JP4105088B2 - Method for producing coating agent comprising solution containing phosphoric acid residue-containing unsaturated monomer homopolymer - Google Patents

Description

The present invention includes a phosphoric acid residue-containing unsaturated monomer containing a phosphoric acid residue-containing unsaturated monomer homopolymer, which does not cause gelation during polymerization and has excellent long-term storage stability. It relates to how to manufacture by solution polymerization of the dimer.

  Conventionally, when an unsaturated monomer having a phosphoric acid residue (phosphorus acid residue-containing unsaturated monomer) is solution polymerized and the polymer is synthesized, gelation is likely to occur in the polymerization stage [for example, Abstracts of the 35th Polymer Research Presentation, page 95 (issued July 6, 1989)], which was insoluble in various solvents. In addition, a solution obtained by dissolving a polymer composed only of a phosphoric acid residue-containing unsaturated monomer (phosphoric acid residue-containing unsaturated monomer homopolymer) in an organic solvent forms an antistatic coating. Although it is useful as a coating agent, a gel is easily formed by cross-linking by a strong interaction of phosphorus acid residues, and there is a problem that long-term storage is difficult.

  For this reason, when producing a polymer using a phosphoric acid residue-containing unsaturated monomer, it is often copolymerized with another unsaturated monomer which usually does not have a phosphoric acid residue. For example, International Publication No. 01/006519 pamphlet (Patent Document 1) describes: (a) at least one phosphorus system selected from the group consisting of phosphoric acid, phosphonic acid, phosphinic acid, halides thereof, and salts thereof in the molecule; Disclosed is a tooth coating composition containing an acid residue and a weight average molecular weight of 10,000 to 5,000,000, and (b) water or an alcohol having 1 to 5 carbon atoms. However, the polymer prepared in the examples of Patent Document 1 includes an unsaturated monomer containing a phosphorus acid residue and an unsaturated monomer having no phosphorus acid residue (non-phosphorous unsaturated monomer). And a non-phosphorous unsaturated monomer as a main component, not a homopolymer of a phosphoric acid residue-containing unsaturated monomer.

  A polymer using a phosphoric acid residue-containing unsaturated monomer is promising as a conductive resin. For example, Japanese Patent Application Laid-Open No. 2001-123151 (Patent Document 2) discloses (A) (meth) acrylate monomer having a phosphoric acid group 1 to 60% by weight, (B) (meth) acrylate having a polyoxyalkylene glycol chain. An antistatic agent composition obtained by copolymerizing 1 to 50% by weight of a monomer and (C) 5 to 80% by weight of a (meth) acrylate monomer having an alkyl group having 1 to 18 carbon atoms is described. Such an antistatic agent composition can be imparted with long-term antistatic properties and water resistance by being added to a thermoplastic resin. However, since the content of the phosphoric acid group-containing (meth) acrylate monomer is 60% by weight or less, the antistatic agent composition of Patent Document 2 cannot be said to have sufficient antistatic properties.

WO 01/006519 pamphlet JP 2001-123151 A

Accordingly, a first object of the present invention comprises a phosphorus-based acid residues containing unsaturated monomer alone polymer, gelation does not occur during the polymerization, and excellent coating for long-term storage stability, a phosphorus it is to provide a method for producing a soluble solution polymerization of acid residues containing unsaturated monomer.

As a result of diligent research in view of the above object, the present inventors have used methanol containing 1 to 20% by mass of water as a solvent with 100% by mass of the entire solvent, and 100% by mass of the entire polymerization solution as a phosphoric acid residue. By setting the concentration of the group-containing unsaturated monomer to 14% by mass or less, a coating agent that does not cause gelation during polymerization and has excellent long-term storage stability can be obtained. It was discovered that it can be produced by solution polymerization of The present inventors also used ethanol containing 3 to 30% by mass of water as a solvent with 100% by mass of the entire solvent as a solvent, and 100% by mass of the entire polymerization solution of the phosphoric acid residue-containing unsaturated monomer. It was discovered that by making the concentration 14% by mass or less, a coating agent that does not gel during polymerization and has excellent long-term storage stability can be produced by solution polymerization of unsaturated monomers containing phosphorus acid residues. did. The present inventors also used isopropyl alcohol containing 10 to 30% by mass of water as a solvent with 100% by mass of the entire solvent as a solvent, and 100% by mass of the polymerization solution as a phosphoric acid residue-containing unsaturated monomer. It is possible to produce a coating agent that does not cause gelation during polymerization and has excellent long-term storage by solution polymerization of a phosphoric acid residue-containing unsaturated monomer. discovered. The present invention has been completed based on this invention.

That is, the first method for producing a coating agent of the present invention comprises a phosphoric acid residue-containing unsaturated monomer having one or more phosphoric acid residues and one or more ethylenically unsaturated bonds in the molecule. A coating agent comprising a solution containing a homopolymer of the phosphoric acid residue-containing unsaturated monomer by polymerizing only the body in a solvent, wherein the solvent is 100% by mass and 1 to 20 with methanol containing% by weight of water as a solvent, the whole polymerization solution the concentration of phosphorus-based acid residues containing unsaturated monomer is 14 mass% or less as 100 mass%, residues containing not the phosphorous-based acid After polymerizing the saturated monomer, the resulting polymer solution is left unpurified . The production method of the second coating agent of the present invention includes only a phosphoric acid residue-containing unsaturated monomer having one or more phosphoric acid residues and one or more ethylenically unsaturated bonds in the molecule. Is coated in a solvent to produce a coating agent comprising a solution containing a homopolymer of the phosphoric acid residue-containing unsaturated monomer, the total amount of the solvent being 100% by mass, and 3 to 30% by mass. Ethanol containing water as a solvent, the polymerization solution as a whole is 100% by mass, the concentration of the phosphoric acid residue-containing unsaturated monomer is 14% by mass or less, and the phosphoric acid residue-containing unsaturated monomer After the polymer is polymerized, the resulting polymer solution is left unpurified. The third method for producing a coating agent of the present invention includes only a phosphorus acid residue-containing unsaturated monomer having one or more phosphorus acid residues and one or more ethylenically unsaturated bonds in the molecule. Is coated in a solvent to produce a coating agent comprising a solution containing a homopolymer of the phosphoric acid residue-containing unsaturated monomer, the total amount of the solvent being 10% by mass, and 10-30% by mass Using the isopropyl alcohol containing water as a solvent, the total polymerization solution is 100% by mass, the concentration of the phosphoric acid residue-containing unsaturated monomer is 14% by mass or less, and the phosphoric acid residue-containing unsaturated monomer is After polymerizing the monomer, the resulting polymer solution is left unpurified.

