JPS6023788B2 - Method for producing phenol formaldehyde polymer aqueous suspension - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing a suspension of a phenol formaldehyde polymer, in particular an aqueous suspension of a phenol formaldehyde polymer for use as a material for pressure-sensitive copying paper.

More specifically, the present invention relates to a method for producing an aqueous suspension of a phenol-formaldehyde polymer for pressure-sensitive copying paper, which has significantly improved hue, storage stability of the dispersion, and dispersion stability of the coating material for coating base paper. In general, pressure-sensitive copying paper is a sheet (CB paper) coated with microcapsules of a nonvolatile organic solvent containing an electron-donating organic compound (so-called pressure-sensitive dye), and a water-based coating composition containing an electron-accepting color developer. Sheet coated with (
CF paper), the coated surfaces of each were placed opposite each other, and the microcapsules were destroyed by the printing pressure of a ballpoint pen, typewriter, etc., and the pressure-sensitive dye solution that flowed out came into contact with the color developer, resulting in a star-colored color. It is something.

Therefore, by changing the combination of the pressure-sensitive dye-containing microcapsule layer and the color developer layer, it is possible to make multiple copies, and also to make pressure-sensitive copying paper (S
C paper) is also possible. Pressure-sensitive dyes used in such pressure-sensitive copying paper include (1) triphenylmethane dyes such as crystal violet lactone, (2)
Methylene flu dyes such as penzoyl and leucomethylene flu, '3} Fluoran dyes such as rhodamine lactam, {4) Leuco auramine dyes, {5} Spi.

One or more kinds of pyran-based pigments are appropriately selected and used. On the other hand, as an electron-accepting color developer, '1)
Inorganic solid acids such as acid Shirashi, activated clay, (2-certain phenol-formaldehyde polymers and their metal modified products, 3'-substituted salicylic acid derivatives, etc.) are used.

Among these color developers, certain phenol-formaldehyde polymers and their derivatives have {1} excellent coloring performance, {2- excellent coating suitability (rheological properties) of aqueous coating liquids, and {3- excellent coating properties). It has advantages such as the excellent water resistance of paper and low cost, and has come to be widely used both domestically and internationally. In order to coat and fix these phenol-formaldehyde polymers and their derivatives on the surface of base paper as color developers for pressure-sensitive copying paper, the polymers are pulverized using a green method in the presence of a surfactant and then added to an aqueous suspension. After it is made into a cloudy liquid, it must be mixed with other components that are included in water-based paints, such as kaolin, calcium carbonate, latex, starch, etc., and then coated and dried using a coater. Therefore, the first object of the present invention is to produce an aqueous suspension of phenol-formaldehyde polymer that does not cause sedimentation or agglomeration even when stored for a long period of time, and is stable during long-term storage, especially at high temperatures. be.

The second purpose is that the aqueous coating liquid obtained by mixing the aqueous suspension with other components has excellent coating suitability (rheological properties), heat resistance, and mechanical stability, and that the aqueous suspension has low ultrafoaming properties. It is to produce liquid.

A third object is to provide an aqueous suspension with a high degree of whiteness, which makes it possible to produce a pressure-sensitive copying paper that is less colored and thus highly white and has excellent commercial value. A fourth object is to produce an aqueous suspension in which the pressure sensitive copying paper prepared does not contain components that change color upon exposure to light or upon storage.

Furthermore, the fifth objective is that when wet pulverization is performed to form an aqueous suspension, the work can be carried out in a wide pH range, and the workability will not be reduced by foaming, thickening, etc. during atomization. An object of the present invention is to provide a method for producing a phenol formaldehyde polymer using a dispersant.

In general, there are a wide variety of dispersants, and they are used in combination with particles to obtain good dispersion depending on the purpose. Selection of the combination of particles and dispersant is mostly based on experience, and there are no general rules.

Conventionally, as a dispersant for an aqueous suspension of phenol formaldehyde polymer, '1} British Patent No. 523222'
This, phenolsulfonic acid formaldehyde condensate,■
Mochiko Sho 46-37451, Polycarboxylic acid type surfactant, [3' Hakama Kosho 48-6948, Inorganic salt of formaldehyde condensate of naphthalene sulfonic acid or alkylnaphthalene sulfonic acid, (4' Japanese Patent Publication Sho 48-16341
discloses lignin sulfonate or a combination of lignin sulfonate and alcohol, etc.
There has not yet been anything that completely satisfies the properties desired for an aqueous suspension of a phenol formaldehyde polymer, the liquid properties of an aqueous coating solution, and the performance desired for a pressure-sensitive copying paper, which are the objects of the present invention.

