. I found it. Specifically (meta)
Monomers having a carboxylic acid group such as acrylic acid, crotonic acid, and maleic acid, and monomers having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid and vinylsulfonic acid are preferable. It is preferable to introduce it into the polymer in a range of 1-30% by weight.
上記のようなモノマー（Ｉ）および（Ｉｔ）を用いて水
溶液中で重合を行った場合、重合開始後しばらくして溶
液全体がゲル化するのが通常である。When polymerization is carried out in an aqueous solution using monomers (I) and (It) as described above, the entire solution usually gels some time after the start of polymerization.
特に実用上少なくとも２０重量％以上のモノマー濃度で
重合を行った場合、重合が完了するはるか以前に系全体
がゲル化し、塗液として使用不可能なものが得られるの
が通常である。重合中のゲル化を抑えるために、モノマ
ー（ＩＩ）の比率を低下させると、得られるポリマーの
熱硬化性が減少し、十分な耐水性が得られない。本発明
のめざすようなすぐれた耐水性を発揮させるためにはモ
ノマー（ＩＩ）の比率は全重合性モノマーに対して少な
くとも１０重量％以上であることが必要であり、こうし
た組成のポリマーは通常の水溶液重合では、溶液の形で
得ることは極めて困難であった。In particular, when polymerization is carried out at a monomer concentration of at least 20% by weight for practical purposes, the entire system usually gels long before the polymerization is completed, resulting in a product that cannot be used as a coating liquid. If the ratio of monomer (II) is lowered in order to suppress gelation during polymerization, the thermosetting properties of the resulting polymer will decrease, making it impossible to obtain sufficient water resistance. In order to exhibit the excellent water resistance aimed at by the present invention, the proportion of monomer (II) must be at least 10% by weight based on the total polymerizable monomers, and polymers with such a composition are In aqueous solution polymerization, it is extremely difficult to obtain a solution in the form of a solution.
本発明では、上記のようなモノマー組成で重合を行う際
に、重合溶媒として水と水混和性有機溶媒の混合溶媒を
使用することで、生成するポリマーを粒子状もしくは分
散体として得ることができ、系全体をゲル化から防止で
きることを見いだした。In the present invention, by using a mixed solvent of water and a water-miscible organic solvent as a polymerization solvent when performing polymerization with the above monomer composition, the resulting polymer can be obtained in the form of particles or a dispersion. , found that the entire system could be prevented from gelling.
即ち、重合中に生成するポリマーを粒子状に析出させる
ことで熱硬化性置換基を粒子内部に保護し、粒子間での
架橋反応を防止することで、ゲル化することなく多量の
熱硬化性置換基を含むポリマ−を得るものである。この
ような方法により例えばモノマー（ｎ）を９０重量％以
上含むようなポリマーもゲル化物の生成なく得ることが
可能であるが、目的とする帯電防止性能を発揮させるた
めにはモノマー（１）を少なくとも４０重量％以上共重
合させることが好ましい。In other words, by precipitating the polymer produced during polymerization into particles, the thermosetting substituents are protected inside the particles, and crosslinking reactions between the particles are prevented. A polymer containing substituents is obtained. By such a method, for example, it is possible to obtain a polymer containing 90% by weight or more of monomer (n) without forming a gelled product, but in order to exhibit the desired antistatic performance, it is necessary to add monomer (1). It is preferable to copolymerize at least 40% by weight.
