JPH02136285A - Conductivity treating agent for thermal recording paper - Google Patents

Abstract

PURPOSE:To enhance preservation stability and prevent corrosion of a head by using as an effective constituent a polymer in which a group of an alkanolamine salt of an aromatic sulfonic acid or the like is contained as a building block of a polymeric chain of an ethylenically unsaturated monomer. CONSTITUTION:A conductivity treating agent for a thermal recording paper is prepared by using as an effective constituent a polymer in which a group of an alkanolamine salt of an aromatic sulfonic acid and/or an alkanolamine salt of an aromatic sulfate is contained as at least part of building blocks of a polymeric chain of an ethylenically unsaturated monomer. It is recommendable that at least 50mol%, preferably at least 70mol%, of the building blocks of the polymeric chain of the polymer comprise aromatic sulfonic acid groups and/or aromatic sulfate groups. The amount of the conductivity treating agent applied to the thermal recording paper, calculated as the effective constituent, is preferably 0.1-10g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a conductive treatment agent for thermal paper, and more particularly to a conductive treatment agent for thermal paper that does not discolor the thermal paper during storage.

Conventional Technologies and Issues] Conventionally, conductive treatment has not been applied to thermal paper for boat fishing.

However, in recent years, the proportion of parts used in thermal recording devices using synthetic resin has been increasing year by year in order to reduce weight and cost in the manufacturing of thermal recording devices. Clinging is becoming a problem.

In order to solve this problem, conventionally known conductive treatment agents, such as various inorganic salts such as common salt, various polyamine hydrochlorides,
Attempts have been made to add polyquaternary ammonium salts (for example, polyvinylbenzyltrimethylammonium chloride), alkali metal and alkaline earth metal salts of polystyrene sulfonic acids, but these salts have been used in facsimiles, which are the main uses of thermal paper. This was not practical for use with thermal paper because it could cause corrosion of the recording head material.

To solve this drawback, it is effective to use ammonium salts of polystyrene sulfonic acids, but ammonium salts of polystyrene sulfonic acids accelerate the reaction of color developers and dyes in thermal paper at low temperatures. There is a problem in that the thermal paper develops color and the entire thermal paper turns black or gray during storage.

Therefore, an object of the present invention is to provide a conductive treatment agent for thermal paper which does not corrode the bed of facsimile machines and has excellent storage stability.

[Means for Solving the Problems] The present inventors completed the present invention as a result of intensive research in view of the above problems.

That is, the present invention effectively uses a polymer containing an alkanolamine salt of an aromatic sulfonic acid and/or an alkanolamine salt of an aromatic sulfuric acid ester as at least a part of the constituent units of the polymer chain of an ethylenically unsaturated monomer. Concerning a conductive treatment agent for thermal paper as a component.

[Function] The active ingredient used in the conductive treatment agent for thermal paper of the present invention is a monomer polymer containing an ethylenic double bond and an aromatic sulfonic acid group and/or an aromatic sulfuric acid ester group in the molecule. A copolymer with a monomer having an ethylenic double bond that can be polymerized or copolymerized with this monomer, or a polymer of a monomer containing an ethylenic double bond and an aromatic group in the molecule; Alkanolamine salts of aromatic sulfonated products or aromatic sulfate esterified products of copolymers with monomers having ethylenic double bonds that can be copolymerized with monomers, or copolymers with ethylenic double bonds in the molecule. bond, and a polymer of a monomer containing an aromatic sulfonate alkanolamine group and/or an aromatic sulfate alkanolamine group or a monomer having an ethylenic double bond copolymerizable with this monomer. A copolymer can be used.

Examples of monomers containing an ethylenic double bond and an aromatic sulfonic acid group in the molecule used in the present invention include styrene sulfonic acid, α-methylstyrene sulfonic acid, alkylated styrene sulfonic acid, alkoxylated styrene sulfonic acid, Examples of monomers containing an ethylenic double bond and an aromatic sulfuric acid ester group in the molecule include vinylnaphthalene sulfonic acid, vinylnaphthalene sulfonic acid ester, vinylnaphthol vi acid ester, etc. The invention is not limited to these examples.