In the first method for producing a coating agent, the content of water in the solvent composed of methanol and water is preferably 1 to 15% by mass. In the second method for producing a coating agent, the content of water in the solvent composed of ethanol and water is preferably 5 to 30% by mass. In the third method for producing a coating agent, the content of water in the solvent composed of isopropyl alcohol and water is preferably 15 to 25% by mass.

（但しR₁は水素基又はアルキル基を示し、Xは−O−基又は−NH−基を示し、Y₁は−O−基を含んでもよい２価の炭化水素基を示し、Zはリン酸残基、ホスホン酸残基、ホスフィン酸残基又はジリン酸残基を示す。）により表される化合物が好ましく、下記式(2)；

（但しR₁は水素基又はアルキル基を示し、Y₂は炭素数２〜20のオキシアルキレン基又はアルキレン基を示し、nは１〜10の整数である。）により表される化合物がより好ましく、下記式(3)；

（ただしR₁は水素基又はアルキル基であり、R₂は水素基又は置換もしくは無置換のアルキル基であり、mは１〜６の整数である。）により表される化合物が特に好ましい。 The phosphoric acid residue-containing unsaturated monomer has the following formula (1):

(Wherein R ₁ represents a hydrogen group or an alkyl group, X represents an —O— group or —NH— group, Y ₁ represents a divalent hydrocarbon group which may contain an —O— group, and Z represents phosphorus. An acid residue, a phosphonic acid residue, a phosphinic acid residue or a diphosphoric acid residue.) Is preferred, and the following formula (2);

(Wherein R ₁ represents a hydrogen group or an alkyl group, Y ₂ represents an oxyalkylene group or alkylene group having 2 to 20 carbon atoms, and n is an integer of 1 to 10). , The following formula (3);

A compound represented by (wherein R ₁ is a hydrogen group or an alkyl group, R ₂ is a hydrogen group or a substituted or unsubstituted alkyl group, and m is an integer of 1 to 6) is particularly preferable.

The coating agent obtained by the first to third production methods does not generate gel for 6 months or more under storage at ordinary temperature or under refrigeration at 10 ° C. or lower. In the first to third coating agent production methods, after preparing the phosphoric acid residue-containing unsaturated monomer homopolymer, a vinyl hydrophilic polymer and / or polyacetal may be added. Polyvinyl alcohol is preferably used as the vinyl-based hydrophilic polymer. It is preferable to add a polyamide resin or a melamine resin together with the polyvinyl alcohol.

  The method for producing a phosphoric acid residue-containing unsaturated monomer homopolymer by solution polymerization of the present invention uses an aliphatic lower alcohol containing 0.1 to 35% by mass of water as a solvent, with the entire solvent being 100% by mass. Since the entire polymerization solution is 100% by mass and the concentration of the phosphoric acid residue-containing unsaturated monomer is 14% by mass or less, gelation does not occur during the polymerization.

  In the method for producing a solution of a phosphoric acid residue-containing unsaturated monomer homopolymer according to the present invention, an aliphatic lower alcohol containing 0.1 to 35% by mass of water is used as a solvent. The total polymerization solution is 100% by mass and the concentration of the phosphoric acid residue-containing unsaturated monomer is 14% by mass or less. An acid residue-containing unsaturated monomer homopolymer solution can be easily obtained. Since the phosphoric acid residue-containing unsaturated monomer homopolymer is excellent in electrical conductivity, a solution containing this is useful for coating agent applications.

  The conductive resin composition of the present invention obtained by heat-treating a polymer solution containing a phosphoric acid residue-containing unsaturated monomer homopolymer and a vinyl-based hydrophilic polymer and / or polyacetal is conductive. Excellent chemical resistance, flexibility, transparency and adhesion to various substrates. The conductive resin composition of the present invention having such characteristics is useful as a conductive resin composition for a bioelectrode that is interposed between the skin and the electrode element when the bioelectrode is mounted.

[1] Production method by solution polymerization of phosphoric acid residue-containing unsaturated monomer homopolymer Production method by solution polymerization of a polymer comprising only the phosphoric acid residue-containing unsaturated monomer of the present invention comprises: Using aliphatic lower alcohol containing 0.1-35% by weight of water as the solvent with 100% by weight of the whole solvent as the solvent, the concentration of the phosphoric acid residue-containing unsaturated monomer is 14% with the entire polymerization solution being 100% by weight. % Or less.

により表されるものが挙げられる。中でもリン系酸残基としては、式(4)により表されるリン酸残基、式(9)により表されるホスホン酸残基、式(13)により表されるホスフィン酸残基及び式(6)により表されるジリン酸残基からなる群から選ばれた少なくとも一種がより好ましい。リン系酸残基は錯塩を形成していても良い。錯塩を形成する場合、ハロゲンイオン、アンモニウムイオン又はアミン残基と錯塩を形成するのが好ましい。 (1) Phosphoric acid residue-containing unsaturated monomer Phosphoric acid residue-containing unsaturated monomer having one or more phosphoric acid residues and one or more ethylenically unsaturated bonds in the molecule As the phosphorus acid residue, those derived from at least one phosphorus acid selected from the group consisting of phosphoric acid, phosphonic acid and phosphinic acid are preferable. Specific examples of the phosphorus acid residue include the following formulas (4) to (14):

The thing represented by these is mentioned. Among them, as the phosphoric acid residue, a phosphoric acid residue represented by the formula (4), a phosphonic acid residue represented by the formula (9), a phosphinic acid residue represented by the formula (13) and the formula ( More preferred is at least one selected from the group consisting of diphosphate residues represented by 6). The phosphorus acid residue may form a complex salt. When forming a complex salt, it is preferable to form a complex salt with a halogen ion, an ammonium ion or an amine residue.