水混和性有機溶剤としてはメタノール、エタノール、イ
ソプロパツール、ブタノールのようなアルコールの使用
が特に好ましいが、これ以外にアセトン、ジオキサン、
テトラヒドロフランといった種々の有機溶剤が使用可能
である。これら水混和性有機溶剤と水との比率は、モノ
マー（Ｉ）および（Ｉｔ）の混合物を溶解する範囲で設
定し、かつ生成するポリマーを少なくとも部分的に不溶
化するような混合比をとることが重要である。即ち、有
機溶剤の割合が多き過ぎればモノマー（Ｉ）あるいは（
ｎ）のいずれかを完全に溶解するに至らず、重合当初か
ら不均一のため重合が円滑に進行しない場合が多々あり
好ましくない。逆に有機溶剤の割合が少なすぎれば、生
成するポリマーは可溶性のため、しだいに熱硬化性モノ
マー（Ｉｆ）の重合と熱硬化反応が平行して進行するた
め、系全体のゲル化を生ずるようになる。従って、モノ
マー混合物を溶解し、かつ生成ポリマーを不溶化するよ
うな溶剤混合比を選ぶことが重要である。As water-miscible organic solvents, it is particularly preferred to use alcohols such as methanol, ethanol, isopropanol, butanol, but also acetone, dioxane,
Various organic solvents can be used, such as tetrahydrofuran. The ratio of these water-miscible organic solvents to water can be set within a range that dissolves the mixture of monomers (I) and (It), and the mixing ratio can be such that at least partially insolubilizes the resulting polymer. is important. That is, if the proportion of organic solvent is too high, monomer (I) or (
(n) is not completely dissolved, and the polymerization is not uniform from the beginning, so the polymerization often does not proceed smoothly, which is not preferable. On the other hand, if the proportion of the organic solvent is too small, the resulting polymer is soluble, so the polymerization of the thermosetting monomer (If) and the thermosetting reaction gradually proceed in parallel, leading to gelation of the entire system. become. Therefore, it is important to select a solvent mixing ratio that will dissolve the monomer mixture and insolubilize the resulting polymer.
上記のような方法により生成するポリマーを粒子状に析
出させることが可能であるが、重合を開始する前にあら
かじめ系内に鹸化度９５％以上のポリビニルアルコール
を添加しておくことで、生成する粒子の安定性をさらに
高めることが可能である。この場合のポリビニルアルコ
ールの作用は、粒子表面に吸着することで、粒子上に吸
着保護層を形成し、粒子同士の合一とそれより引き起こ
される粒子間での架橋反応を抑制することで凝集物の発
生を防止し、均一な安定粒子を形成することが達成され
る。It is possible to precipitate the polymer produced by the above method in the form of particles, but by adding polyvinyl alcohol with a saponification degree of 95% or more to the system before starting polymerization, it is possible to precipitate the polymer produced in the form of particles. It is possible to further increase the stability of the particles. In this case, polyvinyl alcohol acts by adsorbing to the particle surface, forming an adsorbing protective layer on the particle, and suppressing the coalescence of particles and the resulting crosslinking reaction between particles, thereby preventing aggregates. The formation of uniform, stable particles is achieved.
こうしたいわゆる分散安定剤としてのポリビニルアルコ
ールの使用量は粒子を安定に形成するのに最低必要量使
用するのにとどめておくことが好ましい場合がある。特
に、ポリビニルアルコールのような分散安定剤を多量使
用した場合、得られる皮膜の接着性が低下する場合があ
り、こうした見地から通常使用するポリビニルアルコー
ルの量は他の全モノマーに対し、約１０重量％以下にと
どめておくことが好ましい。The amount of polyvinyl alcohol used as a so-called dispersion stabilizer may be preferably limited to the minimum amount required to stably form particles. In particular, when a large amount of a dispersion stabilizer such as polyvinyl alcohol is used, the adhesion of the resulting film may be reduced.From this perspective, the amount of polyvinyl alcohol normally used is approximately 10% by weight based on all other monomers. It is preferable to keep it within %.