For example, the formalin condensate of phenolsulfonic acid disclosed in UK Pat. No, '2
) Polycarboxylic acid type surfactants (e.g., sodium salt of maleic acid-isobutylene copolymer) described in Kochiko Sho 46-37451 do not exhibit sufficient dispersion performance at pH 6 or lower, and are used in aqueous suspensions and paint components. Aqueous suspensions have the disadvantage that dispersion stability fluctuates due to the presence of acids, salts, and polyvalent metal ions (FeH, Fe, NW, etc.) in them, and the foaming properties of aqueous suspensions and water-based paints. It has disadvantages such as liquefaction, water-based paint, and reduced workability during coating;
The inorganic salt of the formaldehyde condensate of naphthalene sulfonic acid or alkylnaphthalene sulfonic acid disclosed in '3' Japanese Patent Publication No. 48-19868 has yellowing behavior when exposed to light, so that the resulting pressure-sensitive copying paper The yellowing caused by the lignin sulfonic acid is severe, and problems remain in actual use. Since salt is a natural product, it has become difficult to obtain high-quality glue sulfonate because it is highly colored and reduces the whiteness of pressure-sensitive copying paper, and because wood resources, especially softwood sources, are depleted. Things like that. The present inventors have high whiteness,
We have conducted extensive research into an aqueous suspension of phenol-formaldehyde polymer that has low foaming properties, good dispersion stability, excellent coating suitability, and provides a high-quality color developing sheet for pressure-sensitive copying paper. However, the general formula (wherein R is H
or C. ~C, o alkyl group, M is Na+, K+,
Li+, Cs+, NIL, Ca, Mg, Zn”+
, n is an integer of 5 to 1000, and m is an integer of 1 to 1000 not exceeding n.

In addition, it is possible to use an inorganic salt of an oligostyrene sulfonic acid derivative represented by the formula (a copolymer having two or more different R groups in one molecule) as a dispersant, or use the general formula (1) as a dispersant. ) and the general formula (〇) (wherein R is C.
~C,2 alkylene group, phenyl-substituted alkylene group, two or more types may be present in one molecule, M is Na
+, K, Li+, Cs+, N ratio +, Na, MgH, Z
By using it as a dispersant in combination with an inorganic salt of an alternating polymer of maleic acid and olefin (generally a polycarboxylic acid type surfactant) represented by nH, where n is an integer from 5 to loo. 1) Highly white with little coloration; 2) Extremely stable dispersion, resulting in stable aqueous suspensions over a wide pH range with low agglomeration and sedimentation, even during long-term storage at high temperatures. can, and
It is less susceptible to the effects of acids, alkalis, and salts that coexist with phenol-formaldehyde polymers (4) It is less likely to thicken or foam during the aqueous suspension process, and [5] water-based paints for pressure-sensitive copying paper production (other water-based (mixed with the paint components) has excellent thermal and mechanical stability, ■ There is little foaming of the circulating paint during water-based paint preparation and coating, and the coating workability is excellent.
}A phenol-formaldehyde polymer water-repellent suspension has excellent characteristics such as providing excellent pressure-sensitive copying paper in which the dispersant itself does not deteriorate due to discoloration and quality deterioration during exposure to light or storage. The present invention was achieved by discovering a manufacturing scale.

The aqueous suspension of the phenol formaldehyde polymer having excellent quality of the present invention is produced by wet atomization using an inorganic salt of an oligostyrene sulfonic acid converter represented by the general formula (1) as a dispersant. can be obtained,
To provide an aqueous suspension of a phenol-formaldehyde polymer for use in pressure-sensitive copying paper of excellent quality that cannot be obtained using known prior art.

Furthermore, by using an inorganic salt of an oligostyrene sulfonic acid derivative represented by the general formula (1) and an inorganic salt of an alternating polymer of maleic acid olefin represented by the general formula (0) as a dispersant, Because it can further improve the dispersion stability of turbid liquids and the thermal and mechanical stability of water-based paints, it is particularly useful for coating machines that use high-concentration water-based paints, such as blade coaters and roll coaters. It is clear that the color development performance of the pressure-sensitive copying paper produced is improved, and that the water-based paint is less prone to thickening, so it has a remarkable effect on improving the workability during coating.