（但しR₁は水素基又はアルキル基を示し、Xは−O−基又は−NH−基を示し、Y₁は−O−基を含んでもよい２価の炭化水素基を示し、Zはリン酸残基、ホスホン酸残基、ホスフィン酸残基又はジリン酸残基を示す。）により表されるものが好ましい。Y₁の具体例としては、オキシアルキレン基、アルキレン基、オキシアリーレン基、アリーレン基等が挙げられる。一般式(1)で表されるリン系酸残基含有不飽和単量体は単独で用いてもよいし、２種以上を併用しても良い。 Examples of the phosphoric acid residue-containing unsaturated monomer include the following formula (1);

(Wherein R ₁ represents a hydrogen group or an alkyl group, X represents an —O— group or —NH— group, Y ₁ represents a divalent hydrocarbon group which may contain an —O— group, and Z represents phosphorus. An acid residue, a phosphonic acid residue, a phosphinic acid residue or a diphosphoric acid residue is preferred). Specific examples of Y ₁ include an oxyalkylene group, an alkylene group, an oxyarylene group, an arylene group, and the like. The phosphoric acid residue-containing unsaturated monomer represented by the general formula (1) may be used alone or in combination of two or more.

（但しR₁は水素基又はアルキル基を示し、Y₂は炭素数２〜20のオキシアルキレン基又はアルキレン基を示し、nは１〜10の整数である。）により表されるリン酸残基含有不飽和単量体がより好ましく、下記式(3)；

（ただしR₁は水素又はアルキル基であり、R₂は水素又は置換もしくは無置換のアルキル基であり、mは１〜６の整数である。）により表されるリン酸残基含有不飽和単量体（以下「単量体(I)」と呼ぶ）が特に好ましい。R₁はH又はCH₃であり、R₂はH、CH₃又はCH₂Clであるのが好ましい。 As an unsaturated monomer containing a phosphorus acid residue, the following formula (2):

(Wherein R ₁ represents a hydrogen group or an alkyl group, Y ₂ represents an oxyalkylene group or alkylene group having 2 to 20 carbon atoms, and n is an integer of 1 to 10). Containing unsaturated monomer is more preferred, the following formula (3);

Where R ₁ is hydrogen or an alkyl group, R ₂ is hydrogen or a substituted or unsubstituted alkyl group, and m is an integer of 1 to 6. A monomer (hereinafter referred to as “monomer (I)”) is particularly preferred. R ₁ is preferably H or CH ₃ and R ₂ is preferably H, CH ₃ or CH ₂ Cl.

  The structural formulas and physical properties of typical monomers (I) are shown in Tables 1 and 2, respectively. These monomers are sold by Unichemical Corporation under the trade name Phosmer (registered trademark). However, the phosphoric acid residue-containing unsaturated monomer that can be used in the present invention is not limited thereto.

注：(1) Brookfield型粘度計により測定（括弧内はロータNo.を示す）。
(2) 単位は質量％。

Note: (1) Measured with a Brookfield viscometer (the rotor number is shown in parentheses).
(2) The unit is mass%.

The phosphate residue of monomer (I) may be dissociated or may form a complex salt. When forming a complex salt, in order to neutralize the charge, for example, ammonium ions containing mono-, di- or tri-alkyl groups such as primary, secondary, tertiary or quaternary alkyl groups, allyl groups, aralkyl groups, etc. It is preferable to form a complex salt with an alkanolamine residue, particularly N ⁺ R ³ _4-f (OH) _f (where R ³ is an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and carbon). It represents at least one selected from the group consisting of alicyclic groups of formula 6 to 12, and f represents a positive integer of 1 to 3).

（ただしR₄及びR₅はそれぞれ独立に水素基又はアルキル基であり、R₆及びR₇はそれぞれ独立に水素基又は置換もしくは無置換のアルキル基であり、q及びrはそれぞれ独立に１〜６の整数である。）により表される化合物（以下「単量体(II)」と呼ぶ）も使用可能である。 As the phosphoric acid residue-containing unsaturated monomer, the following general formula (15):

(However, R ₄ and R ₅ are each independently a hydrogen group or an alkyl group, R ₆ and R ₇ are each independently a hydrogen group or a substituted or unsubstituted alkyl group, and q and r are each independently 1 to 1) A compound represented by the formula (hereinafter referred to as “monomer (II)”) can also be used.

（ただしR₁は水素基又はアルキル基であり、R₂は水素基又は置換もしくは無置換のアルキル基であり、mは１〜６の整数である。）により表される2-ヒドロキシ（メタ）アクリレートと、五酸化リンとを反応原料としてエステル化反応を行うことにより得られる。 Monomer (I) and monomer (II) are represented by the following general formula (16):

(Wherein R ₁ is a hydrogen group or an alkyl group, R ₂ is a hydrogen group or a substituted or unsubstituted alkyl group, and m is an integer of 1 to 6). It can be obtained by carrying out an esterification reaction using acrylate and phosphorus pentoxide as reaction raw materials.

により表される2-ヒドロキシエチルメタクリレートを用い、単量体(I)としてアシッド・ホスホオキシエチルメタクリレート（別名：メタクリロイルオキシエチルホスフェート）を調製し、単量体(II)としてジ（メタクリロイルオキシエチル）ホスフェートを調製する例を説明する。 Hereinafter, as 2-hydroxy (meth) acrylate represented by the general formula (16), the following formula (17):

Prepared acid phosphooxyethyl methacrylate (aka methacryloyloxyethyl phosphate) as monomer (I) and di (methacryloyloxyethyl) as monomer (II) using 2-hydroxyethyl methacrylate represented by An example of preparing a phosphate will be described.