上記のような方法により熱硬化性置換基を有するポリマ
ーを粒子状もしくは分散体として得ることが可能である
が、重合終了後さらに水を添加することでポリマーを溶
解し、均一な溶液を得ることが可能である。溶液とする
ことでポリマー粒子もしくは分散体の分散安定性を考慮
する必要がなくなり、実用上より好ましい。さらに上記
のような方法で製造したポリマーは分子内に多量の未反
応の熱硬化性基を含有するにもかかわらず、保存性は極
めて良好であることを見いだした。即ち、溶液中でのポ
リマーの安定性がきわめて良好なため塗液とした場合で
もポットライフが非常に長く、一方で熱硬化性基を未反
応のまま有しているため、例えばフィルム等の支持体に
塗布、乾燥した場合の硬化性が極めて良好であることが
見いだされた。Although it is possible to obtain a polymer having a thermosetting substituent in the form of particles or dispersion by the method described above, it is also possible to dissolve the polymer and obtain a uniform solution by adding water after the polymerization is completed. is possible. Forming a solution eliminates the need to consider the dispersion stability of the polymer particles or dispersion, which is more preferable from a practical standpoint. Furthermore, it has been found that the polymer produced by the method described above has extremely good storage stability despite containing a large amount of unreacted thermosetting groups in the molecule. In other words, the stability of the polymer in solution is extremely good, so even when used as a coating liquid, the pot life is very long.On the other hand, since it has thermosetting groups unreacted, it can be used as a support for films, etc. It was found that the curing property when applied to the body and dried was extremely good.
本発明により得られる帯電防止剤はこれを単独もしくは
ゼラチンその他の水溶性ポリマーと混合して皮膜形成す
ることが可能であり、形成する帯電防止層の位置は感光
材料を構成する種々の層の任意の位置に形成して良く、
例えば乳剤層上部、乳剤層下部もしくは乳剤層のある面
と反対側の面にバックコートする等積々の形で形成する
ことが可能である。The antistatic agent obtained by the present invention can be used alone or mixed with gelatin or other water-soluble polymers to form a film, and the position of the antistatic layer to be formed can be determined at any position in the various layers constituting the photosensitive material. It may be formed at the position of
For example, it can be formed in a stacked manner by backcoating the upper part of the emulsion layer, the lower part of the emulsion layer, or the opposite side of the emulsion layer.
さらに該帯電防止層中には種々の目的で添加物を導入す
ることも可能である。例えば、ブロッキング防止の目的
でシリカ微粒子やポリマー微粒子をマット剤として導入
可能であり、あるいは他の導電性成分として酸化錫等の
金属微粒子を導入することも出来る。Furthermore, it is also possible to introduce additives into the antistatic layer for various purposes. For example, fine silica particles or fine polymer particles can be introduced as a matting agent for the purpose of preventing blocking, or fine metal particles such as tin oxide can be introduced as another conductive component.
本発明で得られる熱硬化性帯電防止剤は、これを単独も
しくは他の成分とともにフィルム等の支持体上に皮膜形
成し、例えば、５０℃程度の加熱条件で数時間のうちに
完全に硬化するものであるが、さらに硬化触媒として硫
酸、塩酸、燐酸、ｐ−トルエンスルホン酸といった酸を
少量添加することで、さらに硬化速度を高めることが可
能である。The thermosetting antistatic agent obtained in the present invention is formed into a film on a support such as a film alone or together with other components, and is completely cured within several hours under heating conditions of, for example, about 50°C. However, the curing speed can be further increased by adding a small amount of an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or p-toluenesulfonic acid as a curing catalyst.
（実施例）
以下に実施例により本発明帯電防止剤の合成例及びそれ
により得られた帯電防止剤を写真感光材料に適用した際
の効果の確認を示すが、もとより効果を含めてこれに限
定されるものではない。(Example) Examples of synthesis of the antistatic agent of the present invention and confirmation of the effect when the antistatic agent obtained thereby is applied to a photographic light-sensitive material are shown below, but the scope is limited to this including the effect. It is not something that will be done.
合成例１
撹拌機、温度計、窒素導入管および還流冷却管を備えた
５００ｍ１４ツロフラスコにポリビニルアルコール（Ｐ
ＶＡ１０５．鹸化度９８．５％、クラレ■製）８ｇ、ｐ
−スチレンスルホン酸ナトリウム７０ｇおよびＮ−ヒド
ロキシメチルアクリルアミド３０ｇを仕込み、エタノー
ル１５０ｇおよび蒸留水１５０ｇを加え、７０℃で溶解
した。Synthesis Example 1 Polyvinyl alcohol (P
VA105. Saponification degree 98.5%, manufactured by Kuraray ■) 8g, p
- 70 g of sodium styrene sulfonate and 30 g of N-hydroxymethylacrylamide were charged, 150 g of ethanol and 150 g of distilled water were added, and the mixture was dissolved at 70°C.