Monomers containing an ethylenic double bond and an aromatic sulfonic acid group and/or an aromatic sulfate group in the molecule or an ethylenic double bond and an aromatic sulfone in the molecule that can be used in the present invention Monomers having an ethylenic double bond that can be copolymerized with a monomer containing an acid alkanolamine group and/or an aromatic sulfuric acid ester alkanolamine group include, but are not limited to, examples include ethylene, propylene, and acetic acid. Examples include vinyl, (meth)acrylic acid, esters of (meth)acrylic acid, styrene, maleic acid, and vinylsulfonic acid.

In addition, in the case of sulfonation or sulfate esterification after polymerization, unsulfonated or unsulfated esterified monomers corresponding to the above can be used, and when using monomers containing alkanolamine groups as the monomers. Alkanolamine salt monomers corresponding to those described above can also be used.

In the present invention, preferably at least 50 mol%, more preferably 70 mol% or more of the structural units of the polymer chain contain an aromatic sulfonic acid group and/or an aromatic sulfate group.

In addition, when the sulfonation rate or the sulfuric acid esterification rate is carried out after polymerization, the sulfonation rate or the sulfuric acid esterification rate is preferably 50%, more preferably 70% or more.

In the present invention, it is not necessary to use a sulfonated or sulfuric acid esterified monomer,
Sulfonation or sulfuric acid esterification may be performed after polymerization, and in these cases, various known sulfonation or sulfuric acid esterification methods can be used for -m.

Further, in the present invention, it is not necessarily necessary to add an alkanolamine salt after polymerization, and a monomer that is an alkanolamine salt can be used.

The alkanolamines used in the present invention are not particularly limited, but are preferably represented by the following formula (1) (wherein R' is hydrogen, or may be saturated or unsaturated and has 1 to 18 carbon atoms). It is a branched, straight-chain or cyclic aliphatic group, or an aromatic group, and R2 has 1 to 18 carbon atoms.
, preferably 2 to 8, more preferably 2 to 3 saturated or unsaturated aliphatic groups that may be linear or branched, and may be the same or different groups, n is 0, 1 or 2
Preferred examples include alkanolamines represented by the following formulas: monoethanolamine, jetanolamine, triethanolamine, isopropanolamine, methylethanolamine, diethylethanolamine, and the like.

In the present invention, an ethylenic double bond in the molecule,
and a polymer of a monomer containing an aromatic sulfonic acid group and/or an aromatic sulfuric acid ester group, or a copolymer with a monomer having an ethylenic double bond that can be copolymerized with this monomer,
Alternatively, a heavy polymer containing an ethylenic double bond and an aromatic group in the molecule or an aromatic sulfone 1 of a copolymer with a monomer having an ethylenic double bond copolymerizable with this monomer At least the alkanolamine salts or the corresponding alkanolamine salt monomer polymers are used as alkanolamine salts or aromatic sulfate esters, but other bases may be used within the scope of the present invention. For example, ammonia, various amines, etc. can also be used in combination.

However, in this case, preferably the alkanolamine is 5
The content is preferably 0 mol% or more, more preferably 70 mol% or more.

In the present invention, the above-mentioned alkanolamine etc.
A polymer of monomers containing an ethylenic double bond and an aromatic sulfonic acid group and/or an aromatic sulfuric acid ester group in the above molecule, or an ethylenic double bond that can be copolymerized with this monomer. A copolymer with a monomer or a polymer of a monomer containing an ethylene double bond and an aromatic group in the molecule, or a monomer having an ethylenic double bond that can be copolymerized with this monomer. It is not necessary to neutralize 100% of the aromatic sulfonated product or aromatic sulfate esterified product of the copolymer with the copolymer. It is sufficient that more than the type, more preferably 0.7 equivalent or more, is neutralized, and there is no problem even if the base is in excess.

