JPH0615592B2 - Method for producing allylthiourea polymer - Google Patents
Method for producing allylthiourea polymerInfo
- Publication number
- JPH0615592B2 JPH0615592B2 JP15636885A JP15636885A JPH0615592B2 JP H0615592 B2 JPH0615592 B2 JP H0615592B2 JP 15636885 A JP15636885 A JP 15636885A JP 15636885 A JP15636885 A JP 15636885A JP H0615592 B2 JPH0615592 B2 JP H0615592B2
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- Prior art keywords
- zinc chloride
- allylthiourea
- polymer
- polymerization
- producing
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Description
【発明の詳細な説明】 技術分野 本発明は、アリルチオ尿素系重合体の製造方法に関す
る。本発明により得られるアリルチオ尿素系重合体は、
これに限定されるものではないが、酸性インヒビター、
アフイニテイークロマトグラフイー用担体として好まし
く用いられる。TECHNICAL FIELD The present invention relates to a method for producing an allylthiourea polymer. The allyl thiourea-based polymer obtained by the present invention,
But not limited to, acid inhibitors,
It is preferably used as a carrier for affinity chromatography.
従来技術及びその問題点 特開昭５８−２０１８１１号公報に記載されたように、
本発明者の一人（原田）によつて初めて経済的に合成す
ることに成功したポリアリルアミンは第一アミノ基だけ
を持つカチオン性高分子であるため、紙の導電加工剤、
凝集剤、染料の固着剤、殺菌剤の用途に利用される他に
反応性に富む第一アミノ基を利用して各種機能性高分子
の出発原料としての用途が考えられる。Prior art and its problems As described in JP-A-58-201811,
One of the present inventors (Harada) succeeded in economically synthesizing polyallylamine for the first time because it is a cationic polymer having only primary amino groups.
In addition to being used as an aggregating agent, a fixing agent for dyes, and a bactericidal agent, it can be used as a starting material for various functional polymers by utilizing a highly reactive primary amino group.
しかしながら、ポリアリルアミンは分子中の第一アミノ
基濃度が高すぎるために用途によつては不都合を生じる
ことがある。However, polyallylamine may cause inconvenience in some applications because the concentration of primary amino groups in the molecule is too high.
例えば、ポリアリルアミンの第一アミノ基に、ある特異
的リガンドを反応させアフイニテイークロマトグラフイ
ーに応用した場合、全ての第一アミノ基に特異的リガン
ドを反応させることは困難であり、未反応の第一アミノ
基が多く残存する可能性がある。この様な状態で酵素を
選択的に吸着分離させると、pHの制御に障害を生じた
り、残存する第一アミノ基によつて酵素が失活する可能
性が生じる。For example, when a specific ligand is reacted with the primary amino group of polyallylamine and applied to affinity chromatography, it is difficult to react the specific ligand with all primary amino groups, and unreacted Many primary amino groups may remain. When the enzyme is selectively adsorbed and separated in such a state, there is a possibility that pH control may be impaired and the enzyme may be deactivated by the remaining primary amino group.
分子中の第一アミノ基濃度が高いことによるこの様な弊
害を解消するため、一般的には、モノアリルアミンの重
合により得られたポリアリルアミンの高分子側鎖に中性
の基を導入することが行なわれているが、この方法は重
合を行なつた後に高分子側鎖の反応を行なうために、工
程数が多くなり、経済性の面から望ましくない。In order to eliminate such adverse effects due to the high concentration of primary amino groups in the molecule, it is generally necessary to introduce a neutral group into the polymer side chain of polyallylamine obtained by polymerization of monoallylamine. However, this method is not desirable from the economical point of view because the number of steps increases because the reaction of the polymer side chain is performed after the polymerization.
このためモノアリルアミン無機酸塩をこれに類似する中
性の単量体に変えて重合させるか、場合によりこの単量
体にモノアリルアミン無機酸塩を加えて重合させること
ができれば、一段の重合工程によつて、上記ポリアリル
アミンの第１アミノ基濃度が高いことによる弊害が除去
できると考えられるので、このような重合体の製造方法
の開発が望まれていた。Therefore, if the monoallylamine inorganic acid salt is changed to a similar neutral monomer to polymerize, or if it is possible to add the monoallylamine inorganic acid salt to this monomer and polymerize, a one-step polymerization step Therefore, it is considered that the adverse effect due to the high concentration of the primary amino group of the polyallylamine can be eliminated, and therefore the development of such a method for producing a polymer has been desired.