窒素雰囲気下７５℃でＡＩＢＮｌｇを添加し重合を開始
し、この温度で２．５時間撹拌した。生成物は白色のエ
マルジョン状であり、水中に投入して固形分１５％の均
一なポリマー溶液を得た。分子量は約１００万であり水
溶液中での粘度は３０ｃｐｓであった。Polymerization was initiated by adding 1 g of AIBN at 75° C. under a nitrogen atmosphere, and the mixture was stirred at this temperature for 2.5 hours. The product was a white emulsion and was poured into water to obtain a homogeneous polymer solution with a solids content of 15%. The molecular weight was about 1 million, and the viscosity in an aqueous solution was 30 cps.
比較合成例
上記合成例１において重合媒体として蒸留水３５０ｇを
加え、エタノールを使用しない系において同様な重合を
行ったが、重合開始後すみやかにゲル化が進行し、固形
状のゲル化物を得るにとどまった。Comparative Synthesis Example In Synthesis Example 1 above, 350 g of distilled water was added as a polymerization medium and the same polymerization was carried out without using ethanol, but gelation proceeded immediately after the start of polymerization, and it was difficult to obtain a solid gelled product. I stayed.
合成例２
合成例１と同様に、ポリビニルアルコール（ＰＶＡ１１
７、鹸化度９８．５％、クラＶ■製）３ｇＳｐ−スチレ
ンスルホン酸カリウム５５ｇ１アクリルアミド１０ｇ１
メタクリル酸５ｇおよびエトキシメチルメタアクリルア
ミド３０ｇを７０°Ｃにおいて蒸留水２００ｇおよびイ
ソプロパツール１５０ｇに溶解し、７５℃においてＡ
Ｉ ＢＮｏ。Synthesis Example 2 Similar to Synthesis Example 1, polyvinyl alcohol (PVA11
7. Degree of saponification 98.5%, manufactured by Kura V ■) 3gSp-Potassium styrene sulfonate 55g1 Acrylamide 10g1
5 g of methacrylic acid and 30 g of ethoxymethylmethacrylamide were dissolved in 200 g of distilled water and 150 g of isopropanol at 70°C, and A
IBNo.
８ｇを添加し、窒素雰囲気下３時間加熱撹拌を行った。8 g was added, and the mixture was heated and stirred for 3 hours under a nitrogen atmosphere.
重合終了後得られた分散体を蒸留水を加えて１５％溶液
とした。After the polymerization was completed, distilled water was added to the resulting dispersion to make a 15% solution.
合成例３
合成例１と同様に、ポリビニルアルコール（ＰＶＡＫＬ
−１１８、鹸化度９７．５％、クラレ■製）５ｇ、２−
アクリルアミド−２−メチルプロパンスルホン酸ナトリ
ウム５０ｇＸＮ−ヒドロキシメチルアクリルアミド４０
ｇ１アクリル酸２ｇおよびスチレン１０ｇを蒸留水１６
０ｇおよびエタノール１００ｇ、１．４−ジオキサン５
０ｇに溶解し、７５℃にてＡＩＢＮｏ、７ｇを添加し、
窒素雰囲気下で２時間加熱撹拌を行った。Synthesis Example 3 Similar to Synthesis Example 1, polyvinyl alcohol (PVAKL)
-118, degree of saponification 97.5%, manufactured by Kuraray ■) 5g, 2-
Sodium acrylamide-2-methylpropanesulfonate 50gXN-hydroxymethylacrylamide 40
g1 2 g of acrylic acid and 10 g of styrene in 16 g of distilled water
0 g and 100 g of ethanol, 1,4-dioxane 5
0g, add 7g of AIBNo at 75°C,
The mixture was heated and stirred for 2 hours under a nitrogen atmosphere.
