JPH02223467A - Color developer sheet for carbonless copy paper - Google Patents

Abstract

PURPOSE:To minimize the transfer of desensitizing ink to an unprinted part by forming a developing layer containing an electron acceptive organic developer such as salicylic acid derivative, adhesive, and inorganic or organic compound particles on a supporter. CONSTITUTION:An application liquid for formation of a developing layer is prepared by dissolving and dispersing in water, etc., such principal components as an electron acceptive organic developer composed of salicyclic acid derivative and/or polyvalent metal salt thereof, an adhesive and inorganic and/or organic compound particles wherein the particle diameter of at least 30wt.% (per developing layer) is 10mum or more. The liquid is applied to the supporter such as wood freed paper through the use of an air knife, etc., and is dried, to form the developing layer of 20 to 60sec of Bekk smoothness, ultimately, the developing sheet for carbonless copying paper can be obtained. Some type of salicyclic acid derivative has 1-4 groups of alkyl cycloalkyl, aryl, etc., in salicyclic acid or in its benzene ring.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color developer sheet for carbonless copying paper, and particularly to a developer sheet that uses a salicylic acid derivative and/or its polyvalent metal salt as a color developer. Regarding color sheets.

(Prior Art) Carbonless copy paper is well known, for example, as disclosed in U.S. Pat.
No. 50470, No. 2730465, No. 2505489
No. 2,730,457, etc., a nearly colorless organic compound (hereinafter referred to as a color former) having electron-donating properties, adsorption properties, and color-forming reactivity is dissolved in an organic solvent and microcoated. It utilizes a contact reaction between the encapsulated material and an electron-accepting, reactive, adsorbent substance (hereinafter referred to as a color developer).

In general, carbonless copy paper is used by placing the coated side of the top paper coated with microcapsules containing a color former on the coated side of the bottom paper coated with a color developer and applying pressure to release the microcapsules. It is destroyed to obtain a colored image.

In this application, a color forming agent and a color developer are applied separately to the back and front sides of a single sheet, and the paper is inserted between the upper and lower sheets for use in making multiple copies. There are self-contained types in which a color former and a color developer are applied to the same side of the body.

In the past, clay-based inorganic solid acids such as activated clay, acid clay, and attapulgide were frequently used as color developers.
Currently, novolac type phenol-formalin resins, salicylic acid derivatives and/or their polyvalent metal salts are often used.

However, when salicylic acid derivatives and/or their polyvalent metal salts are used as color developers, desensitization printing is performed using desensitizing ink in order to partially create areas where color development is not desired on the color developer sheet surface. If the sheet surfaces are stacked in a zigzag pattern in a "fold" configuration, the surface of the color developer sheet with desensitization printing will be replaced by the surface of the color developer sheet that is facing and in contact with the surface of the color developer sheet that has not been desensitized. The desensitized ink transfers to the surface and inhibits color development on the surface of the unprinted color developer sheet, which should develop color, resulting in a fatal drawback that the print becomes unreadable or difficult to read even if the color is desired to be developed. there were.

Hereinafter, such a phenomenon will be referred to as "desensitized ink transfer stain."

(Problem to be Solved by the Invention) Therefore, the present invention uses a salicylic acid derivative and/or its polyvalent metal salt to achieve good visibility with less "transfer stain of desensitizing ink" and no problem in actual use. It provides a means for obtaining colored sheets.