問題点を解決するための手段 本発明者らは、上述の問題点を解決するために種々検討
した結果、アリルチオ尿素が、それ自体又はこれにモノ
アリルアミン無機酸塩を加えても、極性溶媒中で、分子
中にアゾ基とアミジン基とを有するラジカル開始剤及び
塩化亜鉛の存在下で重合可能であること及びこの重合に
よつて得られた重合体が前述のポリアリルアミンの欠点
を有さず、例えばアフイニテイークロマトグラフイー用
担体や、スケールのみ除去し鋼材は溶出しないようにす
る酸洗インヒビターとして好ましく用いられることを見
出し、本発明を完成させた。Means for Solving the Problems As a result of various studies for solving the above-mentioned problems, the present inventors have found that allylthiourea is in a polar solvent even if it is added to itself or a monoallylamine inorganic acid salt. In addition, it is possible to polymerize in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride, and the polymer obtained by this polymerization does not have the above-mentioned drawbacks of polyallylamine. For example, they have found that they can be preferably used as a carrier for affinity chromatography or as a pickling inhibitor that removes only scales and prevents elution of steel materials, and completed the present invention.
従つて本発明の要旨は、アリルチオ尿素を、水又は溶
媒中で、分子中にアゾ基とアミジン基とを有するラジカ
ル開始剤及び塩化亜鉛の存在下に重合させることを特徴
とするアリルチオ尿素系重合体の製造方法、と アリルチオ尿素にモノアリルアミン無機酸塩を加え
て、水又は溶媒中で、分子中にアゾ基とアミジン基とを
有するラジカル開始剤及び塩化亜鉛の存在下に重合させ
ることを特徴とするアリルチオ尿素系重合体の製造方
法、とにある。Therefore, the gist of the present invention is to polymerize allylthiourea in water or a solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. A method for producing a combined product, and adding monoallylamine inorganic acid salt to allylthiourea and polymerizing in water or a solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. And a method for producing an allylthiourea polymer.
以下本発明を更に詳細に説明する。The present invention will be described in more detail below.
本発明において用いられるラジカル開始剤は、分子中に
アゾ基とアミジン基とを有するものであり、その代表例
として下記の一般式を有するものが挙げられるが、これ
に限定されるものではないことはもちろんである。The radical initiator used in the present invention has an azo group and an amidine group in the molecule, and typical examples thereof include those having the following general formula, but the invention is not limited thereto. Of course.
このラジカル開始剤の添加量は、単量体に対して一般に
０．２〜１０モル％好ましくは０．５〜２モル％、特に
好ましくは１モル％である。 The amount of the radical initiator added is generally 0.2 to 10 mol%, preferably 0.5 to 2 mol%, and particularly preferably 1 mol% based on the monomers.
本発明においては上述のラジカル開始剤とともに重合促
進剤として塩化亜鉛を使用することを必須要件とし、例
えば塩化亜鉛を単量体に対して２５モル％以上加えると
収率良く重合体が得られる。一般に塩化亜鉛の添加量の
増加に伴い重合体の収率が増加するが、塩化亜鉛を端極
に多く加えると塩化亜鉛を溶解させるための極性溶媒が
多く必要になり、単量体濃度が下がり好ましくない。In the present invention, it is essential to use zinc chloride as a polymerization accelerator together with the above radical initiator. For example, when zinc chloride is added in an amount of 25 mol% or more based on the monomer, a polymer can be obtained in good yield. Generally, the polymer yield increases as the amount of zinc chloride added increases, but adding a large amount of zinc chloride to the end electrode requires a large amount of a polar solvent to dissolve zinc chloride, resulting in a decrease in the monomer concentration. Not preferable.
従つて、重合を効率良く行なうためには、特に塩化亜鉛
を単量体に対して５０〜１５０mole％加えるのが望まし
い。Therefore, in order to carry out the polymerization efficiently, it is desirable to add zinc chloride in an amount of 50 to 150 mole% relative to the monomer.