生成した分散体を蒸留水で希釈し、１５％濃度の均一な
溶液を得た。The resulting dispersion was diluted with distilled water to obtain a homogeneous solution with a concentration of 15%.
合成例４
合成例１と同様に、ポリビニルアルコール（ＰＶＡ１０
３、鹸化度９８．６％、クラレ■製）５ｇ１ｐ−スチレ
ンスルホン酸ナトリウム５５ｇ１２−アクリルアミド−
２−メチルプロパンスルホン酸５ｇ、Ｎ−ヒドロキシメ
チルアクリルアミド３０ｇおよびメタクリル酸メチル１
０ｇを蒸留水２００ｇおよびメタノール１７０ｇに加え
、６０℃で過硫酸アンモニウム１ｇを添加し、この温度
で窒素雰囲気下２０時間撹拌を行った。その後室温にて
蒸留水を加え、１５％濃度の溶液を得た。Synthesis Example 4 Similar to Synthesis Example 1, polyvinyl alcohol (PVA10
3. Degree of saponification 98.6%, manufactured by Kuraray ■) 5g1 Sodium p-styrene sulfonate 55g12-Acrylamide-
2-methylpropanesulfonic acid 5g, N-hydroxymethylacrylamide 30g and methyl methacrylate 1
0g was added to 200g of distilled water and 170g of methanol, 1g of ammonium persulfate was added at 60°C, and the mixture was stirred at this temperature under a nitrogen atmosphere for 20 hours. Distilled water was then added at room temperature to obtain a 15% solution.
実施例１
合成例１〜４および比較合成例で得たサンプルについて
水性下引処理したポリエステルフィルム上に塗布膜厚が
約１ミクロンになるように両面に塗布、乾燥した。乾燥
条件として５０℃において４時間加熱乾燥を行なった。Example 1 The samples obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example were coated on both sides of an aqueous subbing-treated polyester film to a coating thickness of about 1 micron, and dried. As a drying condition, heat drying was performed at 50° C. for 4 hours.
このようにして帯電防止処理を施したフィルム上に、通
常の方法で物理熟成を施した塩化銀９８モル％を含む平
均粒径０．２μの単分散塩臭化銀乳剤を脱塩処理後、有
機減感剤としてピナクリプトールイエローを５■１モル
Ａｇ添加し、更にゼラチン水溶液、硬膜剤、界面活性剤
を加えて得られた乳剤層を５ｇ／ｆｆｌとなるように塗
布、乾燥した。このようにして得られた試料を明室用プ
リンターを用いて露光を施し、現像、定着、水洗処理を
施した。After desalting a monodisperse silver chlorobromide emulsion containing 98 mol% silver chloride and having an average grain size of 0.2 μm, which had been subjected to physical ripening in a conventional manner, on the film which had been subjected to antistatic treatment in this way, An emulsion layer obtained by adding 5 x 1 mol Ag of pinacryptol yellow as an organic desensitizer, an aqueous gelatin solution, a hardening agent, and a surfactant was coated at a concentration of 5 g/ffl and dried. The sample thus obtained was exposed to light using a printer for bright rooms, developed, fixed, and washed with water.
現像処理前後での乳剤層を設けていない面での表面抵抗
値を測定した結果を表１に示した。合成例１〜４で得た
サンプルを塗布したものについては現像処理後も低い表
面抵抗値を有し、良好な帯電防止能を有することが分か
った。なお比較例として合成したサンプルについては熱
硬化性基の割合が低く、充分な硬化皮膜を形成するに至
らなかった。Table 1 shows the results of measuring the surface resistance values on the surface without the emulsion layer before and after development. It was found that the samples coated with the samples obtained in Synthesis Examples 1 to 4 had low surface resistance values even after development, and had good antistatic properties. Note that the sample synthesized as a comparative example had a low proportion of thermosetting groups and could not form a sufficient cured film.