(Means for Solving the Problems) Salicylic acid derivatives used in the present invention include salicylic acid or salicylic acid whose benzene nucleus has 1 to 4 substituents such as alkyl, cycloalkyl, aryl, or halogen or hydroxy; Alternatively, a polymer of salicylic acid or a salicylic acid whose benzene nucleus has one to three of the above substituents and an aldehyde can be mentioned. The most typical examples include salicylic acid, 5-tert-butylsalicylic acid, and 3,5-tert-butylsalicylic acid.
ert-butylsalicylic acid, 3,5-di-tert-amylsalicylic acid, 3.5-sec-butylsalicylic acid, 5
-nonylsalicylic acid, 3methyl-5-isoamylsalicylic acid, 5-isoamylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3,5-
Dicyclohexylsalicylic acid, 3,5-di(α,α-dimethylbenzyl)salicylic acid, 3,5-dibenzylsalicylic acid, 3-(α,α-dimethylbenzyl)5-tert
-Butylsalicylic acid, 3,5 di(α-methylbenzyl)
Salicylic acid, 3-phenylsalicylic acid, 3,5-diphenylsalicylic acid, 3-phenyl-5-tert-butylsalicylic acid, 3-benzyl-5-phenylsalicylic acid,
3.5-dichlorosalicylic acid, 3-chloro-5-methylsalicylic acid, 3-chloro-5-ethylsalicylic acid, 3-
Chloro-5-phenylsalicylic acid, salicylic acid-formaldehyde polymer, 2,6 dihydroxybenzoic acid-formaldehyde polymer, etc. are used. The above salicylic acid derivatives all form salts with polyvalent metals, and the polyvalent metals used include zinc, magnesium, titanium,
These include aluminum, calcium, cobalt, nickel, manganese, tin, and copper. Further, the derivative in the form of an acid that is not a salt and a metal compound may be used in combination.

In addition, polyvalent metallized salicylic acid resins, which have been proposed in many ways in recent years, can also be used in the present invention, and these color developers include polyvalent metallized resins of salicylic acid and co-condensed resins such as α, α-dialkoxy p-xylene. Metal compounds (JP-A-62-1
76875.62178387.62-178388.
63-53092.63-159082.63-160
877), Polyvalent metallized resin obtained by reacting a styrene derivative with a salicylic acid derivative having an aromatic substituent (JP 63-186729), Reacting a salicylic acid derivative having an aromatic substituent with a benzyl halide Polyvalent metal compound of resin obtained by JP-A-63-25412
4), and other resin polyvalent metal compounds described in JP-A No. 63-289017.

These polyvalent metallized salicylic acid resins are characterized by high solubility in various solvents, but they also have high solubility in desensitizers, and therefore tend to cause transfer stains of desensitized ink. However, the present invention has an effect that more than covers the difference in the solubility of the color developer, and thus showed a particularly remarkable effect on polyvalent metallized salicylic acid resins.

As the inorganic and/or organic compound particles of 10 μm or more used in the present invention, pigment particles, vegetable particles, plastic particles, wax particles, etc. are used. As the pigment, both inorganic pigments and organic pigments can be used, and examples of the organic pigments include polystyrene, polyvinyltoluene, styrene-divinylbenzene copolymer, polymethyl methacrylate, and urea-formaldehyde polymer. Can be done.

Inorganic pigments refer to natural, semi-synthetic, and synthetic mineral substances that are substantially insoluble in water, such as calcium carbonate,
Talc, silica powder, clay, barium sulfate, barium carbonate, magnesium carbonate, magnesium silicate, lead sulfate,
Lead white, zinc white, zinc sulfide, satin white, titanium oxide, antimony oxide, mica, bentonite, calcium silicate,
Examples include gypsum, aluminum hydroxide, etc.

Plant particles include potatoes, corn, rice, konjac, millet, millet, kudzu, buckwheat, linden,
Japanese potato, sweet potato, capocha, wasabi, ginger,
Starch particles and cellulose powders such as tapioca, ginkgo, wheat, bracken, fava bean, quail, pea, banana, Japanese radish, adzuki bean, peanut, kwai, and ginger can be used.

Wax particles include paraffin wax, microcrystalline wax, petrolatum, rice wax, carnauba wax, candelilla wax, beeswax, wood wax, polyethylene wax, shellac wax,
etc. are cited as examples of such materials.