また重合反応は極性溶媒中で行なわれる。溶媒の例とし
ては、水、ＤＭＦ、ＤＭＳＯ等が挙げられる。Further, the polymerization reaction is carried out in a polar solvent. Examples of the solvent include water, DMF, DMSO and the like.
本発明の一態様によれば、アリルチオ尿素を極性溶媒中
で前述のラジカル開始剤と塩化亜鉛の存在下に重合させ
ることにより、一般式 を有するアリルチオ尿素重合体が収率よく得られる。According to one aspect of the present invention, by polymerizing allylthiourea in a polar solvent in the presence of the above-mentioned radical initiator and zinc chloride, a compound of the general formula An allyl thiourea polymer having is obtained in good yield.
また本発明の他の態様によれば、アリルチオ尿素にモノ
アリルアミン無機酸塩を加えて、極性溶媒中で前述のラ
ジカル開始剤と塩化亜鉛の存在下で重合させることによ
り、一般式 を有するアリルチオ尿素系重合体が収率良く得られる。According to another aspect of the present invention, by adding a monoallylamine inorganic acid salt to allylthiourea and polymerizing in a polar solvent in the presence of the above-mentioned radical initiator and zinc chloride, a compound of the general formula An allyl thiourea-based polymer having is obtained in good yield.
（実施例） 以下に、実施例を比較例と対比しながら説明するが、本
発明はこれらの実施例に限定されるものではない。(Examples) Hereinafter, examples will be described in comparison with comparative examples, but the present invention is not limited to these examples.
実施例１ モノアリルアミン塩酸塩（ＭＡＡ・ＨＣｌ）、アリルチ
オ尿素（ＡＴＵ）を所定のの比で混合し、塩化亜鉛を全
モノマーに対して５０、１００、１５０mole％加え、水
を添加して７０％水溶液を調製した。Example 1 Monoallylamine hydrochloride (MAA.HCl) and allylthiourea (ATU) were mixed at a predetermined ratio, and zinc chloride was added in an amount of 50, 100, and 150 mole% based on all monomers, and water was added to 70%. An aqueous solution was prepared.
これらの溶液に、記の開始剤 を全モノマーに対して１mole％添加して、６０℃、５０
時間静置重合した。Add these initiators to these solutions. 1 mole% to all the monomers, 60 ° C, 50
Polymerization was allowed to stand for a period of time.
重合後、重合系をアセトンに注入して１日放置した。析
出した沈殿をメタノールで充分洗浄した後、濾取乾燥す
ると白色粉末が得られた。After the polymerization, the polymerization system was poured into acetone and left for 1 day. The deposited precipitate was thoroughly washed with methanol and then filtered and dried to obtain a white powder.
得られた物質の収率、溶解性及び粘度を表１に示す。The yield, solubility and viscosity of the obtained substance are shown in Table 1.
ただし、表１のＮｏ．１、８及び１５は参考例である。However, No. 1 in Table 1 1, 8 and 15 are reference examples.
なお、これらの物質中に塩化亜鉛が含まれる可能性があ
るので、原子吸光分析により塩化亜鉛の含有量を求め、
その塩化亜鉛含有量を差し引いて全モノマーに対する収
率を決定した。Since zinc chloride may be contained in these substances, determine the content of zinc chloride by atomic absorption spectrometry,
The zinc chloride content was subtracted to determine the yield based on total monomer.
表１から、塩化亜鉛の添加量の増加によつて収率が増加
していることが解かる。また、アリルチオ尿素の仕込み
モル比の増加に伴い、得られた物質の水に対する溶解性
が低下している。 It can be seen from Table 1 that the yield increases with an increase in the amount of zinc chloride added. Further, the solubility of the obtained substance in water decreases as the charged molar ratio of allylthiourea increases.
表１に示すＮｏ．１１で得られた物質の赤外吸収スペク
トルを第１図に示す。この図によれば第一アミノ基と塩
化亜鉛がキレートを形成したために生じると考えられる
吸収が１６７５cm-1に観察され、チオ尿素基による吸収
が１６２５、１５６５cm-1に検出される。No. shown in Table 1 The infrared absorption spectrum of the substance obtained in Example 11 is shown in FIG. According to this figure, the absorption considered to be caused by the formation of a chelate between the primary amino group and zinc chloride was observed at 1675 cm -1, and the absorption by the thiourea group was detected at 1625 and 1565 cm -1 .