の裏面に実施例１で述べた乳剤層を同様に塗布、乾燥し
た。明室用プリンターを用いて露光し、現像、定着、水
洗処理を施し、現像処理前後における帯電防止層の表面
抵抗値を測定した。結果を表２に示した。合成例１〜４
で得た帯電防止剤は良好な耐水性に優れた帯電防止層を
与えることが分かった。The emulsion layer described in Example 1 was similarly coated on the back side of the sample and dried. The antistatic layer was exposed to light using a bright room printer, developed, fixed, and washed with water, and the surface resistance value of the antistatic layer was measured before and after the development process. The results are shown in Table 2. Synthesis examples 1 to 4
It has been found that the antistatic agent obtained above provides an antistatic layer with good water resistance.
実施例２
合成例１〜４で得たサンプルについて水性下引処理を施
したポリエステルフィルム上に塗布膜厚が約１ミクロン
になるように片面に塗布乾燥した。Example 2 The samples obtained in Synthesis Examples 1 to 4 were coated on one side of a polyester film subjected to an aqueous subbing treatment to a coating thickness of about 1 micron and dried.
更にこの上に同一の帯電防止剤を１０％含有するゼラチ
ン水溶液および硬膜剤からなる塗液を塗布し、乾燥させ
た。このようにして得たフィルム実施例３
合成例１〜４で得たサンプルに、重量比にして２５％に
相当するポリビニルアルコール１０％水溶液に添加した
塗液を得た。このものを実施例１と同様に水性下引処理
したポリエステルフィルム上に塗布、乾燥し、更に実施
例１と同一の乳剤層を形成させた。それぞれの試料につ
いて現像処理前後の表面抵抗値を測定したが現像処理前
後で１０８Ωの殆んど変化しない結果を得た。Furthermore, a coating solution consisting of a gelatin aqueous solution containing 10% of the same antistatic agent and a film hardener was applied thereon and dried. Film Example 3 Thus Obtained A coating solution was obtained by adding a 10% aqueous solution of polyvinyl alcohol corresponding to 25% by weight to the samples obtained in Synthesis Examples 1 to 4. This product was coated on a polyester film subjected to an aqueous subbing treatment in the same manner as in Example 1, and dried to form the same emulsion layer as in Example 1. The surface resistance value of each sample was measured before and after the development process, and the result was 108Ω, which was almost unchanged before and after the development process.
（発明の効果）
本発明帯電防止剤は、耐水性に優れ、例えば写真材料に
於て写真処理を施した後にも良好な帯電防止作用を有す
る帯電防止能を与え、これをフィルム感材に適用するこ
とによって現像処理前後において静電気の発生による種
々のトラブルを解消することができる。(Effects of the Invention) The antistatic agent of the present invention has excellent water resistance and, for example, provides antistatic ability that has a good antistatic effect even after photographic processing is applied to photographic materials, and it can be applied to film-sensitive materials. By doing so, it is possible to eliminate various troubles caused by the generation of static electricity before and after the development process.
手続補正書（自発）
１、事件の表示 平成 ２年特許願第２０６３２４号２
、発明の名称
帯電防止剤ポリマー分散液
３、補正をする者
事件との関係 特許出願人
住 所 東京都千代田区丸の内圧丁目４番２号名
称 （５９Ｂ）三菱製紙株式会社連絡先 〒１２５
東京都葛飾区東金町−丁目４番１号三菱製紙株式会社
特許部
１１！ （６１）Ｏ） ２４８］
方式 帛
（１）明細書の「特許請求の範囲」を別紙のとおり訂正
。Procedural amendment (voluntary) 1. Indication of the case 1990 Patent Application No. 206324 2
, Title of the invention: Antistatic agent polymer dispersion 3, Relationship with the case of the person making the amendment Patent applicant address: 4-2 Marunouchi Atsushi-chome, Chiyoda-ku, Tokyo Name (59B) Mitsubishi Paper Mills Co., Ltd. Contact address: 125
Mitsubishi Paper Mills Co., Ltd., 4-1 Toganemachi-chome, Katsushika-ku, Tokyo
Patent Department 11! (61) O) 248] Form (1) The "Claims" in the specification are corrected as shown in the attached sheet.
