JPH039368A - Recording material for laser beam printer - Google Patents

Abstract

PURPOSE:To improve dimensional stability and antistatic effect by using paper coated with a sulfonic acid (sulfonate)- contg. polymer as the recording paper to be used. CONSTITUTION:This recording material consists of the paper coated with the sulfonic acid (sulfonate)-contg. polymer. The sulfonic acid-contg. polymer is a water dispersible or water soluble polymer and is exemplified by the polymer or copolymer contg. the sulfonide of polystyrenes and/or the salt thereof as well as the monomers selected from the group consisting of arom. hydrocarbon vinyl sulfonic acid, sulfonic acid group-contg. (meth)acrylamide, sulfonic acid group-comtg. (meth)acrylate, aliphat. hydrocarbon vinyl surfonic acid, and the salts thereof. The polymer is more preferably the salt of the sulfonide of the polystyrenes. The less elongation and contraction of the paper by moisture, the excellent dimensional stability, the small specific surface resistance value and the excellent antistatic effect are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to recording materials for laser, vino, and printers. More specifically, it relates to 1) - Zerbino and printer recording materials that do not cause paper feeding troubles.

[Prior Art] In recent years, a method of recording using a laser beam printer has become popular in the field of facsimile. The recording paper used for this purpose is doped with sodium chloride, sulfuric acid, etc. to prevent static electricity by +1. An I-quality paper has been proposed.

[Problems to be Solved by the Invention] However, these have little antistatic effect in low humidity applications, and also have large expansion and contraction due to humidity. Because there is not enough stable bamboo, often when receiving paper! This may cause problems such as soot.

[! ! I! Means for Solving the Problem] The inventors of the present invention have studied recording materials for continuous norther beam printers that solve the above problem, and as a result, they have arrived at the present invention.

That is, the present invention is a laser beam printer recording material comprising paper coated with a polymer containing sulfonic acid (salt) groups. Hereinafter, the sulfonic acid it-containing polymer will be abbreviated as a sulfonic acid group-containing polymer.

In the present invention, the sulfonic acid group-containing polymer is a water-dispersible or water-soluble polymer, including sulfonated polystyrenes and/or salts thereof, aromatic hydrocarbon vinyl sulfonic acid, sulfonic acid group-containing (meth) ) Acrylamide, sulfonic acid group-containing (meth)acrylate, aliphatic hydrocarbon vinyl sulfonic acid, and salts thereof. Preferred are salts of sulfonated polystyrenes.

Specifically, the following sulfonic acid group-containing polymers may be mentioned.

(A) Sulfonated polystyrenes Polystyrenes include styrene, α-methylstyrene, α
- Includes homopolymers of styrenes such as ethylstyrene and copolymers of styrenes and w-mers copolymerized therewith.

The fil vessels copolymerized with styrenes include (meth)acrylic acid alkyl esters [methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid-2-J (prohexyl, stearyl (meth)acrylate, etc.), fatty acid vinyl [vinyl acetate, etc.], aromatic hydrocarbon vinyl monomers [vinylnaphthalene, vinyltoluene, p-methylstyrene, etc.], full carboxylic acid or Its anhydrides [(meth)acrylic acid, maleic anhydride, itaconic anhydride, etc.], olefins [α-olefin, isoprene, isobutylene, diisobutylene, butadiene, chlorobrene, etc.], nitrile group-containing vinyl monomers [( (meth)acrylonitrile, etc.].

The styrene content of the styrene copolymer is 30,000%
The above amount is preferably 50 mol% or more.

The molecule m of polystyrenes is usually 500 to i, ooo,
.

OO1 is preferably 2.000 to 500,000, more preferably 3.000 to ioo, ooo.

The sulfonated product can be produced by a known method using a conventional sulfonating agent in a solvent.

As the solvent, those inert to the sulfonating agent are usually used, such as aliphatic halogenated hydrocarbons having 1 to 2 carbon atoms and nitrated aliphatic hydrocarbons having 1 to 3 carbon atoms.