このＮｏ．１１の物質の１Ｈ−ＮＭＲスペクトルを第２
図に示す。この図からチオ尿素基による７．６９、７．
０９ppmの吸収がポリアリルアミン塩酸塩のスペクトル
に加わつて観察された。This No. 1 H-NMR spectrum of the substance of 11
Shown in the figure. From this figure, 7.69, 7.
An absorption of 09 ppm was observed in addition to the polyallylamine hydrochloride spectrum.
また、表１に示すＮｏ．２〜６、Ｎｏ．９、１０、１
２、１３、Ｎｏ．１６〜２０の物質の赤外吸収スペクト
ル及び１Ｈ−ＮＭＲスペクトルも上述のＮｏ．１１で得
られた結果と同様の結果が得られた。In addition, No. 1 shown in Table 1. 2-6, No. 9, 10, 1
2, 13, No. The infrared absorption spectrum and 1 H-NMR spectrum of the substances of 16 to 20 are also as described in No. Results similar to those obtained in 11 were obtained.
以上の事により表１に示すＮｏ．２〜６、Ｎｏ．９〜１
３、Ｎｏ．１６〜２０の物質は下記に示す式（IV）の化
学構造を持つポリマーの塩化亜鉛錯体であると考えられ
る。これを塩酸などの鉱酸で処理することによつて錯体
を形成している塩化亜鉛を除くことができた。As a result of the above, No. 2-6, No. 9-1
3, No. The substances of 16 to 20 are considered to be zinc chloride complexes of polymers having the chemical structure of formula (IV) shown below. By treating this with a mineral acid such as hydrochloric acid, zinc chloride forming a complex could be removed.
また表１に示すＮｏ．１４で得られた物質の赤外吸収ス
ペクトルを第３図に示す。この図によればチオ尿素基に
よる吸収が１６２５、１５６５cm-1に検出される。この
Ｎｏ．１４の物質の１Ｈ−ＮＭＲスペクトルから、チオ
尿素基による７．６９、７．０９ｐｐｍの吸収が観察さ
れた。 In addition, No. 1 shown in Table 1 The infrared absorption spectrum of the substance obtained in 14 is shown in FIG. According to this figure, absorption by the thiourea group is detected at 1625 and 1565 cm -1 . This No. From the 1 H-NMR spectrum of the substance of 14, the absorption of 7.69 and 7.09 ppm by the thiourea group was observed.
またＮｏ．７、２１で得られた物質の赤外吸収スペクト
ル及び１Ｈ−ＮＭＲスペクトルも同様な結果であつた。In addition, No. The infrared absorption spectrum and 1 H-NMR spectrum of the substance obtained in Nos. 7 and 21 showed similar results.
これらの事により、表１に示すＮｏ．７、１４、２１で
得られた物質は下記の式（III）で示される化学構造を
持つポリマー又はその塩化亜鉛錯体であると考えられ
る。これを塩酸などの鉱酸で処理することによつてその
塩化亜鉛錯体を形成している塩化亜鉛を除くことができ
た。Due to these things, No. 1 shown in Table 1 was obtained. The substances obtained in Nos. 7, 14, and 21 are considered to be a polymer having a chemical structure represented by the following formula (III) or a zinc chloride complex thereof. By treating this with a mineral acid such as hydrochloric acid, the zinc chloride forming the zinc chloride complex could be removed.
比較例１ モノアリルアミン塩酸塩（ＭＡＡ・ＨＣｌ）とアリルチ
オ尿素（ＡＴＵ）を実施例１と同じ比で混合し、塩化亜
鉛を加えずに、水を添加して７０％水溶液を調製した。 Comparative Example 1 Monoallylamine hydrochloride (MAA.HCl) and allylthiourea (ATU) were mixed in the same ratio as in Example 1, and water was added without adding zinc chloride to prepare a 70% aqueous solution.
これらの溶液に実施例１で用いた開始剤を全モノマーに
対して１mole％添加し、６０℃、５０時間静置重合を行
なつた後、実施例１と同様に処理を行ない、白色粉末を
得た。ここで得られた物質の収率、溶解性及び粘度を表
２に示す。The initiator used in Example 1 was added to these solutions in an amount of 1 mole% based on all the monomers, and the mixture was allowed to stand at 60 ° C. for 50 hours for polymerization, and then treated in the same manner as in Example 1 to obtain a white powder. Obtained. The yield, solubility and viscosity of the substance obtained here are shown in Table 2.