（２）明細書の第７頁第４〜８行。(2) Page 7, lines 4-8 of the specification.
「 ＣＨ２＝ＣＨ−Ｃｏ−Ｎ−ＣＨ２０Ｒ３」 を ［ ＣＨｚ ＝ＣＣｏ Ｎ ＣＨ２０Ｒ３」 に訂正。" CH2=CH-Co-N-CH20R3" of [ CHz = CCo N CH20R3” Corrected.
「１．水と水混和性有機溶剤の混合溶媒中で、鹸化度９
５％以上のポリビニルアルコールの存在下、重合性全モ
ノマーに対しスルホン酸基もしくはその塩を置換基とし
て有する重合性ビニルモノマー（１）を少なくとも４０
重量％以上及び下記一般式で表わされるモノマー（ＩＩ
）を少なくとも１０重量％以上含む二成分もしくはこれ
以上の重合性モノマー成分混合物を重合して得られる硬
化性帯電防止剤ポリマー分散液。1. In a mixed solvent of water and a water-miscible organic solvent, the degree of saponification is 9.
In the presence of 5% or more polyvinyl alcohol, at least 40% of the polymerizable vinyl monomer (1) having a sulfonic acid group or a salt thereof as a substituent is added to all polymerizable monomers.
% by weight or more and the monomer (II
) A curable antistatic agent polymer dispersion obtained by polymerizing a mixture of two or more polymerizable monomer components containing at least 10% by weight of
ＲＩ Ｒ２
ＣＨ２＝ＣＣｏ Ｎ ＣＨ２ＯＲ” （ＩＩ）
（式■においてＲ１及びＲ２は水素原子又はメチル基、
Ｒ３は水素原子又は炭素数１から８個のアルキル基であ
る。）
２、請求項１におけるモノマー（Ｉ）がｐ−スチレンス
ルホン酸もしくはそのアルカリ金属塩もしくはアンモニ
ウム塩、２−アクリルアミド−２−メチルプロパンスル
ホン酸もしくはそのアルカリ金属塩もしくはアンモニウ
ム塩もしくは有機アミンによる中和塩、あるいは２−ス
ルホエチル（メタ）アクリル酸ナトリウムであることを
特徴とする硬化性帯電防止剤ポリマー分散液。RI R2 CH2=CCo N CH2OR” (II)
(In the formula (■), R1 and R2 are hydrogen atoms or methyl groups,
R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) 2. Monomer (I) in claim 1 is neutralized with p-styrenesulfonic acid or its alkali metal salt or ammonium salt, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt or ammonium salt, or an organic amine. A curable antistatic agent polymer dispersion, characterized in that it is a salt or sodium 2-sulfoethyl (meth)acrylate.
３、請求項１におけるこれ以上の重合性モノマー成分が
分子内に酸性基と重合性二重結合とを有するモノマーで
ある硬化性帯電防止剤ポリマー分散液。3. The curable antistatic agent polymer dispersion according to claim 1, wherein the further polymerizable monomer component is a monomer having an acidic group and a polymerizable double bond in the molecule.
４、請求項１におけるポリビニルアルコールの重合性全
モノマーに対する含有率が１０重量％以下である帯電防
止剤ポリマー分散液。4. The antistatic agent polymer dispersion according to claim 1, wherein the content of polyvinyl alcohol based on the total polymerizable monomers is 10% by weight or less.