に示すように2-ヒドロキシエチルメタクリレートと五酸化リンを反応させることにより、ジ（メタクリロイルオキシエチル）アシッド・ピロホスフェートを調製し、次いで下記式(19)：

に示すように、ジ（メタクリロイルオキシエチル）アシッド・ピロホスフェートに2-ヒドロキシエチルメタクリレートを反応させることにより得られる。 Acid phosphooxyethyl methacrylate and di (methacryloyloxyethyl) phosphate are represented by, for example, the following formula (18):

Di (methacryloyloxyethyl) acid pyrophosphate is prepared by reacting 2-hydroxyethyl methacrylate and phosphorus pentoxide as shown in the following formula (19):

As shown in the above, it can be obtained by reacting di (methacryloyloxyethyl) acid pyrophosphate with 2-hydroxyethyl methacrylate.

  The esterification reaction for obtaining the monomer (I) and the monomer (II) includes a known method for producing a phosphate ester by an esterification reaction using an organic hydroxy compound and phosphorus pentoxide as raw materials. Applicable. For example, phosphorus pentoxide can be added stepwise to 2-hydroxy (meth) acrylate, or the addition rate of phosphorus pentoxide can be appropriately adjusted.

  As the monomer (II), the di (methacryloyloxyethyl) phosphate is preferable. Monomer (II) may be used alone or in combination of two or more thereof.

  Monomer (I) has excellent electrical conductivity, and monomer (II) has a crosslinking action and excellent film-forming properties, so both monomer (I) and monomer (II) May be used. When both monomers (I) and (II) are used, the blending molar ratio of [monomer (I)] / monomer (II)] is preferably 1 / 0.1 to 1/2.

（ただしR₈及びR₁₁はそれぞれ独立に水素基又はアルキル基であり、R₉及びR₁₀はそれぞれ独立に水素基又は置換もしくは無置換のアルキル基であり、s及びtはそれぞれ独立に１〜６の整数である。）により表されるピロリン酸基含有不飽和単量体が挙げられる。上記式(20)により表されるピロリン酸基含有不飽和単量体は架橋作用を有し、造膜性に優れている。上記式(20)により表されるピロリン酸基含有不飽和単量体は単量体(I)とともに用いてもよい。上記式(20)により表されるピロリン酸基含有不飽和単量体としては、ジ（メタクリロイルオキシエチル）アシッド・ピロホスフェートが好ましい。 As the phosphoric acid residue-containing unsaturated monomer, the following general formula (20):

(Wherein R ₈ and R ₁₁ are each independently a hydrogen group or an alkyl group, R ₉ and R ₁₀ are each independently a hydrogen group or a substituted or unsubstituted alkyl group, and s and t are each independently 1 to 1) 6 is an integer of 6 pyrophosphate group-containing unsaturated monomer. The pyrophosphate group-containing unsaturated monomer represented by the above formula (20) has a crosslinking action and is excellent in film forming property. The pyrophosphate group-containing unsaturated monomer represented by the above formula (20) may be used together with the monomer (I). The pyrophosphate group-containing unsaturated monomer represented by the above formula (20) is preferably di (methacryloyloxyethyl) acid pyrophosphate.

に示すように、2-ヒドロキシエチルメタクリレートと五酸化リンを反応させることにより、アシッド・ホスホオキシエチルメタクリレートとジ（メタクリロイルオキシエチル）ホスフェートとジ（メタクリロイルオキシエチル）アシッド・ピロホスフェートとが得られる。 Di (methacryloyloxyethyl) acid pyrophosphate can be prepared, for example, according to the above formula (18). For example, the following formula (21):

As shown in the above, by reacting 2-hydroxyethyl methacrylate and phosphorus pentoxide, acid phosphooxyethyl methacrylate, di (methacryloyloxyethyl) phosphate and di (methacryloyloxyethyl) acid pyrophosphate are obtained.

(2) Solvent As the solvent, an aliphatic lower alcohol containing 0.1 to 35% by mass of water with 100% by mass as the whole solvent is used. When the water content is less than 0.1% by mass or more than 35% by mass, the polymer is gelled during the polymerization, or the storage stability of the resulting polymer solution is deteriorated. The water content is preferably 1 to 25% by mass, and more preferably 1 to 20% by mass. The aliphatic lower alcohol preferably has 3 or less carbon atoms. Of these, methanol, ethanol and isopropyl alcohol are more preferred as the aliphatic lower alcohol. Two or more aliphatic lower alcohols may be used in combination.

  Hereinafter, preferable water content in a solvent using methanol, ethanol, and isopropyl alcohol will be described. When using a solvent consisting of methanol and water, the content of water is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, based on 100% by mass of the whole solvent, and 0.1 to 10% by mass. Is particularly preferred. When using a solvent comprising ethanol and water, the water content is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, based on 100% by mass of the entire solvent, and 3 to 10% by mass. Is particularly preferred. When a solvent composed of isopropyl alcohol and water is used, the content of water is preferably 10 to 30% by mass, more preferably 15 to 20% by mass, based on 100% by mass of the entire solvent.

  In addition, as long as the effect of this invention is not impaired, you may coexist another solvent with a solvent as needed. Examples of other solvents include esters.

  Since aliphatic lower alcohol solvents have a large growth chain reaction constant of the solvent itself, the growth of the polymer is relatively suppressed in the solvent containing this, and the degree of polymerization is difficult to increase. Is easily generated. It is preferable to prepare a polymer having a relatively low degree of polymerization from the viewpoint of setting the viscosity of a phosphoric acid residue-containing unsaturated monomer homopolymer solution described later to an appropriate range.

(3) Polymerization solution concentration In the polymerization solution, the initial concentration of the unsaturated monomer component needs to be 14% by mass or less, and preferably 12% by mass or less. When the initial concentration of the unsaturated monomer component in the polymerization solution is more than 14% by mass, the polymer gels during the polymerization, or the long-term storage stability of the resulting polymer solution is deteriorated. Although there is no restriction | limiting in particular in the minimum of initial concentration, It is preferable that it is 5 mass% or more from a viewpoint of manufacturing efficiency.

(4) Reaction method The polymerization reaction was conducted in the above solvent using 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis ( 2-methylpropionate), azo initiators such as dimethyl 2,2'-azobisisobutyrate, or peroxide initiators such as lauryl peroxide, benzoyl peroxide, tert-butylperoxy pivalate The polymerization is performed by radical polymerization using a polymerization initiator such as The total amount of the polymerization initiator used is preferably 0.005 to 0.05, more preferably 0.01 to 0.03 in terms of weight ratio when the monomer component is 1. If the amount of the polymerization initiator used is not within the above preferred range, the polymer is likely to gel and become insoluble in the solvent.