アリルチオ尿素が含まれる系（表２中のＮｏ．２３〜２
８）の収率は１１％以下であり、実施例１と比較すると
かなり低い収率である。 System containing allylthiourea (Nos. 23 to 2 in Table 2)
The yield of 8) is 11% or less, which is considerably lower than that of Example 1.
実施例２ ７０％モノアリルアミン塩酸塩（ＭＡＡ・ＨＣｌ）水溶
液、アリルチオ尿素（ＡＴＵ）、７０％塩化亜鉛水溶液
を所定の比で混合した。Example 2 A 70% monoallylamine hydrochloride (MAA.HCl) aqueous solution, allylthiourea (ATU), and a 70% zinc chloride aqueous solution were mixed at a predetermined ratio.
実施例１で用いた開始剤を全モノマーに対して１mole％
添加して、６０℃、５０時間静置重合した。The amount of the initiator used in Example 1 was 1 mole% based on all monomers.
After the addition, static polymerization was carried out at 60 ° C. for 50 hours.
重合後の処理を実施例１と同様に行なうと、白色粉末が
得られた。When the treatment after the polymerization was carried out in the same manner as in Example 1, a white powder was obtained.
得られた物質の収率、溶解性及び粘度を表３に示す。The yield, solubility and viscosity of the obtained substance are shown in Table 3.
ここで得られた全ての物質（Ｎｏ．２９〜３４）の赤外
吸収スペクトルと１Ｈ−ＮＭＲスペクトルは実施例１の
Ｎｏ．１１で得られた物質の結果と同様な結果を示し
た。 The infrared absorption spectra and 1 H-NMR spectra of all the substances (Nos. 29 to 34) obtained here are shown in No. 1 of Example 1. Similar results to those of the material obtained in 11.
それ故、これらの物質は実施例１に示す式（IV）の化学
構造を持つポリマーの塩化亜鉛錯体であると考えられ
る。これを塩酸などの鉱酸で処理することにより錯体を
形成している塩化亜鉛を除くことができた。Therefore, these substances are considered to be polymer zinc chloride complexes having the chemical structure of formula (IV) shown in Example 1. By treating this with a mineral acid such as hydrochloric acid, zinc chloride forming a complex could be removed.
実施例３ モノアリルアミン塩酸塩（ＭＡＡ・ＨＣｌ）、アリルチ
オ尿素（ＡＴＵ）を所定の比で混合し、塩化亜鉛を全モ
ノマーに対して１００mole％加え、水を添加して７０％
水溶液を調製した。Example 3 Monoallylamine hydrochloride (MAA.HCl) and allylthiourea (ATU) were mixed in a predetermined ratio, zinc chloride was added at 100 mole% to all monomers, and water was added to 70%.
An aqueous solution was prepared.
これらの溶液に、下記の開始剤 を全モノマーに対して１mole％添加して、６０℃、５０
時間静置重合した。Add these initiators to these solutions 1 mole% to all the monomers, 60 ° C, 50
Polymerization was allowed to stand for a period of time.
重合後の処理を実施例１と同様に行なうと、白色粉末が
得られた。When the treatment after the polymerization was carried out in the same manner as in Example 1, a white powder was obtained.
得られた物質の収率、溶解性及び粘度を表４に示す。The yield, solubility and viscosity of the obtained substance are shown in Table 4.
表４に示すＮｏ．３６〜４０の物質の赤外吸収スペクト
ルと１Ｈ−ＮＭＲスペクトルは実施例１のＮｏ．１１で
得られた物質の赤外吸収スペクトル及び１Ｈ−ＮＭＲス
ペクトルと同様な結果を示した。 No. shown in Table 4 The infrared absorption spectra and 1 H-NMR spectra of the substances of Nos. 36 to 40 are shown in No. 1 of Example 1. Similar results to the infrared absorption spectrum and 1 H-NMR spectrum of the substance obtained in Example 11 were shown.