These inorganic and/or organic compound particles having a size of 10 μm or more may be contained in the color developing layer in an amount of 30% or more by weight, preferably 35% to 60%.

If it is less than 30%, the transfer of desensitized ink is not sufficiently prevented, and if it is more than 60%, the transfer of printing ink from the plate to the paper surface may not be sufficient during printing.

Further, the inorganic and/or organic compound particles having a size of 10 μm or more may be used alone or in various combinations of two or more types to achieve the object of the present invention.

The color developing sheet of the present invention can be used with ordinary air knives, rolls,
It is applied using methods such as blades and size presses. And usually machine calendar super calendar,
In the present invention, using a calendar such as a gloss calendar, the smoothness is adjusted from 20 seconds to 60 seconds with a Beck smoothness meter. 6
If it is longer than 0 seconds, the transfer stain of the desensitized ink will be large, and if it is shorter than 20 seconds, the transfer of printing ink from the plate to the paper surface during printing will deteriorate.

The inorganic and/or organic compound particles of 10 μm or more according to the present invention include color developers, pigments, antifoaming agents, lubricants, dispersants, penetrants, waterproofing agents, etc. selected as necessary, and adhesives. It is applied to the support together with an adhesive, and any conventionally known adhesive can be used as the adhesive.

For example, water-soluble natural polymer compounds such as proteins such as casein and gelatin, cellulose derivatives such as carboxymethylcellulose and hydroxymethylcellulose, and sucrose such as oxidized starch and esterified starch;
Furthermore, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, styrene-butadiene latex,
Water-soluble synthetic polymer compounds and latexes such as acrylonitrile-butadiene-acrylic acid latex, polyacrylamide, styrene-maleic anhydride copolymer, etc. can be used.

(Function) In the present invention, "transfer stain of desensitized ink" is improved, but the reason for this is extremely physical and can be attributed to a decrease in the optical contact ratio. That is, the contact of the unprinted part with the desensitized printed part is 10 μm or more with inorganic and/or
Alternatively, this may be due to the effect of being hindered by organic compound particles and reducing the transfer of desensitized ink to unprinted areas.

(Example) Examples of the present invention will be described below, but the present invention is not limited thereto.

Note that (parts) and (%) in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified.

Example 1 0.5 part of sodium pyrophosphate was dissolved in 90 parts of water, and 50 parts of calcium carbonate (Brilliant 15, manufactured by Shiroishi Kogyo KK) having a particle size of 0.2 μm was added and sufficiently dispersed.

Next, 150 parts of 10% oxidized starch and 30 parts of 40% zinc 3,5-di-1er(-butylsalicylate) ground to 3 μm were added. 50 parts of wheat starch having a particle size of 20 μm was added thereto to form a carbonless A color developer sheet paint for copying paper was prepared, and 8 g/rrf was applied to high quality paper.
(g/a) using an air knife coater and drying to obtain a color developing sheet for carbonless copying paper with a smoothness of 30 seconds.

Example 2 The wheat starch of Example 1 was mixed with 12 μm calcium carbonate (
A color developing sheet for carbonless copying paper having a smoothness of 46 seconds was obtained in the same manner as in Example 1 except that Maruo calcium (Super S made by Kiki Co., Ltd.) was substituted.

Example 3 Same as Example 1 except that the wheat starch in Example 1 was replaced with 14 μm corn starch, and the smoothness was 34.
A second color developing sheet for carbonless copying paper was obtained.

Example 4 A color developing sheet for carbonless copying paper having a smoothness of 22 seconds was obtained in the same manner as in Example 1 except that the wheat starch in Example 1 was replaced with cellulose powder having a major diameter of 30 μm.

Example 5 A color developer sheet for carbonless copying paper having a smoothness of 44 seconds was obtained in the same manner as in Example 1, except that the wheat starch in Example 1 was replaced with 15 μm polyethylene powder.