  The polymerization procedure is described. First, a solution comprising [phosphorus acid residue-containing unsaturated monomer + solvent] is charged into a reactor equipped with a stirrer and a reflux condenser, and the temperature is raised to 40 ° C. to 90 ° C., preferably 50 ° C. to 80 ° C. . A polymerization initiator is added immediately after reaching the predetermined temperature. At this time, there is slight heat generation, and the start of polymerization can be confirmed. A polymerization initiator is added again after a lapse of a predetermined time (usually about 2 hours) after reaching a predetermined temperature, and then the polymerization reaction is continued for about 1 hour. The reaction temperature does not need to be constant from the beginning to the end, and a method of increasing the temperature at the end of the polymerization to minimize the unreacted monomer may be used.

  The polymer solution after the reaction can be used as it is as a coating agent, as will be described later. When isolating an unsaturated monomer homopolymer containing a phosphorus acid residue, concentrate until the solid content of the polymerization solution is 10 to 80% by weight, and then add the concentrated solution into a poor solvent. To precipitate a viscous solid and filter it off. However, the solution after the reaction includes not only the desired phosphoric acid residue-containing unsaturated monomer polymer but also impurities such as free phosphoric acid, unreacted monomers, and components with insufficient polymerization degree. Therefore, it is preferable to carry out purification. However, it is not intended to limit the purification. Purification is performed by concentrating the polymerization solution until the solid content concentration becomes 10 to 80% by weight, and then pouring the concentrated solution into a poor solvent to precipitate a viscous solid and removing the poor solvent by a decantation method. Do. As the poor solvent, acetone, 1,1,1-trichloroethane and the like are preferable. The poor solvent is used in a large excess amount of 2 to 15 times the volume of the reaction product. The washing operation of the viscous solid with the poor solvent may be repeated as necessary. By performing such purification, the impurities can be removed.

[2] Phosphoric acid residue-containing unsaturated monomer homopolymer The phosphoric acid residue-containing unsaturated monomer homopolymer obtained by the method as described above is a polymer having a relatively low molecular weight. . Usually, it is preferable that the degree of polymerization is such that the viscosity is 3 to 30 mPa when a methanol solution having a polymer solid concentration of 15 to 25% by weight is obtained. Such a low-polymerization degree phosphoric acid residue-containing unsaturated monomer homopolymer exhibits excellent proton conductivity of 10 ⁻⁴ to 10 ⁻² S · cm ⁻¹ , chemical resistance and flexibility Excellent in transparency, transparency and adhesion to various substrates.

[3] Method for Producing Phosphoric Acid Residue-containing Unsaturated Monomer Homopolymer Solution The method for producing a phosphorus acid residue-containing unsaturated monomer homopolymer solution of the present invention is a homopolymer after reaction. Except for not isolating the homopolymer from the solution, it is the same as the solution polymerization method of the phosphoric acid residue-containing unsaturated monomer described in [1] above. Accordingly, the polymer does not gel during polymerization.

[4] Phosphoric acid residue-containing unsaturated monomer homopolymer solution The phosphoric acid residue-containing unsaturated monomer homopolymer solution obtained by the production method of the present invention is excellent in long-term storage stability. . Specifically, even when stored at room temperature or refrigerated at 10 ° C. or lower, gel does not occur for more than 6 months and there is almost no change in viscosity. Moreover, since the phosphoric acid residue-containing unsaturated monomer homopolymer is excellent in conductivity, the present solution containing this is useful for preparing a conductive resin composition and a coating agent described below.

[5] Conductive resin composition The conductive resin composition of the present invention is obtained by adding at least a vinyl-based hydrophilic polymer and / or polyacetal to the above-mentioned phosphoric acid residue-containing unsaturated monomer homopolymer solution. The obtained polymer solution is obtained by heat treatment. The phosphoric acid residue-containing unsaturated monomer homopolymer is excellent in compatibility with the vinyl hydrophilic polymer and polyacetal. Therefore, the conductive resin composition of the present invention in which a homopolymer of a phosphorus acid residue-containing unsaturated monomer is mixed with a vinyl hydrophilic polymer and / or polyacetal has a vinyl hydrophilic polymer or polyacetal. It has both excellent physical properties such as film-forming properties and chemical resistance, which are inherent, and excellent conductivity of the homopolymer of an unsaturated monomer containing a phosphorus acid residue.

  As the vinyl hydrophilic polymer, polyvinyl alcohol is preferable. Polyvinyl alcohol has an effect of improving the conductivity of the conductive resin composition. When using polyvinyl alcohol, the degree of polymerization, melting point, degree of saponification, etc. are taken into consideration as appropriate, and those selected as necessary are selected. When preparing a conductive resin composition using polyvinyl alcohol, it is preferable to add a polyamide resin or a melamine resin in order to have water resistance. As the polyamide resin, N-alkoxyalkylated polyamides described in JP-A No. 2003-138088 are preferable.

  If necessary, the conductive resin composition of the present invention may be blended with other lower alcohol-soluble polymer, hydrophilic polymer, a small amount of water-absorbing polymer, rubber or the like. Examples of other lower alcohol-soluble polymers include water-soluble urethane. Examples of other hydrophilic polymers include polyacrylamide, polyacrylic acid, cellulose, and modified products thereof.

  Ratio of phosphoric acid residue-containing unsaturated monomer homopolymer to other resin (resin mainly composed of vinyl hydrophilic polymer and / or polyacetal) [(phosphorus acid residue-containing unsaturated monomer) Body homopolymer) / (other resin)] is preferably in the range of 0.05 to 5, more preferably 0.1 to 1, on a solids weight basis. If the ratio exceeds 5, it becomes difficult to form a film. On the other hand, if it is less than 0.05, the conductivity is insufficient. Moreover, it is preferable that the resin solid content concentration of the polymer solution when preparing the conductive resin composition is 5 to 30% by weight. Thereby, a uniform and highly transparent polymer solution is obtained.