従つて、Ｎｏ．３６〜４０の物質は実施例１に示した式
（IV）の化学構造を持つポリマーの塩化亜鉛錯体である
と考えられる。これを塩酸などの鉱酸で処理することに
よつて錯体を形成している塩化亜鉛を除くことができ
た。Therefore, no. The substances of 36 to 40 are considered to be zinc chloride complexes of the polymer having the chemical structure of the formula (IV) shown in Example 1. By treating this with a mineral acid such as hydrochloric acid, zinc chloride forming a complex could be removed.
また、表４のＮｏ．４１で得られた物質は実施例１のＮ
ｏ．１４で得られた物質と同様な赤外吸収スペクトル及
び１Ｈ−ＮＭＲスペクトルを示した。In addition, in Table 4, No. The substance obtained in 41 is N of Example 1.
o. The infrared absorption spectrum and 1 H-NMR spectrum similar to those of the substance obtained in Example 14 were shown.
この事から、このＮｏ．４１の物質は実施例１に示した
式（III）の化学構造を持つポリマー又はその塩化亜鉛
錯体であると考えられる。これを塩酸などの鉱酸で処理
することによつてその塩化亜鉛錯体を形成している塩化
亜鉛を除くことができた。From this, this No. The substance 41 is considered to be a polymer having the chemical structure of formula (III) shown in Example 1 or a zinc chloride complex thereof. By treating this with a mineral acid such as hydrochloric acid, the zinc chloride forming the zinc chloride complex could be removed.
発明の効果 本発明によれば、ポリアリルアミンの欠点を解消したア
リルチオ尿素系重合体が一段の重合操作で高収率で得ら
れ、得られた重合体はアフイニテイークロマトグラフイ
ー用担体や酸洗インヒビターとして好ましく用いられ
る。EFFECTS OF THE INVENTION According to the present invention, an allylthiourea-based polymer that has solved the drawbacks of polyallylamine is obtained in a high yield in a single-stage polymerization operation, and the obtained polymer is a carrier for affinity chromatography or pickling. It is preferably used as an inhibitor.
第１図及び第２図は本発明により得られたアリルチオ尿
素系重合体の赤外吸収スペクトル図及び１Ｈ−ＮＭＲス
ペクトル図を示し、 第３図は、本発明により得られたアリルチオ尿素重合体
の赤外吸収スペクトル図を示す。1 and 2 show the infrared absorption spectrum and 1 H-NMR spectrum of the allylthiourea polymer obtained by the present invention, and FIG. 3 shows the allylthiourea polymer obtained by the present invention. The infrared absorption spectrum of is shown.
Claims (2)
中にアゾ基とアミジン基とを有するラジカル開始剤及び
塩化亜鉛の存在下に重合させることを特徴とするアリル
チオ尿素系重合体の製造方法。1. A method for producing an allylthiourea polymer, which comprises polymerizing allylthiourea in water or a solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. Method.
塩を加えて、水又は溶媒中で、分子中にアゾ基とアミジ
ン基とを有するラジカル開始剤及び塩化亜鉛の存在下に
重合させることを特徴とするアリルチオ尿素系重合体の
製造方法。2. A monoallylamine inorganic acid salt is added to allylthiourea and polymerized in water or a solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. A method for producing an allylthiourea polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15636885A JPH0615592B2 (en) | 1985-07-16 | 1985-07-16 | Method for producing allylthiourea polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15636885A JPH0615592B2 (en) | 1985-07-16 | 1985-07-16 | Method for producing allylthiourea polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6218408A JPS6218408A (en) | 1987-01-27 |
| JPH0615592B2 true JPH0615592B2 (en) | 1994-03-02 |
Family
ID=15626223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15636885A Expired - Lifetime JPH0615592B2 (en) | 1985-07-16 | 1985-07-16 | Method for producing allylthiourea polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615592B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1609613A1 (en) | 2004-06-22 | 2005-12-28 | Fuji Photo Film Co., Ltd. | Image recording medium manufacturing method |
| EP2436740A1 (en) | 2003-09-29 | 2012-04-04 | Fujifilm Corporation | Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method |
-
1985
- 1985-07-16 JP JP15636885A patent/JPH0615592B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2436740A1 (en) | 2003-09-29 | 2012-04-04 | Fujifilm Corporation | Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method |
| EP1609613A1 (en) | 2004-06-22 | 2005-12-28 | Fuji Photo Film Co., Ltd. | Image recording medium manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6218408A (en) | 1987-01-27 |
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