In addition, when the inorganic salt of the oligostyrene sulfonic acid converter of the general formula (1) and the inorganic salt of the maleic acid-olefin alternating polymer of the general formula (D) are used together, very excellent quality can be obtained. Since it is possible to provide an aqueous suspension of the phenol formaldehyde polymer, and by controlling the ratio of the two types of dispersants used, the use of expensive dispersants can be avoided depending on the phenol formaldehyde polymer being made into the aqueous suspension. This method has the great advantage of reducing the absolute amount compared to the prior art, which in turn leads to a reduction in the cost of pressure-sensitive copying paper.

However, in the combination system of (1) and (b), it is desirable that the inorganic salt of the oligostyrene sulfonic acid derivative accounts for 20% or more of the total weight of the dispersant used, from the viewpoint of further improving the foaming suppressing ability. . The inorganic salt of oligostyrene sulfonic acid derivative used in the present invention is m-styrene or Q
- Oligostyrene obtained by ionic or radical polymerization of Q-alkylstyrene such as methylstyrene or Q-ethylstyrene, or oligostyrene obtained by sulfonating oligo-Q-alkylstyrene to a degree of sulfonation of 20 to 100%. an inorganic salt of a derivative sulfonic acid, and (2
}An inorganic salt of styrene sulfonic acid, or an oligostyrene derivative sulfonic acid obtained by ionic or radical polymerization of styrene sulfonic acid, Q-methylstyrene sulfonic acid, Q-ethylstyrene sulfonic acid, etc.
- An inorganic salt of oligostyrene sulfonic acid obtained by polymerizing inorganic salts such as methylstyrene sulfonic acid and Q-ethylstyrene sulfonic acid using HBr, HCI, etc. as a catalyst, and the degree of polymerization n is A group of compounds containing two or more types of styrene derivatives as constituent groups in one molecule, which is a general term for water-soluble salts in the range of 5 to 1000, where m is adjusted so that m is 1 to 1000 and does not exceed n. Also included.

In addition, the cation species of the oligostyrene sulfonate include alkali metals such as Na+, K+, Li+, Cs+, N+(ammonium ion), Ca juice, Mg+,
Nz soup is an example.

The inorganic salts of oligostyrene sulfonic acid derivatives used as surfactants in the aqueous suspensions of the present invention are generally
It includes a group of compounds known as conductive treatment agents for electrophotographic paper and electrostatic recording paper, and antistatic agents for paper, films, etc.; It was completely unknown that it exhibited excellent properties as a dispersant for cloudy liquids.

In addition, in the present invention, the inorganic salt of an alternating polymer of maleic acid olefin used in combination with the inorganic salt of an oligostyrene sulfonic acid derivative refers to maleic anhydride and C, to C
, 2 olefins or phenyl-substituted olefins are alternately polymerized in the presence of a catalyst, and then saponified to form an inorganic salt. It is a general term for a group of compounds prepared to have a degree of polymerization in the range of 5 to 100. . The cation species of the inorganic salt of the maleic acid olefin alternating polymer include N, K+, and L.
Examples include alkali metal ions such as i+ and Cs+, NH40 (ammonium ion), Ca2, Mg2, and Zn2, and also includes a group of compounds containing two or more types of alkylene groups in one molecule. Specific compounds used include maleic acid-ethylene alternating polymers, maleic acid-isobutylene alternating polymers, maleic acid-hexene alternating polymers, maleic acid monopentene alternating polymers, and maleic acid-diisobutylene alternating polymers. , maleic acid nonene alternating polymer, maleic acid-decene alternating polymer, maleic acid-styrene alternating polymer, maleic acid-Q-methylstyrene alternating polymer, etc., respectively, including Na salt, K salt, Cs salt, N salt, etc. . In the present invention, the amount of the inorganic salt of an oligostyrene sulfonic acid derivative or the inorganic salt of an alternating polymer of an oligostyrene sulfonic acid derivative and an olefin maleate used as a dispersant depends on the properties of the aqueous suspension to be obtained. Although not particularly limited, it is practically 0.5 parts by weight or more, preferably 2 to 2 parts by weight, based on the weight of the phenol formaldehyde polymer 10.

The raw material phenol species for the phenol formaldehyde polymer used in the present invention is mphenol (C6 day 50
H), [2} p-cresol, p-ethylphenol,
C7 to C,5 p-alkylphenols represented by p-rt-butylphenol, p-rt-amylphenol, p-rt-octylphenol, p-nonylphenol, p-dodedecylphenol, etc. '3'p
-p-cycloalkylphenol represented by cyclohexylphenol ・[4'p-chlorophenol, p-
p-halophenol represented by furomophenol, (5) p-allylphenol represented by p-phenylphenol, (6) represented by 4-Q-methylbenzylphenol, 4-Q,Q-dimethylbenzylphenol, etc. One type or a mixture of two or more types selected from p-aralkyl fer/- may be used.