By heating the polymer solution to evaporate and remove the solvent, and then heating to 100 to 140 ° C., a conductive resin composition that is a solid homogeneous composition is obtained. The conductive resin composition of the present invention thus obtained is a uniform composition having flexibility and transparency. The surface specific resistance of the conductive resin composition of the present invention is 10 ⁵ to 10 ¹¹ Ω · cm under the condition of relative humidity 50 to 75% / room temperature, particularly 10 ⁵ under the condition of relative humidity 75% / room temperature. It is ˜10 ⁷ Ω · cm, which is superior to the surface specific resistance value of a standard conductive resin composition. Furthermore, the conductive resin composition of the present invention is excellent in water resistance, chemical resistance and adhesion to various substrates. The conductive resin composition of the present invention having such characteristics is useful as a conductive resin composition for a bioelectrode that is interposed between the skin and the electrode element when the bioelectrode is mounted. In addition, since the conductive resin composition of this invention contains the phosphorus atom, it is excellent also regarding the flame retardance and the dispersibility of an inorganic filler.

  A cast film is mentioned as an example of the molded object which consists of the conductive resin composition of this invention. The cast film is obtained, for example, by casting a polymer solution on a substrate such as a glass plate installed horizontally, evaporating the solvent, and then heating to 100 to 140 ° C. The thickness of the cast film is usually 30 to 500 μm, preferably about 50 to 200 μm. The mechanical strength can be increased by further stretching the cast film thus formed. Stretching preferably involves heating.

[6] Coating Agent The coating agent of the present invention contains the phosphoric acid residue-containing unsaturated monomer homopolymer solution described in [4] above. The coating agent of the present invention preferably contains a hydrophilic polymer and / or a lower alcohol-soluble polymer. As the hydrophilic polymer, a vinyl-based hydrophilic polymer is preferable, and the above-described polyvinyl alcohol is more preferable. Polyacetal is preferred as the lower alcohol-soluble polymer. When adding polyvinyl alcohol, it is also preferable to add a polyamide resin or a melamine resin. As the polyamide resin, the N-alkoxyalkylated polyamide is preferable. Ratio of phosphoric acid residue-containing unsaturated monomer homopolymer to other resin (resin mainly composed of hydrophilic polymer and / or lower alcohol-soluble polymer) [(phosphoric acid residue-containing Saturated monomer homopolymer) / (other resin)] is preferably in the range of 0.05 to 5, more preferably 0.1 to 1, on a solids weight basis. The coating agent of the present invention may be blended with other lower alcohol-soluble polymer, hydrophilic polymer, a small amount of water-absorbing polymer, rubber, etc., as in the case of the conductive resin composition described above. .

  When using the coating agent, it is preferable to dilute the coating agent to a concentration suitable for coating using a good solvent. As the good solvent, the same aliphatic lower alcohol used in the reaction is preferable. The coating agent of the present invention includes the following additives used in ordinary coating agents, such as viscosity modifiers (for example, thickeners), various coloring pigments for beautifying purposes, fillers for increasing hiding power, Leveling agent added for the purpose of improving smoothness, coupling agent added for the purpose of improving adhesion to the substrate, conventionally known antioxidants, lubricants, anti-blocking agents, anti-aging agents, difficulty A flame retardant, a conductive agent, an antifoaming agent and the like can be arbitrarily selected and added.

The antistatic property or electroconductivity can be provided by apply | coating the coating agent of this invention with respect to a to-be-coated article so that it may become 1-10 g / m < ² > on solid content basis, and forming a coating film by heating. As a method for applying to the substrate surface, there is a method of coating or dipping the substrate surface by brush coating, bar coater coating, spraying, dipping, roll coating, blade coating, flow coating or electrostatic coating. The coating agent of the present invention can be applied to any of a metal plate, a plastic molding, a sheet or film, a fiber, a woven fabric or a non-woven fabric, and is in close contact with the surface thereof.
The coating film obtained by curing the coating agent of the present invention is excellent in adhesion to a substrate, solvent resistance, water resistance, hardness, gloss, weather resistance, rust resistance, and the like.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
To an automatic synthesis reactor (internal volume 500 mL, manufactured by Unichemical Co., Ltd.) connected with a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet tube, 30 g of Phosmer M (acid phosphooxyethyl methacrylate), and Methanol / water solvent [mass ratio: methanol / water = 99/1] 255 g was added and stirred at 140 to 150 rpm while introducing nitrogen gas, and the temperature was raised to a polymerization temperature of 63 ° C. After confirming that the internal temperature reached 63 ° C., 0.15 g of 2,2′-azobisisobutyronitrile (AIBN) dissolved in 5 g of the solvent having the same composition as the charged solvent was added. At this time, a slight polymerization exotherm occurred and the start of polymerization was confirmed. Two hours and three hours after the internal temperature reached 63 ° C, 0.1 g of AIBN dissolved in 5 g of the same composition as the charged solvent was added to polymerize the residual monomer for about 1 hour. As a result, a solution of a homopolymer of Phosmer M was obtained.

Comparative Examples 1 and 2
Phosmer M was solution polymerized in the same manner as in Example 1 except that the amount and composition of the solvent were as shown in Table 3.

Example 2
A solution of each homopolymer was prepared in the same manner as in Example 1 except that ethanol / water solvent [mass ratio: ethanol / water = 95/5] was used as the solvent.

Comparative Examples 3-5
Phosmer M was solution polymerized in the same manner as in Example 2 except that the amount and composition of the solvent shown in Table 4 were used.

Examples 3 and 4
A solution of each homopolymer was prepared in the same manner as in Example 1 except that an isopropanol / water solvent having the composition shown in Table 5 was used as the solvent.

Comparative Examples 6-9
Phosmer M was solution polymerized in the same manner as in Examples 3 and 4 except that the amount and composition of the solvent were as shown in Table 5.

Examples 5-7
The same procedure as in Example 1 was conducted except that Phosmer PE (acid phosphooxypolyoxyethylene glycol monomethacrylate) was used as the phosphoric acid residue-containing unsaturated monomer, and a methanol / water solvent having the composition shown in Table 6 was used. A solution of each homopolymer was prepared.