Example 6 A color developing sheet for carbonless copying paper with a smoothness of 41 seconds was obtained in the same manner as in Example 1 except that the wheat starch in Example 1 was used as 40 parts and the 0.2 μm calcium carbonate was used as 60 parts. .

Example 7 A color developing sheet for carbonless copying paper with a smoothness of 26 seconds was obtained in the same manner as in Example 1 except that the wheat starch in Example 1 was used as 70 parts and the 0.2 μm calcium carbonate was used as 30 parts. .

Example 8 The color developer of Example 1 (zinc 3,5-di-butylsalicylate) was mixed with 6-9 g (0.02 mol) of 3,5-di(4-methylbenzyl)salicylic acid using sulfuric acid as a catalyst. The smoothness was 45. A second color developing sheet for carbonless copying paper was obtained.

Comparative Example 1 The color developer sheet for carbonless copying paper obtained in Example 1 was smoothed to a smoothness of 80 seconds using a super calendar.

Comparative Example 1 The color developing sheet for carbonless copying paper obtained in Example 1 was smoothed to a smoothness of 200 seconds using a super calendar.

Comparative Example 3 The total amount of wheat starch in Example 1 was reduced to 0. The smoothness was 70 in the same manner as in Example 1 except that the substitution was made with Kashiram carbonate having a thickness of 2 μm.
A second color developing sheet for carbonless copying paper was obtained.

Comparative Example 4 A color developer sheet for carbonless copying paper with a smoothness of 55 seconds was obtained in the same manner as in Example 1 except that the wheat starch in Example 1 was reduced to 35 parts and the 0°2 μm calcium carbonate was changed to 65 parts. Ta.

Comparative Example 5 The wheat starch of Example 1 was mixed with polyethylene (trade name Chemipearl M20) manufactured by Mitsui Petrochemical Industries ■ having a particle size of 5 μm.
A color developer sheet for carbon-free copying paper having a smoothness of 53 seconds was obtained in the same manner as in Example 1, except that the same amount of solid content was substituted for 0).

Comparative Example 6 A smoothness of 6 was obtained in the same manner as in Example 8, except that the entire amount of wheat starch in Example 8 was replaced with 0.2 μm calcium carbonate.
A color developing sheet for carbonless copying paper of 8 seconds was obtained.

Desensitizing ink (Fuji Photo Film Co., Ltd. F
N103) was folded using a printing machine so as to have a weight of 2g1rd, and a load of 100g/rrf was applied. And 1
After 0 days, the printed matter was taken out, and the developer sheet superimposed on the desensitized printed area was colored using a color developer spray checker for color developer sheets, and transfer stains of the desensitized ink were visually determined.

◎・・・・・・Transfer stain is not observed at all.

○... Almost no transfer stains are observed.

△... Some transfer stains are generated.

×...Transfer stains are significantly generated.

(Effects of the Invention) As described above, the color developing sheet for carbonless copying paper according to the present invention has almost no transfer stains of desensitizing ink and has practical characteristics.

Procedural amendment (voluntary) 2. Name of the invention Color developer sheet for carbonless copying paper 3. Person making the amendment fl! (600) 2481 4. Column 5 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment (1) “Corn starch” in lines 5-6 of page 12 of the specification is amended to “cornstarch” do.

(2) Change “Comparative Example 1” to “Comparative Example 2” on page 14, line 2.
Correct to.

Claims (1)

[Claims] Basically, in a color developer sheet for carbonless copying paper, which has a color developer layer mainly containing a) an electron-accepting organic color developer, b) an adhesive, and c) inorganic and/or organic compound particles, The color developer is a salicylic acid derivative and/or
or a polyvalent metal salt thereof, 30% by weight of the color developing layer
The above particles are inorganic and/or organic compound particles having a particle size of 10 μm or more, and the Bekk smoothness of the color developing layer is 20 μm or more.
A color developing sheet for carbonless copying paper, characterized in that it lasts from seconds to 60 seconds.