Specific examples of aliphatic halogenated hydrocarbons include 1.2-
Dichloroethane, methylene dichloride, ethyl chloride, carbon tetrachloride, 1. I-dichloroethane, 1. I, 2I2-
Examples include tetrachloroethane, chloromethane, and J ethylene dibromide. Examples of diI-1 aliphatic hydrocarbons include nitromethane, nitroethane, l-nitropropane, 2. - Nitropropane is reduced. Preferred are aliphatic halogenated hydrocarbons.

The dissolution of polystyrenes depends on the molecular weight of the polymer, but the amount of polystyrenes is usually 1 to 1% per part by weight of dissolved Bio.
100mmff1, better, 5-50In m K
Dissolve.

As the sulfonating agent, sulfuric anhydride, chlorosulfuric acid, etc. are used. Preferred is sulfuric anhydride.

Liquid sulfuric anhydride, liquid sulfuric anhydride mixed with an inert gas such as nitrogen φ dry air, and a solvent inert to the sulfonating agent such as an aliphatic halogenated hydrocarbon having 1 to 2 carbon atoms such as 1,2-dichloroethane or ethyl chloride. Anhydrous sulfuric acid diluted with The concentration of sulfuric anhydride diluted with inert gas is usually 1 to 1.
15% by volume, preferably 3-5% by volume. Concentration of anhydrous sulfuric acid diluted with an inert solvent, usually 1 to 50% by weight,
Preferably t I, < LL 5” 20:) If Ja%.

Moreover, a complex of sulfuric anhydride and Lewis base can also be used. Examples of Lewis bases include trialkyl phosphates such as triethyl phosphate and trimethyl phosphate, fatty acid alkyl esters such as ethyl acetate and ethyl valmitate, and ethers or thioethers such as dioxane, thioxane and diethyl ether. Preferred Lewis bases are trialkyl phosphates and fatty acid alkyl esters.

The amount of the sulfonating agent used is usually 0.4 to 2 moles per mole of styrene units in the polystyrene.

The sulfonation reaction is usually carried out at 0 to 80°C, preferably at I
It is carried out at 0 to 50°C and under anhydrous conditions.

Sulfonates are typically hydroxides, carbonates, or ammonia, such as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium,
It is neutralized with a neutralizing agent such as amines, such as alkylamines such as triethylamine, dimethylamine, laurylamine, and stearylamine, and alkanolamines such as monoethanolamine and jetanolamine.

Preferred are sodium salts, potassium salts, and ammonium salts.

The solvent is removed by conventional methods such as branching, filtration, and distillation to obtain a water-dispersible or water-soluble aqueous liquid or powdered sulfonic acid (salt) group-containing polymer.

Patent application No. 1-1 for which the present applicant has applied for a patent for a method other than the above-mentioned method.
Specification No. 8111i9 (Method of Y, dated May 8, 1989, title of the invention ``Method for sulfonating octaroaromatic polymers'' and dated May 8, 1989, title of the invention ``Method of sulfonated polymer aqueous polymers'') Sulponization can also be carried out by the "Production method".

(B) Heavy polymers of sulfonic acid group-containing monomers Examples of polymers of sulfonic acid group-containing monomers include aromatic nuclear hydrocarbon purple vinyl sulfonic acid, sulfonic acid group-containing (meth)acrylamide, and sulfonic acid group-containing (meth)acrylamide; Examples include polymers or copolymers whose essential constituent units are monomers selected from the group consisting of meth)acrylates, aliphatic hydrocarbon vinyl sulfonic acids, and salts thereof. Preferably, it is a polymer or copolymer containing a sulfonic acid group-containing monomer as an essential structural unit. Examples of the sulfonic acid (salt) group-containing monomer include the following monomer.