Comparative Examples 10-13
Phosmer PE was solution polymerized in the same manner as in Examples 5 to 7 except that the amount and composition of the solvent were as shown in Table 6.

Examples 8-12
The same procedure as in Example 1 was conducted except that Phosmer PE (acid phosphooxypolyoxyethylene glycol monomethacrylate) was used as the phosphoric acid residue-containing unsaturated monomer and an ethanol / water solvent having the composition shown in Table 7 was used. A solution of each homopolymer was prepared.

Comparative Examples 14-20
Phosmer PE was solution polymerized in the same manner as in Examples 8 to 12 except that the amount and composition of the solvent were as shown in Table 7.

Examples 13 and 14
As in Example 1, except that Phosmer PE (acid phosphooxypolyoxyethylene glycol monomethacrylate) was used as the phosphoric acid residue-containing unsaturated monomer and an isopropanol / water solvent having the composition shown in Table 8 was used. A solution of each homopolymer was prepared.

Comparative Examples 21-24
Phosmer PE was solution polymerized in the same manner as in Examples 13 and 14 except that the amount and composition of the solvent were as shown in Table 8.

  The gelled state immediately after completion of the polymerization reaction of each solution obtained in Examples 1-14 and Comparative Examples 1-24, and each solution obtained in Examples 1-14 and Comparative Examples 1-24 sealed in a sample bottle Then, the gelation state after storage for 6 months at 5 ° C. and room temperature was examined. The gelled state was determined by visually examining the fluidity when the sample bottle sealed with each solution was inverted. The results are shown in Tables 3-8. Symbols indicating the judgment criteria indicate ◯: “good” and x: “no fluidity”, respectively.

Examples 15 and 16
The 10.5 mass% solution of the Phosmer M homopolymer of Example 1 and a 10 mass% aqueous solution of polyvinyl alcohol (trade name “Poval RS-2113”, manufactured by Kuraray Co., Ltd.) are mixed in the solid content shown in Table 9. The polymer solution was prepared by mixing according to the ratio. The obtained polymer solution is cast into a container (bottom surface: 10 cm × 10 cm) made of a polypropylene film, placed in an air circulation dryer, and heated from room temperature to 50 ° C. for about 12 hours. Dried. The formed film was peeled off with a spatula, and this was heat-treated at 130 ° C. for 3 minutes with a high-temperature air circulation dryer to produce a conductive resin film having a thickness of 100 μm.

Examples 17, 18
10.5% by weight solution of Phosmer M homopolymer of Example 1, 10% by weight aqueous solution of Poval RS-2113, trimethoxymethylmelamine (trade name “Smitex Resin M-3”, manufactured by Sumitomo Chemical Co., Ltd.) A conductive resin film was prepared in the same manner as in Example 15 except that a polymer solution was prepared by mixing an 80% by weight aqueous solution of

Examples 19-21
Except that a polymer solution was prepared by mixing a 10.5 mass% solution of the Phosmer PE homopolymer of Example 5 and a 10 mass% aqueous solution of Poval RS-2113 in accordance with the solid content ratio shown in Table 10. In the same manner as in Example 15, a conductive resin film was produced.

Examples 22-24
10.5 mass% solution of Phosmer PE homopolymer of Example 5, 10 mass% aqueous solution of Poval RS-2113, and 80 mass% aqueous solution of Sumtex Resin M-3 A conductive resin film was produced in the same manner as in Example 15, except that a polymer solution was prepared by mixing according to the procedure described in Example 15.

Comparative Example 25
A conductive resin film was produced in the same manner as in Example 15 except that only a 10% by mass aqueous solution of Poval RS-2113 was used.

Comparative Example 26
Example 15 with the exception that a polymer solution was prepared by mixing a 10% by weight aqueous solution of Poval RS-2113 and an 80% by weight aqueous solution of Smitex Resin M-3 according to the blending ratio of the solids shown in Table 12. Similarly, a conductive resin film was produced.

  The physical properties of the conductive resin films produced in Examples 15 to 24 and Comparative Examples 25 and 26 were measured by the following methods. The results are shown in Tables 9-12.

(1) Appearance: Transparency was evaluated visually. Symbols indicating the judgment criteria indicate ◎: “colorless and transparent”, ○: “slightly cloudy”, and Δ: “whitening or cloudiness”, respectively.
(2) Tackiness: The conductive resin film was allowed to stand for more than half a day at a temperature of 20 ° C. and a relative humidity of 50%, touched with a finger, and judged by its tactile feel. Symbols indicating the determination criteria indicate ◎: “none”, ◯: “slightly sticky”, and Δ: “obviously sticky”, respectively.
(3) Flexibility: A conductive resin film cut out to a size of 10 cm ² was allowed to stand for at least half a day at a temperature of 20 ° C. and a relative humidity of 50%, and then evaluated when folded in half ( 180 ℃ bending test). Symbols indicating the judgment criteria indicate ◎: “particularly good” and ◯: “good”, respectively.
(4) Water resistance: A 1 cm long x 4 cm wide strip sample was cut out, and the vertical x horizontal area was measured and used as a reference. This was immersed in water at room temperature, taken out after 30 minutes and 2 days, the length and width were measured, the area of the length and width was calculated, and the swelling ratio was obtained. The state after 2 days was evaluated visually. The symbols indicating the judgment criteria are ◎: “colorless and transparent”, ○: “slightly cloudy”, and Δ: “whitening or cloudiness”, respectively.
(5) Methanol resistance: A strip sample measuring 1 cm in length × 4 cm in width was cut out, and the area in the length and width was measured and used as a reference. This was immersed in methanol at room temperature, taken out after 30 minutes and 2 days, the length and width were measured, the area of the length and width was calculated, and the swelling ratio was obtained. The state after 2 days was evaluated visually. The symbols indicating the judgment criteria are ◎: “colorless and transparent”, ○: “slightly cloudy”, and Δ: “whitening or cloudiness”, respectively.
(6) Surface resistivity: RH 50% / 22 ° C. (Examples 15 to 18 and Comparative Examples 25 and 26), RH 50% / with a surface resistivity meter (SME-8310, manufactured by Toa Denpa Kogyo Co., Ltd.) 20 ° C. (Examples 19 to 24), RH 65% / 19 ° C. (Examples 15 to 24 and Comparative Examples 25 and 26), RH 75% / 19 ° C. (Examples 15 to 18 and Comparative Examples 25 and 26), And RH 72% / 19 ° C. (Examples 19 to 24).