In addition, when using heavy bodies containing an ethylenic double bond and an aromatic sulfonic acid alkanolamine group and/or an aromatic sulfuric acid ester alkanolamine group in the molecule, these heavy bodies must be 100% neutralized. Preferably, 0.5 equivalent or more, more preferably 0.7 equivalent or more per aromatic sulfonic acid group and 7/or aromatic sulfate group should be neutralized, and it is sufficient to neutralize the base. There is no problem even if it is.

The molecular weight of the above-mentioned active ingredient in the present invention is not particularly limited, but is approximately 1.000 to 1.000.000.
'L is fine.

In the present invention, other additives may be used in combination as necessary without departing from the purpose of the present invention, and in general, various water-soluble polymers (starch, poval, etc.) may be used in combination, carbonic acid Various pigments such as calcium can be used in combination as desired. Further, additives such as a water resistance agent and a sizing agent may also be used in combination.

The amount of the conductive treatment agent for thermal paper of the present invention to be used in thermal paper is not particularly limited, but preferably from 0.1 to 0.1 as an active ingredient.
10 g/m2, more preferably 0.5 to 7 g/m2.

EXAMPLES] The present invention will be further explained with reference to Examples below, but it should be understood that the present invention is not limited thereto.

Example 1 - Conductivity, discoloration, and corrosivity were tested using the following conductive treatment agent for thermal paper of the present invention and a conductive treatment agent for comparison. The results are shown in Table 1.

Conductive agent 1: Polystyrene sulfonic acid monoethanolamine salt (molecular weight: 10,000) Conductive agent 2: Polymer of polystyrene sulfonic acid jetanolamine salt (molecular weight: to, ooo) Conductive agent 3: Polystyrene sulfonic acid triethanolamine salt (Molecular weight 3,000) Conductive agent 4: Poly-α-methylstyrene sulfonic acid monoethanolamine salt (molecular weight too, ooo) Conductive agent 5: Poly-p-vinylphenol sulfate ester monoethanolamine salt (molecular weight too, ooo) 50.000) Conductive agent 6: Styrene sulfonic acid/ethylene (molar ratio 7/
3) Copolymer monoethanolamine salt (molecular weight 10,
000) Conductive agent 7: Styrene sulfonic acid/ethylene (molar ratio 7/
3) Copolymer monoethanolamine salt (molecular weight 150
,000) Conductive agent 8: Monoethanolamine salt of sulfonated polystyrene (sulfonation rate 80%) (molecular weight 10,0%)
00) Comparative conductive agent 1: polystyrene sulfonate ammonium salt (molecular weight 10,000) Comparative conductive agent 2 niboristyrene sulfonate diethylamine salt (molecular weight 10,000) Comparative conductive agent 3: polystyrene sulfonate sodium salt (
Molecular weight: 10,000 It was coated using a coater and the conductivity after drying was measured.

Measurement 1! 1: Digital electrometer TR8652 manufactured by Advantest Co., Ltd. Voltage 10V Measurement conditions = 20°C, humidity 452≦ Coating m: 4, 3 g, 'In2 light order: 1-tube 1 Commercially available thermal paper was conductive. Immerse in a 5% pure solution and heat at 70°C.
The paper was left in a constant temperature bath for 1 hour, and the paper surface was then observed for discoloration (blackening).

The aluminum test plate of the facsimile ped was immersed in a 1% conductive agent solution at 95°C.
After being left in an atmosphere for one month, the surface condition was observed.

No. 1 - [Effects of the Invention] The conductive treatment agent for heat-sensitive paper of the present invention does not cause corrosion of facsimile heads and has excellent storage stability.

Patent applicant: Asahi Denka Kogyo Co., Ltd. -Ichino Procedural amendment August 18, 1999

Claims (1)

[Claims] A thermal paper containing as an active ingredient a polymer containing an alkanolamine salt of an aromatic sulfonic acid and/or an alkanolamine salt of an aromatic sulfuric acid ester as at least a part of the constituent units of the polymer chain of an ethylenically unsaturated monomer. conductive treatment agent.