(B-1) Aromatic hydrocarbon vinylsulfonic acid P- and 0-styrenesulfonic acid, styrene disulfonic acid, α-
Methylstyrenesulfonic acid, vinylphenylmethanesulfonic acid, etc. and their salts (B-2) Sulfonic acid group-containing (meth)acrylamide 2-(meth)acrylamide-2-methylpropane sulfone M, 3-(meth)acrylamide propane -1-sulfone &, 2-(meth)acrylamidoethyl-1-sulfonic acid, 3-(meth)acrylamido-2-hydroxypropanesulfone M, P-(meth)acrylamidomethylbenzenesulfonic acid, etc. and salts thereof (B -3) Sulfonic acid group-containing (meth)acrylate 3-(meth)acryloyloxypropane sulfonic acid, 4-(meth)acryloyloxybutane-1-sulfonic acid, 4-(meth)acryloyloxybutane-2 -Sulfone fiQ, 2-(meth)acryloyloxyethyl-1-sulfonic acid, 3-(meth)acryloyloxy-2-L droxypropanesulfonic acid, etc. and salts thereof (B-4) Aliphatic hydrocarbon vinyl sulfonic acid Examples of the salts of vinyl sulfonic acid, (meth)allylsulfonic acid, and monomers containing sulfonic acid groups include alkali metal salts such as sodium, potassium, and lithium salts, and alkaline earth metal salts such as calcium and magnesium. , ammonium salt, ethanolamine, jetanolamine, monomethylamine, trimethylamine, triethylamine, and the like, with sodium salt, potassium salt, and ammonium salt being preferred.

Examples of the monomer copolymerized with the sulfonic acid (salt) group-containing monomer include the following monomers.

Examples of water-soluble vinyl monomers include amide group-containing vinyl monomers [(meth)acrylamide, N-methyl(meth)acrylamide, N-methylol(meth)acrylamide,
N, N, -Dimethylacrylamide, etc., hydroxyl group-containing vinyl monomers [hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, triethylene glycol (meth)acrylate (meth)allyl alcohol, etc.], unsaturated ( di)carboxylic acid or its acid anhydride [(meth)acrylic acid, (
anhydride) maleic acid, fumaric acid, itaconic acid, etc.], N-
Examples include vinylpyrrolidone. Examples of poorly water-soluble vinyl monomers include (meth)acrylic acid esters [methyl (meth)acrylate, ethyl (meth)acrylate,
(meth)butyl acrylate, (meth)ethylhexyl acrylate, stearyl methacrylate, etc.], fatty acid vinyl [vinyl acetate, etc.], aromatic δ hydrocarbon vinyl monomers [styrene, α-merolstinone, vinylnaphthalene, vinyl toluene, p-methylsterone, etc.], nitrile-containing vinyl monomers [(meth)acrylic nitrile, etc.]. Preferably, it is a vinyl monomer.

A JJim polymer containing sulfonic acid (salt) groups! ! ! Construction! There is no particular restriction on τ, but it can be produced by a normal solution polymerization method. For example, monomers containing sulfonic acid (salt) groups and if necessary other #! In a solvent such as water; lower methyl alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol; cellosolves such as ethyl cellosolve, ethyl cellosolve, or a combination of two or more of these solvents. 50~150℃
Polymerizes with As a radical polymerization initiator, persulfate,
Azobisisobutyrotolyl, benzoylperoxyi! , - Socumilbame 4: → J-id, etc., is used with 0.1 to 15 heavy fjl 9"o for SomuL1 body. If necessary, a cross-chain transfer agent such as lauryl mercaptan, thioglycolic acid, or mercaptoethanol is used. use

The molecular weight of the sulfone shark group-containing autopolymer in the present invention is usually 1.000-=2.000.000. . Preferably 2. ．． 0110-1.000.000% Good for history
L, < 413,000-201), 000'r: Yes. When the molecular weight is less than 1,000, it is sufficient that the molecular weight is less than 1,000.
If it exceeds 000.000, the viscosity of the aqueous liquid of the polymer (tl) increases, resulting in poor workability. .

When expressed as a 30% by weight aqueous liquid viscosity, approximately to-ioo
,o.

0CI)S, preferably about 20-50.000e
pS'? There is F.

The sulfonic acid group-containing polymer in the sulfonic acid group-containing polymer usually accounts for 20% by weight or more, preferably 30% by weight, in the polymer, expressed as a weight percent based on the polymer excluding the salt component. That's all. If 20% by weight is not added, the stability of the N method will deteriorate.

The paper constituting the recording material of the present invention is high-quality paper or medium-quality paper made from wood valves such as M-string caranal paper, L-BKP, N-BKP, and SCP under acidic, neutral, or alkaline conditions. and coated paper base paper, preferably neutral to alkaline paper which has been internally added with alkyl ketene dimer alkenyl succinic anhydride or the like. These papers contain free materials such as kaolin, talc, and calcium carbonate, usually 3=40%.
, preferably 5 to 20%. The basis weight is usually 35-1
It is 20g/mp.