  As shown in Tables 3-8, according to the solution polymerization method of the present invention, it is possible to produce a polymer composed only of a phosphoric acid residue-containing unsaturated monomer without gelation. The obtained homopolymer solution is excellent in long-term storage stability. On the other hand, in Comparative Examples 1 to 24, the polymerization solution concentration or the solvent composition was outside the scope of the present invention, and thus gelled by long-term storage.

As shown in Tables 9 to 12, the film made of the conductive resin composition of the present invention is excellent in transparency and flexibility and has little or no tackiness. Although the conductive resin film of the present invention swells or is slightly clouded or whitened by immersion in water or methanol, it does not dissolve and is at a level that is not problematic in practice. Regarding the surface resistivity, the conductive resin film of the present invention exhibits 10 ⁸ to 10 ¹¹ Ω · cm in the measurement of RH 50% / 20 to 22 ° C., and 10 ⁵ to 10 in the measurement of RH 65% / 19 ° C. ⁹ Ω · cm was measured, and the measurement at RH 72 to 75% / 19 ° C. showed 10 ⁵ to 10 ⁷ Ω · cm, both of which were superior to the surface specific resistance value of the standard conductive resin composition. On the other hand, since the films of Comparative Examples 25 and 26 do not contain the phosphoric acid residue-containing unsaturated monomer homopolymer of the present invention, they are generally 3 to 4 orders of magnitude higher than the conductive resin films of Examples. The surface resistivity was shown. As described above, the surface specific resistance value of the conductive resin that has been conventionally used can be obtained only by including about 20% by mass of the phosphoric acid residue-containing unsaturated monomer homopolymer of the present invention with respect to the entire resin composition. Can be lowered by about three orders of magnitude.

Claims (13)

Only the phosphoric acid residue-containing unsaturated monomer having at least one phosphorus acid residue and one or more ethylenically unsaturated bonds in the molecule is polymerized in a solvent to form the phosphoric acid residue. A method for producing a coating agent comprising a solution containing a homopolymer of an unsaturated monomer containing, as the solvent, using methanol containing 1 to 20% by mass of water as a whole solvent of 100% by mass, Obtained after polymerizing the phosphoric acid residue-containing unsaturated monomer by setting the concentration of the phosphoric acid residue-containing unsaturated monomer to 14 mass% or less with 100% by mass of the entire polymerization solution. A method characterized in that the polymer solution is left unpurified. The method for producing a coating agent according to claim 1, wherein the water content of the solvent composed of methanol and water is 1 to 15% by mass. Only the phosphoric acid residue-containing unsaturated monomer having at least one phosphorus acid residue and one or more ethylenically unsaturated bonds in the molecule is polymerized in a solvent to form the phosphoric acid residue. A method for producing a coating agent comprising a solution containing a homopolymer of an unsaturated monomer containing, using as the solvent, ethanol containing 3 to 30% by mass of water as 100% by mass of the whole solvent, Obtained after polymerizing the phosphoric acid residue-containing unsaturated monomer by setting the concentration of the phosphoric acid residue-containing unsaturated monomer to 14 mass% or less with 100% by mass of the entire polymerization solution. A method characterized in that the polymer solution is left unpurified. 4. The method for producing a coating agent according to claim 3, wherein the water content of the solvent composed of ethanol and water is 5 to 30% by mass. Only the phosphoric acid residue-containing unsaturated monomer having at least one phosphorus acid residue and one or more ethylenically unsaturated bonds in the molecule is polymerized in a solvent to form the phosphoric acid residue. A method for producing a coating agent comprising a solution containing a homopolymer of an unsaturated monomer containing isopropyl alcohol containing 10 to 30% by mass of water with the total amount of the solvent being 100% by mass. Obtained by polymerizing the phosphoric acid residue-containing unsaturated monomer by setting the concentration of the phosphoric acid residue-containing unsaturated monomer to 14 mass% or less with the entire polymerization solution being 100 mass%. And leaving the polymer solution unpurified. 6. The method for producing a coating agent according to claim 5, wherein the water content of the solvent comprising isopropyl alcohol and water is 15 to 25% by mass. In the manufacturing method of the coating agent in any one of Claims 1-6, the said phosphorus acid residue containing unsaturated monomer is following formula (1);

(Wherein R ₁ represents a hydrogen group or an alkyl group, X represents an —O— group or —NH— group, Y ₁ represents a divalent hydrocarbon group which may contain an —O— group, and Z represents phosphorus. An acid residue, a phosphonic acid residue, a phosphinic acid residue or a diphosphoric acid residue.). In the manufacturing method of the coating agent in any one of Claims 1-7, the said phosphorus acid residue containing unsaturated monomer is following formula (2);

(Wherein R ₁ represents a hydrogen group or an alkyl group, Y ₂ represents an oxyalkylene group or alkylene group having 2 to 20 carbon atoms, and n is an integer of 1 to 10). how to. In the manufacturing method of the coating agent in any one of Claims 1-8, the said phosphorus acid residue containing unsaturated monomer is following formula (3);

(Wherein R ₁ is a hydrogen group or an alkyl group, R ₂ is a hydrogen group or a substituted or unsubstituted alkyl group, and m is an integer of 1 to 6). . In the manufacturing method of the coating agent in any one of Claims 1-9, after preparing the said phosphoric acid residue containing unsaturated monomer homopolymer, vinyl-type hydrophilic polymer and / or polyacetal are added. A method characterized by: 11. The method for producing a coating agent according to claim 10, wherein polyvinyl alcohol is used as the vinyl hydrophilic polymer. 12. The method for producing a coating agent according to claim 11, wherein a polyamide resin or a melamine resin is also added together with the polyvinyl alcohol. 13. The method for producing a coating agent according to claim 12, wherein trimethoxymethylmelamine is used as the melamine resin.