Claims (1)
％以上のポリビニルアルコールの存在下、重合性全モノ
マーに対しスルホン酸基もしくはその塩を置換基として
有する重合性ビニルモノマー（ I ）を少なくとも４０
重量％以上及び下記一般式で表わされるモノマー（II）
を少なくとも１０重量％以上含む二成分もしくはこれ以
上の重合性モノマー成分混合物を重合して得られる硬化
性帯電防止剤ポリマー分散液。 ▲数式、化学式、表等があります▼（II） （式IIにおいてＲ＾１及びＲ＾２は水素原子又はメチル
基、Ｒ＾３は水素原子又は炭素数１から８個のアルキル
基である。） ２、請求項１におけるモノマー（ I ）がｐ−スチレン
スルホン酸もしくはそのアルカリ金属塩もしくはアンモ
ニウム塩、２−アクリルアミド−２−メチルプロパンス
ルホン酸もしくはそのアルカリ金属塩もしくはアンモニ
ウム塩もしくは有機アミンによる中和塩、あるいは２−
スルホエチル（メタ）アクリル酸ナトリウムであること
を特徴とする硬化性帯電防止剤ポリマー分散液。 ３、請求項１におけるこれ以上の重合性モノマー成分が
分子内に酸性基と重合性二重結合とを有するモノマーで
ある硬化性帯電防止剤ポリマー分散液。 ４、請求項１におけるポリビニルアルコールの重合性全
モノマーに対する含有率が１０重量％以下である帯電防
止剤ポリマー分散液。 ５、請求項１、２、３または４記載のポリマー分散液を
水により希釈して得られる、実質的に均一に溶解した硬
化性帯電防止剤ポリマー溶液。[Claims] 1. Saponification degree of 95 in a mixed solvent of water and a water-miscible organic solvent
% or more of polyvinyl alcohol, at least 40% of the total polymerizable monomers contain a polymerizable vinyl monomer (I) having a sulfonic acid group or a salt thereof as a substituent.
Monomer (II) represented by weight% or more and the following general formula
A curable antistatic agent polymer dispersion obtained by polymerizing a mixture of two or more polymerizable monomer components containing at least 10% by weight of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In formula II, R^1 and R^2 are hydrogen atoms or methyl groups, and R^3 is hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. 2. The monomer (I) in claim 1 is neutralized with p-styrenesulfonic acid or its alkali metal salt or ammonium salt, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt or ammonium salt, or an organic amine. salt or 2-
A curable antistatic polymer dispersion characterized in that it is sodium sulfoethyl (meth)acrylate. 3. The curable antistatic agent polymer dispersion according to claim 1, wherein the further polymerizable monomer component is a monomer having an acidic group and a polymerizable double bond in the molecule. 4. The antistatic agent polymer dispersion according to claim 1, wherein the content of polyvinyl alcohol based on the total polymerizable monomers is 10% by weight or less. 5. A substantially uniformly dissolved curable antistatic polymer solution obtained by diluting the polymer dispersion according to claim 1, 2, 3 or 4 with water.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20632490A JPH0489884A (en) | 1990-08-03 | 1990-08-03 | Antistatic polymer dispersion |
| US07/649,963 US5290634A (en) | 1990-02-05 | 1991-02-04 | Antistatic film |
| DE19914103437 DE4103437C2 (en) | 1990-02-05 | 1991-02-05 | Curable acrylic antistatic polymer dispersion and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20632490A JPH0489884A (en) | 1990-08-03 | 1990-08-03 | Antistatic polymer dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0489884A true JPH0489884A (en) | 1992-03-24 |
Family
ID=16521415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20632490A Pending JPH0489884A (en) | 1990-02-05 | 1990-08-03 | Antistatic polymer dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0489884A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08507570A (en) * | 1993-04-20 | 1996-08-13 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesive tape with antistatic properties |
| JP2011231230A (en) * | 2010-04-28 | 2011-11-17 | Kanji Hayashi | Water-soluble anion-type polymer antistatic coating agent |
-
1990
- 1990-08-03 JP JP20632490A patent/JPH0489884A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08507570A (en) * | 1993-04-20 | 1996-08-13 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesive tape with antistatic properties |
| JP2011231230A (en) * | 2010-04-28 | 2011-11-17 | Kanji Hayashi | Water-soluble anion-type polymer antistatic coating agent |
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