When using the sulfonic acid group-containing polymer of the present invention, the coating solution is prepared with other ingredients if necessary. The above-mentioned ingredients include raw starch (hoon starch, tapioca starch, etc.), modified starch (oxidized starch, enzyme-modified starch, etc.), binder such as polyvinyl alcohol, polyacrylamide, vegetable gum, synthetic latex, etc., inorganic pigments (kaolin, talc, etc.). , calcium carbonate, titanium oxide, silica, oxidized surface 66, aluminum hydroxide, barium sulfate, etc.], organic face 1 [urea-
Formalin resin, polystyrene, etc.], a-agents, preservatives, antifoaming agents, etc.

The degree of hydration of the sulfonic acid group-containing polymer in the coating solution in the present invention is determined by the amount of blue oil on the paper at the time of coating, the antistatic properties and dimensional stability required of the paper, etc. 0.
05~! It is O weight ffi%. The coating amount of paper is usually 0.05=I g/m', preferably i, tO, I
-0.5 g/ln'', 4 If the coating amount is too large, the effect will not be exhibited in spite of the coating amount, and if it is too small, the IJ objective of the present invention cannot be achieved.

The sulfonic acid λ (containing polymer is normal) according to the present invention can be applied by the method of λ. In other words, apply the coating liquid to the surface of the paper using a coating device such as a No. 12 press, a gate 12-ru, or a calender air knife coater, or
Alternatively, spray on Sakai paper with Uko Watoba = 1 and dry.

L paper coated with sulfonic acid group-containing 'Jfi coalescence' is 1
・-Used as a recording material for laser sintering. For laser vino and printers, the light source is 1 no.
Use ther beam 17. Electron 'Jj: ): (According to the recording method), a photoreceptor made of a photosemiconductor such as a selenium-deposited film is charged with a corona discharge and exposed to a laser beam to generate a latent image. Make a statue.

If the charge of the latent image is positive (negative), the latent image is developed with negatively (positively) charged toner. The visible image developed on the photoreceptor is transferred to the surface of the recording material of the present invention (not coated with the sulfonic acid group-containing polymer) and fixed thereon. Usually, the recording material of the present invention is stacked on a photoreceptor, and a positive (negative) corona discharge is performed from the back side of the recording material of the present invention to transfer the particles to the surface, and then the particles contained in the toner are transferred. The adhesive resin (for example, styrene non-polymer, styrene-methacrylic acid ester copolymer, etc.) is heated and melted.
9. Fuse to paper to stabilize visible image.

1/-user usually has He −N es A r
-He-Cd laser etc. are used.

Exposure is usually performed by scanning exposure, and in the case of facsimile, electrical signals of sent characters, figures, and other information are converted to laser light and scanned.

This laser beam printer is used for fax machines, office combinations, computers, computer systems, word processors, kanji splitters, etc.

[Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts and percentages in the examples are by weight.

Synthesis Example 1 As a sulfonation reactor, 1040 g of 1,2-dichloroethane and 9.1 g of triethyl phosphate (0
, 05 mol) was added. Also, add 104 g of polystyrene (molecular ff 120,000) (1.0 mol as styrene medium) in advance! , was dissolved in 936 g of 2-dichloroethane to obtain solution A.

The temperature in the reactor was maintained at 20=25° C., and 4 g (0.05 mol) of liquid sulfuric anhydride was gradually added dropwise. Next, add 1040 g to the solution and 80 g of liquid sulfuric anhydride (1,
0 mol) was added dropwise at the same time. The dropping rate was adjusted so that the rate of solution #i, A was 416 g/hour, and the rate of sulfuric anhydride was 32 g/hour. During the addition, cooling was performed to maintain the temperature at 18-22°C.

The sulfonated polystyrene precipitated as it formed. After the sulfonation was completed, the dispersed slurry of sulfonated polystyrene was stirred into 481 g of an aqueous solution containing 44 g of sodium hydroxide at a temperature of 30°C.

It was added gradually. Furthermore, sulfonates in aqueous liquids! , until the odor of 2-dichloroethane disappears.
1,2-dichloroethane was distilled off. Next, adjust the pH to 8.0 with sodium hydroxide and add water to 30%.
A concentration of putrium salt of sulfonated polystyrene was obtained.