Phenol-formaldehyde polymer is produced by condensing the above-mentioned phenols, formaldehyde, or formaldehyde-generating substances in an organic solvent or water as a solvent in the presence of an acidic catalyst, and removing the solvent by heating (
After dehydration), the bulk novolac polymer obtained by cooling,
■ Phenols,
In particular, after condensing p-phenylphenol with formaldehyde or formaldehyde-generating substances,
There are finely powdered novolac polymers that are dissolved in an alkaline aqueous solution, the organic solvent is removed by steam distillation, and mixed with an acid to precipitate the polymer.When used as a color developer for pressure-sensitive copying paper, both It is first made into an aqueous suspension and mixed with other paint components before being applied to base paper.

Among these, the latter, i.e., p-phenylphenol finely powdered novolac polymer obtained by mixing with acid, does not require pulverization in advance when it is made into an aqueous suspension, compared to the former, i.e., bulk novolak polymer. , it is easy to disperse in water, {b) the whiteness of the polymer is high and there is little discoloration over time during storage, 'c) the pressure-sensitive copying paper has high coloring property, especially immediately after coloring. It is widely used because it has characteristics such as high concentration. Also, p-alkylphenol-phenol formaldehyde copolymer,
In particular, p-tert-octylphenol formaldehyde copolymer is widely used as a head coloring agent for monolayer pressure-sensitive copying paper due to its {1} excellent coloring performance and (2) excellent humidity and stain resistance. It is used. The aqueous suspension of these polymers can be atomized by a conventional method using a colloid mill, a roll mill, an attritor, a sand grinder, etc. using an inorganic salt of the oligostyrene sulfonic acid derivative. can be manufactured. The content of the phenol formaldehyde polymer in the aqueous suspension can be arbitrarily produced within a desired range of 6% by weight or less, but the coating equipment (coater) used
In order to facilitate the preparation of aqueous paints ranging from low to high concentrations suitable for the format of the present invention, and from the viewpoint of transportation and handling of the aqueous polymer suspension, it is advantageous to have as high a concentration as possible.

Further, the particle size of the phenol formaldehyde polymer in the aqueous suspension is 5 microns or less, preferably in the range of 1 to 3 microns. If the number of particles exceeding 5 microns is large, the amount of sediment during static storage of the aqueous suspension increases, and the coloring performance of the pressure-sensitive copying paper, especially the density immediately after coloring, decreases.

Below 1 micron, the aqueous suspension exhibits thickening behavior, making it difficult to increase the concentration and handle the aqueous suspension.

When preparing pressure-sensitive copying paper using an aqueous suspension of phenol-formaldehyde polymer, {11 inorganic or organic pigment, ■
A pigment dispersant, {3} coating binder, '4} and other various additives are mixed to prepare a water-based paint according to the coating method, coated on base paper, and dried to obtain pressure-sensitive copying paper.

'1} Inorganic or organic pigments used here include:
Kaolin, bentonite, talc, calcium carbonate, barium sulfate, aluminum oxide (alumina), silicon oxide (silica), satin white, titanium oxide, polystyrene emulsion, etc.'2) As pigment dispersants,
IJ phosphates such as sodium metaphosphate, sodium hexametaphosphate, and sodium tripolyphosphate, and polycarboxylate salts such as sodium polyacrylate, are used as rigid coating binders such as oxidized starch, enzymatic starch, urea phosphate starch, and alkylated starch. modified starches such as casein, water-soluble proteins such as gelatin, styrene-butadiene latex (SBR), methyl methacrylate butadiene latex (MBR), vinyl acetate polymer emulsion, vinyl acetate ethylene latex, etc. Polymer emulsion, polyvinyl alcohol, carboxymethyl cell. Synthetic and semi-synthetic binders such as base, hydroxyethylcellulose, and methylcellulose (4'Other additives include optical brighteners, antifoaming agents, viscosity modifiers, anti-dusting agents, and slime control agents. , a lubricant, a water-resistant agent, etc.A water-based paint prepared by mixing and dispersing the phenol-formaldehyde polymer aqueous suspension of the present invention and the various components described above can be used as
Plaid coater, brush coater, roll coater,
Coat it on the base paper using a /Goo coater or the like and dry it to make a pressure-sensitive copying paper developer sheet.

Generally, the amount of water-based paint applied is at least 0.5 evening/day, preferably from 1 to 10 evening/day, on a dry weight basis.

The color development performance of a sheet coated with water-based paint is mainly controlled by the concentration of the phenol-formaldehyde polymer in the water-based paint, and a coating amount of 10% or more is not effective in improving color performance, and also from a drug standpoint. It is disadvantageous. Hereinafter, the present invention will be specifically described in detail with reference to Examples and Comparative Examples.

The performances of the aqueous suspensions, water-based paints, and pressure-sensitive copying papers obtained in Examples and Comparative Examples are summarized in Table 1.

Various performance test methods are shown below.

A. Performance of aqueous suspension (1) Hue Pour the aqueous suspension onto a high-quality paper with a dry weight of 5.
Four sheets (aqueous suspension coated sheets) coated in the same manner as evening/back were stacked together, and the reflectance was determined using a blue filter with a TSS type Hunter colorimeter (manufactured by Toyo Seiki).

The whiteness (whiteness) of the aqueous suspension coated sheet is expressed as reflectance (■). The higher the reflectance wind, the whiter the aqueous suspension is, and if the difference is about 1 point (%), superiority or inferiority can be discerned with the naked eye.

(0) Viscosity The aqueous suspension obtained by atomization was measured at 25 qo using a B-type viscometer,
M. The viscosity is measured under the conditions of 1 rotor and 6 pm and expressed as a number (unit: cp) (m) A high temperature storage stable aqueous suspension 2K9 was charged into a stainless steel beaker with an internal volume of 2, and a glass impeller ( Kite type, diameter 10) 1
It was stored at 35° C. for one week while being heated at 0 Mpm, and the furnace resistance before and after storage was compared using the furnace time (sec) of a 200 mesh section of 7.5 J.

A long disease time after the high-temperature storage test means that the particles of the phenol-formaldehyde polymer aggregate and close the knots in the aqueous suspension, indicating that the high-temperature dispersibility is poor. (W) Foaming In a measuring cylinder with an internal volume of 1000', add 2 parts of the aqueous suspension.
Nitrogen gas is blown into the tube at a rate of 1400 cc/min for 5 hours from a glass filter-like gas introduction tube placed in a bag at the bottom, and the amount of increase in volume due to bubbles in cc is measured.

In addition, the degree of foaming increase during formation of an aqueous suspension was visually determined and displayed.

B. Performance of water-based paints (1) Mechanical and thermal stability Aqueous phenol-formaldehyde polymers with the following composition were used to produce color developing sheets for biplane pressure-sensitive copying paper in Examples 1 to 5 and Comparative Examples 1 to 3. A water-based paint for a blade coater (55M% solid content) using a suspension was prepared and its performance was measured.

Phenol Formaldehyde Polymer Heavy Aqueous Suspension (Solid Content 40%) Six Power Orin
13 Calcium carbonate
Starch dioxide (20% aqueous solution) 15 Styrene, butadiene, latex (50% aqueous dispersion)
2.5 Sodium metaphosphate 0.1 water
17.9 500 g of the above water-based paint with a solid content of 55% was heated at high speed for 30 minutes at room temperature (25°C) in a homomixer (manufactured by Tokushu Kikako, M type) to determine the paint liquid temperature, paint viscosity, and the following. The color development performance (color development rise speed, color development density) of pressure-sensitive copying paper prepared using the method described above was compared and measured.

Due to the mechanical shear during high-speed sanding and heat, the fine particles of phenol formaldehyde polymer in the paint tend to aggregate, which affects the viscosity of the paint and the coloring performance of pressure-sensitive copying paper, especially the density of the colored image immediately after coloring. give.

If the dispersion state of the phenol formaldehyde polymer particles in the paint is poor, the high-speed fly test shows that the paint tends to increase and the coloring performance deteriorates due to a decrease in the specific surface area due to the aggregation of the phenol formaldehyde polymer. This causes problems in coating and quality of pressure-sensitive copying paper. (
0) Foamability In Examples 6 to 8 and Comparative Examples 4 to 6, an air knife for manufacturing single leaf pressure-sensitive copying paper was used using an aqueous suspension of p-tem-octylphenol-phenol formaldehyde copolymer having the following composition. Water-based paint for coater (3
(wt% solids) was prepared.

Phenol formaldehyde polymer Part by weight Aqueous suspension (50% aqueous suspension) 5-Riki Orin
12 calcium carbonate
Trioxidized starch (20% aqueous solution)
15 Styrene-butadiene latex (50% aqueous dispersion) 2.5 Polyacrylic acid sodium salt
0.05 water
43.87 The water-based paint 200 has an internal volume of 1000
Nitrogen gas is introduced at 1400 cc/min from a glass filter-like gas inlet tube inserted into a measuring cylinder at the bottom.
Measure the increase in volume due to foam by blowing at a speed of 5 minutes.

This means that the greater the foaming property of the water-based paint, the greater the foaming of the water-based paint during the preparation of the water-based paint and the circulating paint in the air-knife coater, resulting in difficulty in workability during coating.

In addition, for highly foaming paints, antifoaming agents can be used to suppress foaming; however, effective antifoaming agents are highly aqueous and prevent the formation of fish-eyes on coated paper. It is not used very often because it causes quality deterioration.

C Performance as pressure-sensitive copying paper The water-based paint described in the previous section was used in Examples 1 to 5 and Comparative Examples 1 to 3.
The water-based paint that has been tested for mechanical and thermal stability using a homomixer is applied to high-quality paper using a Mayer bar to a dry coating amount of 6 days/day, and then dried to form a biplane pressure-sensitive copying paper developer sheet. get.

In addition, for Examples 6 to 8 and Comparative Examples 4 to 6, the dry coating amount was applied to the capsule surface of the undercoat paper for single-leaf type pressure-sensitive copying paper (NW-40U manufactured by Tozai Paper Co., Ltd.) at 5 days/after. It is coated and dried using a Meyer bar to obtain a color developer sheet for single leaf type pressure-sensitive copying paper.

(1) Color development density and speed In the bileaf type pressure-sensitive copying paper color-developing sheet, commercially available paper (NW-4m manufactured by Tohashi Paper Manufacturing Co., Ltd.) containing crystal violet lactone (CVL) as the main pressure-sensitive dye and mauve color were used. With both coated sides of the sheet facing each other, place high-quality paper on the top and bottom, or use high-quality paper on the top and bottom of the single-leaf type pressure-sensitive copying paper developing sheet, and use an electric typewriter to develop the cobalt flu color.
Determine the reflectance using an SS type Hunter colorimeter using an amber filter.

The color density was measured 1 minute after the striking pressure was generated and at the second time after color development, and the initial color development rate was calculated using the reflectance lo, 1, 12 before color development, 1 minute after color development, and 2 periods after color development. J4]
= 1,000; LX・oo (%), achieved color development rate [J2]; 2ヱX,. 〇Displayed in 10 (%).

It is preferable that the difference between the initial color development rate and the final color development rate is small and the final color development rate is high, both in terms of color development rate and density. (0) Whiteness of color developer sheet Four color sheets coated in the manner described above are stacked one on top of the other, and the reflectance is determined using a Hunter colorimeter with a blue filter.

The whiteness (whiteness) of the color developer sheet is expressed as reflectance [F].
The larger [F] is, the whiter the color developing sheet is, and the difference is about 0.5 points and can be determined with the naked eye. (m)
A color developer sheet that has not undergone light yellowing is irradiated with sunlight for one feeding period, and the reflectance K, K2 (Hunter colorimeter, blue filter used) before and after irradiation is measured.

The difference between K and K2 indicates the degree of yellowing of the complexion sheet due to photooxidative yellowing of the phenol-formaldehyde polymer and photoyellowing of the dispersant.

The degree of photoyellowing is expressed as Δk=K, -K2, and the smaller Δk is, the less the photoyellowing of the color developer sheet is.

Synthesis Example 1 25.5k9 of P-phenylphenol, 3.4k9 of formaldehyde (80%), 0.26k9 of para-toluenesulfonic acid and 33.6k9 of benzene were charged into a stainless steel reactor and stirred. 7 while heating the water in the reaction system to the outside of the system through azeotropy with benzene.
The reaction was carried out from 0 to 90 o'clock.

After the reaction was completed, 40.0k9 of a 15% aqueous solution of caustic soda was added and heated to melt the polymer. After distilling off the benzene, it was diluted with 500ml of water, and 15% sulfuric acid was added dropwise under the rope to adjust the pH.
The mixture was neutralized to completely precipitate a white fine powder polymer, which was then separated using a centrifuge.

48.0k of polymer as a wet cake with dry solids content of 55%
9. Obtained 26.5k9 in terms of dry content. Synthesis Example 2 After condensing 2,870 tons of p-ten-octylphenol, 630 tons of phenol (carbolic acid), 137.8 tons of 37% formalin, and 100 tons of 35% HC under water reflux for 6 hours, heat dehydration to 160 degrees. The reaction was terminated to obtain a pale yellow p-te 91 octylphenol-phenol formaldehyde copolymer with a softening point of 102oC.

The p-ten-octylphenol-phenol formaldehyde copolymer was processed in a small pulverizer to obtain a white powder with a 50-mesh size.

Example 1 The p-phenylphenol formaldehyde polymerization temperature cake obtained in Synthesis Example 1 was 3635 mm (2000 mm in terms of dry content),
Oligostyrene sulfonic acid sodium salt (molecular weight 500
0, degree of sulfonation 72%) 20% aqueous solution 800 g (dry content: 160 g) and water 565 g A white aqueous suspension with a combined weight of 40% was obtained in an amount of 5000 g.

Example 2 p-Phenylphenol formaldehyde polymer wet cake obtained in Synthesis Example 1 3635 oligostyrene sulfonate ammonium salt (molecular weight 500 u, degree of sulfonation 80%)
) 30% aqueous solution 330% and water 1065% were dispersed using a sand grinder (SG12 model manufactured by Inoue Seisakusho) to obtain a white aqueous suspension 500% with an average particle size of 2.0 mm.
I got 0 nights.

Example 3 The p-phenol formaldehyde polymer wet cake 3635 obtained in Synthesis Example 1 was mixed with 15% of the sodium salt of oligo-Q-methylstyrene sulfonic acid (molecular weight 7000, degree of sulfonation 75%). After treating the aqueous solution 667 and water 698 with a sand grinder, the pH was adjusted to 7 to 8 with an aqueous sodium hydroxide solution to obtain a white aqueous suspension 5.
I got 000 Yu.

Example 4 p-phenylphenol formaldehyde polymerization temperature cake obtained in Synthesis Example 1 3635 days, potassium salt of oligostyrene sulfonic acid (molecular weight 300, degree of sulfonation 90%)
20% aqueous solution of 150% polycarboxylic acid type surfactant)
Sodium salt of alternating polymerization of isobutylene maleate) 8
After processing 0.0 mL and 1135 mL of water with a sand grinder, the pH was adjusted to 7 to 8 with an aqueous sulfuric acid solution to obtain a white aqueous suspension of 500 mL.

Example 5 P-phenylphenol formaldehyde polymerization temperature cake obtained in Synthesis Example 1 3635 days, 20% aqueous solution of oligo-Q-methylstyrenesulfonic acid ammonium salt (molecular weight 5000, degree of sulfonation 100%) 200 days, polycarboxylic acid Type surfactant (ammonium salt of alternating polymer of mono-Q maleate-methylstyrene) 40 parts and water 112 parts
After processing with a sand grinder, pH was adjusted with dilute sulfuric acid.
was adjusted to 7-8 to obtain a white aqueous suspension of 5,000 g.

Comparative Example 1 3635 kg of p-phenol formaldehyde polymer green cake obtained in Synthesis Example 1, 80 kg of polycarboxylic acid type surfactant (sodium salt of isobutylene maleate alternating polymer) and 1285 kg of water were added. After processing with a sand grinder, dilute sulfuric acid was added to adjust the pH to 7-8 to obtain a white aqueous suspension.

Comparative Example 2 The p-phenylphenol formaldehyde polymer wet cake obtained in Synthesis Example 1 (3635 g), 200 g (200 g) of sodium lignin sulfonate, and 1165 g (1165 g) of water were treated with a sand grinder, and the pH was adjusted with an aqueous NaOH solution to give a brown cutlet color. An aqueous suspension of 5,000 g was obtained.

Comparative Example 3 3635 ml of the p-phenylphenol formaldehyde polymer wet cake obtained in Synthesis Example 1, 200 ml of the sodium salt of naphthalene sulfonic acid formalin condensate, and 1165 ml of water were treated with a sand grinder.
pH adjusted with aqueous NaOH solution and colored aqueous suspension 5
I got 000 Yu.

Example 6 A powder of 200% of the p-ten-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2 was added to oligostyrene sulfonic acid sodium salt (molecular weight 5000,
Degree of sulfonation 95%) 20% aqueous solution 50% and water 15%
A white aqueous suspension 400 was obtained by treating it with Attractor-01 (manufactured by Mitsui Miike Seisakusho).

Example-7 200 yen powder of the p-te-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2, oligostyrene sulfonic acid potassium salt (1 molecular weight 5000,
degree of sulfonation 75%) 25% aqueous solution 24 times, and water 1
76 was treated with an attritor to form a white aqueous suspension 4.
Got 00 evenings.

Example 8 200% of the p-ten-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2, 20% of the sodium salt of oligoQ-methylstyrenesulfonic acid (molecular weight 7000, degree of sulfonation 68%) Aqueous solution 3
0 days, 4 days of N sodium salt of isobutylene maleate alternating polymer and 166 days of water were treated with an attritor,
A white aqueous suspension was obtained.

Comparative Example 4 200 g of the p-ten-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2, 14 g of sodium lignin sulfonate and 186 g of water were treated with an attritor to produce a brown aqueous suspension of 400 g. I got it.

Comparative Example 5 200 g of the p-ten-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2, 8 g of a polycarboxylic acid type surfactant (potassium salt of an alternating condensate of maleic acid and styrene) and 192 g of water were mixed in an attritor. Processing gave a white aqueous suspension of 400ml.

Comparative Example 6 200% p-ten-octylphenol-phenol formaldehyde copolymer obtained in Synthesis Example 2, 10% sodium salt of methylnaphthalesulfonic acid formalin condensate
A light brown aqueous suspension of 400 mL was obtained by treating 190 mL of water and 190 mL of water with an attritor.

Port spot S Recognized trout S Reeds S & A do Shi nose weight, steam, heart, mountain, snake, Yamashita Yoshihiro go pot, steam gutter ll H) I A ■ ■ Ship table - 2 p -tert-butylphenol-phenolformaltehyde copolymer water-bending suspension obtained from the water-bending suspension of the water-bending copying paper single-leaf ■Performance as described above Tables 1 and 2 show the performance of the aqueous suspensions of the Examples and Comparative Examples of the present invention, the aqueous coating liquids obtained therefrom, and the pressure-sensitive copying paper color developing sheets by various performance test methods.

Claims (1)

[Claims] 1. In producing a suspension in which a phenol formaldehyde polymer is dispersed in water, the general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or an alkyl group of C_1 to C_1_0, M is Na^+, K^+, Li^+, Cs^+, NH
_4^+, Ca■, Mg■, Zn■, where n is 5 to 1
000 integer, m is an integer from 1 to 1000 and does not exceed n. Note that it may be a copolymer having two or more different R groups in one molecule. 1. A method for producing an aqueous suspension of a phenol formaldehyde polymer, which comprises using a salt of an oligostyrene sulfonic acid derivative represented by: 2. The method according to claim 1, wherein the phenol formaldehyde polymer is a p-phenylphenol formaldehyde polymer. 3. After the p-phenylphenol formaldehyde polymer condenses p-phenylphenol and formaldehyde or a formaldehyde-generating substance in a hydrophobic organic solvent that is azeotropic with water in the presence of an acid catalyst, and the reaction is completed, The method according to claim 2, which is a finely powdered p-phenylphenol formaldehyde polymer obtained by dissolving it in an aqueous alkaline solution, removing the organic solvent by steam distillation, and precipitating it by adding an acid. 4. The method according to claim 1, wherein the phenol formaldehyde polymer is a p-alkylphenol-phenol formaldehyde copolymer. 5 p-alkylphenol-phenol formaldehyde copolymer is p-tert-octylphenol-
The method according to claim 4, which is a phenol formaldehyde copolymer. 6. When producing a suspension in which a phenol formaldehyde polymer is dispersed in water, the general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or an alkyl group of C_1 to C_1_0, M is Na^+, K^+, Li^+, Cs^+, NH
_4^+, Ca■, Mg■, Zn■, where n is 5 to 1
000 integer, m is an integer from 1 to 1000 and does not exceed n. Note that it may be a copolymer having two or more different R groups in one molecule. ) and the general formula (II) ▲ Numerical formula, chemical formula, table, etc. The above may be included in one molecule, and M is Na^+, K^+, Li^+,
Cs^+, NH_4^+, Ca■, Mg■, Zn■, where n is an integer from 5 to 100. 1. A method for producing an aqueous suspension of a phenol formaldehyde polymer, which comprises using a salt of a maleic acid-olefin alternating polymer represented by: 7. The method according to claim 6, wherein the phenol formaldehyde polymer is a p-phenylphenol formaldehyde polymer. 8 After the p-phenylphenol formaldehyde polymer condenses p-phenylphenol and formaldehyde or a formaldehyde generating substance in the presence of an acid catalyst in a hydrophobic organic solvent that is azeotropic with water, and the reaction is completed, The method according to claim 7, which is a finely powdered p-phenylphenol formaldehyde polymer obtained by dissolving it in an aqueous alkaline solution, removing the organic solvent by steam distillation, and precipitating it by adding an acid. 9. The method according to claim 6, wherein the phenol formaldehyde polymer is a p-alkylphenol-phenol formaldehyde copolymer. 10. The method according to claim 9, wherein the p-alkylphenol-phenol formaldehyde copolymer is a p-tert-octylphenol-phenol formaldehyde copolymer.