The sulfonic acid content of the polymer was 42% by weight, and the viscosity of the aqueous solution was 70 cl)S.

Synthesis Examples 2 to 4 Various polystyrenes were reacted in the same manner as in Synthesis Example 1 to obtain sodium salts of sulfonated polystyrenes. The results are shown in Table 1.

Table 1 Synthesis Example 5 1,0OOCc:J Reuben with stirring blade, cooling tube, dropping D-F, nitrogen blowing tube and thermometer, water t
20 g and 180 g of isopropyl alcohol were charged, and the temperature was raised to reflux temperature under a nitrogen stream. Into a dropping funnel, charge 100 g of water, 60 g of styrene sulfonic acid sorghum, and 40 g of °γcryl 7mid), E, and in another dropping funnel, charge 1 g of persulfuric acid and 1 g of water, and it takes about 2 hours to prepare each at the same time. I passed it on to Kolben. After dropping, the mixture was aged at reflux temperature for about 2 hours.

After aging, the isopropyl alcohol was distilled off and water was added to obtain a water-soluble melon mixture (viscosity: 200 cl) with a concentration of 30%.

Synthesis Examples 6 to 8 Various vinyl monomers were polymerized in the same manner as in Synthesis Example 5 to obtain various sulfonic acid group-containing polymers. J.

The results are shown in Table-2.

Table-2 However, ) is 1 sulfonic acid group in the polymer (weight%) shows.

Examples 1 to 8, Comparative Examples 1 to 2 The sulfonic acid group-containing polymers obtained in Synthesis Examples 1 to 8 were applied onto neutral base paper containing no salt to prepare recording materials of the present invention. This recording material was tested for its dimensional stabilizing effect and antistatic effect. The results are shown in Table-3. A comparison was made with an uncoated base paper and a base paper containing 1% salt (Comparative Example 1°2).

Table-3 Symbol explanation ◎Excellent O Good test conditions〉 △Good Internally added size with alkyl ketene dimer) ■Coating conditions Equipment; Lab size press coating ffi; 0.3 g/m2 Drying - Rotating auto dryer 105℃, 60 seconds ■Measurement conditions Dimensional stability test; Coated paper as sample A piece was left in a constant temperature and humidity room (20° C., 65%) day and night, and the water immersion elongation and air immersion rate were measured. The water immersion elongation is measured at 20°C.
The sample was immersed in water for 10 minutes, and the elongation rate was measured based on the state before immersion. In addition, the air elongation rate is based on a sample piece at 20°C and 33% humidity, and the elongation rate is measured after changing the humidity from 33% to 72% and leaving it at 72% for 24 hours. Similarly, 20℃, 19℃7
The humidity was changed from 72% to 33% using 2% as the base ring, and the shrinkage rate was measured after being left at 33% for 24 hours.

Surface specific resistance value: Using an apparatus specified in JIS-C-2122, the coated sample piece was conditioned and measured in an environment of 20° C. and 40% RH for 4 hours.

[Effects of the Invention] The laser beam printer recording material of the present invention has excellent dimensional stability with less paper expansion and contraction due to moisture.
It produces effects that could not be obtained with conventional paper that has internally added sodium chloride. Furthermore, the surface resistivity value is small and the antistatic effect is excellent. It is particularly effective on base paper made from neutral or alkaline paper. In addition, the curl after copying is appropriate and the tray storage capacity is also good.

Claims (1)

[Claims] 1. A laser beam printer recording material comprising paper coated with a polymer containing sulfonic acid (salt) groups. 2. The recording material according to claim 1, wherein the sulfonic acid (salt) group-containing polymer is a sulfonated polystyrene and/or a salt thereof. 3. The sulfonic acid (salt) group-containing polymer is an aromatic hydrocarbon vinyl sulfonic acid, a sulfonic acid group-containing (meth)acrylamide, a sulfonic acid group-containing (meth)acrylate, an aliphatic hydrocarbon vinyl sulfonic acid, and salts thereof. 2. The recording material according to claim 1, which is a polymer or copolymer whose essential constituent unit is a monomer selected from the group consisting of: