JPH04263986A - Speed-increasing no-carbon paper - Google Patents

Abstract

PURPOSE: To obtain a rapid image generation and a high density image at the time of a low temperature of a carbonless copy composition. CONSTITUTION: A coating composition for use in carbonless copying system including (1) a resin dispersion which is a phenol/aldehyde condensation product formed by an interaction of an alkyl-substituted salicylic acid, an alkyl- substituted phenol, an aldehyde and a metal source, (2) a binder and (3) a pigment. This coating composition provides faster imaging in carbonless system than a conventional coating, at a temperature below room temperature.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION This invention relates to non-carbon copying systems, and more particularly to front non-carbon (C
F) Concerning compositions for use in paper.

0002

BACKGROUND OF THE INVENTION Standard non-carbon copying systems, or pressure sensitive copying paper, include a number of supports, e.g., sheets of paper arranged in a stack, each sheet having one or more coatings on its surface. have. Such a laminate is such that when external pressure applied by a typewriter, pen, or other instrument is applied to the outermost sheet, it will produce a colored image on at least one surface of each sheet of the laminate. It is designed to.

[0003] The top sheet of the laminate to which pressure is applied is
It has a coating on its backside, which typically contains a large number of microcapsules containing an initially colorless, chemically reactive, color-forming dye precursor as a filler material. The surface of the next sheet adjacent to the back side of the top sheet is coated with a material containing components such as phenolic resins or reactive clays capable of reacting with the colorless dye precursor contained in the microcapsules to develop color. . Therefore, an external force applied on the surface of the top sheet ruptures the microcapsules on the back side, liberating the colorless dye precursor, which then reacts with the reactive components on the coated surface of the adjacent sheet, and the external pressure is applied. Generate a colored image corresponding to the range. Similarly, a large number of colored images are generated on each successive sheet making up the laminate by external pressure that destroys the large number of microcapsules supported on the back side of each sheet.

[0004] The plurality of sheets of this non-carbon copying system is known in the art as back non-carbon paper using the term CB.
The front back non-carbon paper is designated as CFB, and the front non-carbon paper is designated as CF. This CB or transmission sheet is usually the top sheet of the laminate and the sheet to which external pressure is applied. Multiple CFB sheets are multiple intermediate sheets in a laminate, each of which can be imaged on its front surface by pressure, and which can be imaged from its reverse side to the surface of the next sheet by microscopic images. It is also possible to convey the contents of the capsule. C.F.
Alternatively, the recording sheet is a bottom sheet, coated only on its surface, so that an image can be formed on the surface.

[0005] Although it is common to have a coating containing a plurality of microcapsules on the back side of these sheets and a coating containing a component reactive with the capsules on each surface of these sheets, the reverse arrangement is also possible. It is possible. Furthermore, one of these reactive components may not only be applied as a surface coating layer, but may also be supported within the sheets themselves. Also, components that react with the colorless dye precursor may be encapsulated in microcapsules.

[0006]

BACKGROUND OF THE INVENTION In recent years, non-carbon copying paper has been used in a wide range of applications outdoors or in rooms affected by outdoor temperatures. There is currently a need for a non-carbon reproduction system that maintains its performance, particularly color development rate and density in any environment, including the low temperatures that may be encountered outdoors. Typical examples of this kind of use are the use of a credit card at an outdoor gas station, the outdoor use of a credit card to deliver food (e.g. pizza), the records and logbooks of police or fire personnel outdoors, etc. including use for.

Generally located in Schenectady, New York. Chemicals (Schenecta)
dy Chemicals, Inc. A zincated alkylphenol novolak resin dispersion manufactured and sold by the Applicant under the trade name "HRJ-2456" is used by the applicant in a non-carbon set and provides rapid image formation at or below room temperature. When it was generated, it was found that there were some defects.

[0008] Accordingly, it is an object of the present invention to provide (i) a composition applicable to at least one sheet of a non-carbon reproduction system to provide rapid image generation when contacted with a dye precursor; (ii) a dye precursor; a composition (i
ii) To provide a composition that can be applied to at least one sheet of a non-carbon reproduction system and that allows the non-carbon reproduction system to operate effectively at or below room temperature.

[0009]

SUMMARY OF THE INVENTION The present invention provides a coating composition comprising a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment. The present invention relates to coating compositions for use in non-carbon reproduction systems that can provide enhanced image generation at temperatures below about 40 degrees Fahrenheit.

The present invention further provides a recording support; (1) a phenol/aldehyde condensation product resin produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; (2) a binder;
and a first image-forming component which is a mixture of a pigment and a pigment; and an auxiliary image-forming component capable of reacting with the first image-forming component and encapsulated in microcapsules to produce a colored product;
a non-carbon copying system in which the image-forming component and the auxiliary image-forming component are arranged in parallel contact with each other such that application of a selected range of pressure on the non-carbon system produces a colored image in a corresponding range of the recording support; Yes, about 4.
Summary: A non-carbon reproduction system that can provide enhanced image generation at temperatures below 40°F.

The present invention also provides a recording support; a transmission support;
A mixture of (1) a phenol/aldehyde condensation product resin produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal, (2) a binder, and (3) a pigment, and the recording support. a first imaging component supported by the transfer support; an auxiliary imaging component encapsulated in a plurality of microcapsules supported by the transfer support and capable of reacting with the first imaging component to produce a colored product; Abstract: A non-carbon reproduction system in which one image-forming component is arranged in parallel contact with the auxiliary image-forming component such that application of a selected area of pressure on the non-carbon system produces a colored image in a corresponding area of the recording support. do.

The invention also provides methods of using the carbonless replication system of the invention at temperatures below room temperature, including temperatures below about 40°F.

[0013]

[Operation] Next, the present invention will be described in detail.

According to the present invention, a coating composition for use in a carbonless reproduction system comprises an alkyl-substituted salicylic acid,
It consists of a resin, which is an aldehyde/phenol condensation product produced by the interaction of an alkyl-substituted phenol, an aldehyde, and a metal source; a binder; and a pigment. Preferably, the coating composition is applied to a front non-carbon (CF) sheet of a non-carbon reproduction system.

According to the applicant, this aldehyde/phenol condensation product resin of the present invention is disclosed in European Patent Application No. 0,338,808. European Patent Application No. 0,338,808 discloses this resin and a method for making this resin.

As disclosed in European Patent Application No. 0,338,808, preferably the alkyl-substituted salicylic acid is substituted with at least one alkyl group containing three or more carbon atoms. Ru. More preferably, the alkyl group contains at least 4 carbon atoms,
Even more preferably it contains 4 to 12 carbon atoms. In particular, the following chemical formula 1

[0017]

[Formula: R is an alkyl group containing 4 to 12 carbon atoms, in particular the R group is octyl or nonyl, especially tertiary octyl (derived from diisobutylene) and nonyl (
(derived from propylene trimer) is preferred. This R group may be a dodecyl group, and preferred groups are:
Salicylic acid with a certain nonyl group is useful.

Preferably the alkyl component contains at least one alkyl group containing at least 3 carbon atoms, more preferably from 4 to 12 carbon atoms. Preferably, the phenols are phenyls substituted in the para position with an alkyl group containing from 4 to 12 carbon atoms, especially in the tertiary
butyl, tertiary octyl, nonyl (derived from propylene trimer) and dodecyl. A preferred material is a tertiary octyl group. The alkyl substituent at the para position is represented by R' in Formula 2 below.

Preferably, the aldehyde is formaldehyde, even though the formaldehyde can be supplied, for example, from paraformaldehyde or a similar source of formaldehyde.

A preferred metal source is zinc oxide.

The exact composition of the product is not known, but formula 2

[0022]

[Case 2] It seems to have.

The phenol/aldehyde condensation product may be synthesized by combining an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde, a metal source, and water and heating.

European Patent Application No. 0,338,808 discloses a suitable method of manufacturing a general example. That is,
750 parts of nonylsalicylic acid, 523 parts of pt-octylphenol, 199 parts of 50% formaldehyde solution, Daxad 30 (W.R.Grace)
R. Grace & Co. ) 3 parts of a proprietary composition of wetting agent available from Co., Ltd., 69 parts of water and 103 parts of zinc oxide are heated, stirred and brought to reflux. After the reaction has occurred, the heating is stopped and the wetting agent is added. The mixture is stirred, cooled, and further diluted with water. The mixture is then filtered to obtain the phenol/aldehyde condensation product.

Preferably, the resin dispersion that is a component of the coating composition of the present invention is manufactured by Schenectady, Inc., Schenectady, New York. The product name of the resin manufactured and sold by Chemicals Co., Ltd. is “HRJ-10176” or “HRJ-
10802".

According to the invention, the resin component of the coating composition of the invention is present in an amount varying preferably from 7 to 40 parts, more preferably from 10 to 20 parts, per 100 parts of pigment and resin. There is. Unless otherwise indicated, "parts" in the present invention mean parts by weight.

The pigment component of the coating composition of the present invention may be any of a number of known pigments useful in coating compositions for non-carbon copying papers. For example, those pigments include, for example, Ansilex (a kaolin product manufactured by Engelhard), Hy-dral (an alumina hydrate manufactured by Alcoa), M-6
0 (calcium carbonate-70% dispersion in water manufactured by Mississippi Lime Company) and Ex-silon
(Kaolin product manufactured by Engelhard)
You can choose from. The pigment is preferably used in amounts varying from 60 to 93 parts, more preferably from 80 to 90 parts per 100 parts pigment and resin.

The binder component of the coating composition of the present invention is:
It can be any of a number of known binders useful in coating compositions for non-carbon copying papers. For example, those binders include Penford G
um (PG) 360, Penford Gum (P
G) 380 (both manufactured by Pennick. & Ford) and latex. The binder is preferably used in amounts varying from 5 to 25 parts, more preferably from 10 to 20 parts per 100 parts pigment and resin.

Other components may be present in the coating composition of the present invention. These are, for example, Tamol
850 (anionic polymer type dispersant) and Col
dispersants such as loid 230 (a dispersant manufactured by Colloid Inc.); pH adjusters such as ammonia 26°Be (alkaline pH adjuster); and Sunrez 7
A crosslinking agent such as 00m (a starch crosslinking agent manufactured by Sun. Chemicals) may also be included.

A non-carbon reproduction system according to the present invention includes a recording support, a first image-forming component, and an auxiliary image-forming component. The first image-forming component according to the invention is a phenol/phenol produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source.
It is a mixture of a resin dispersion that is an aldehyde condensation product; a binder; and a pigment. As previously explained herein, the resin is preferably "HRJ-10176"
Alternatively, it may be "HRJ-10802". The auxiliary image-forming component is encapsulated in a number of microcapsules and can react with the first image-forming component to generate a colored image. The first image-forming component and the auxiliary image-forming component are arranged in parallel contact with each other such that application of a plurality of selected areas of pressure on the non-carbon system produces a colored image on corresponding areas of the recording support. let

In accordance with the present invention, the auxiliary image-forming component is preferably a colorless dye precursor encapsulated in a plurality of microcapsules. Representative colorless dye precursors that can be used as auxiliary imaging components include, for example, crystalline violet lactone, benzolleucomethylene blue, rhodamine lactam, p-toluenesulfonate of Michler's hydrol, and colorless dye precursors that are colorless when in contact with acidic materials. This includes any of the various chromophoric compounds that can vary from color to colored form.

According to the present invention, the microcapsules used to coat the dye precursor can be composed of a shell or wall of polymeric material, can generally have continuous walls, and can have a diameter of about 0.5 mm. It may vary from 1 to 500 microns. Preferably, the auxiliary image generating component is
It is supported by a transmission support in parallel contact with the recording support. The imaging component may be adhered to the transfer support by using known binders.

According to the invention, the recording support and the transmission support are arranged adjacent to each other so that the first imaging component and the auxiliary imaging component are in contact with each other and in juxtaposition, ie, in a pressure sensitive state. . When pressure is applied to the transfer support at a location corresponding to the area containing the auxiliary imaging component, the microcapsules of the auxiliary imaging component are ruptured and the contained dye precursors are released, upon which the standard colored image is produced. contacts and reacts with the first image-forming component on the recording support to produce a.

According to the invention, both the first image-forming component and the auxiliary image-forming component can be applied to the recording support. Additionally, a transfer support can be used, with an auxiliary imaging component supported on the transfer support and a first imaging component supported by a recording support. Accordingly, the external force required to rupture the microcapsules containing the auxiliary imaging component may be applied to the recording support itself or, in implementations using a transfer support, to the transfer support.

According to the present invention, the non-carbon reproduction system of the present invention may include a number of intermediate supports, or CFB sheets, which are placed between the transfer support and the recording support. These intermediate CFB support sheets are coated on the front side of the recording support with a first imaging component (corresponding to the component on the recording support) and coated on the back side with the auxiliary imaging component (corresponding to the component on the transfer support). (corresponding to the ingredients) and are similarly applied. Therefore, those intermediate sheets can serve as both recording and transmission sheets;
They can also produce colored reaction products on their front side, like recording supports, and enable the transfer of auxiliary image-forming components to successive sheets, like transfer supports. This allows the formation of multiple copy sheets, each sheet containing a standard colored image.

[0036]

EXAMPLES The following specific examples are provided to provide a better understanding of the invention, but they are given by way of teaching and are not meant to be limiting in any way.

The coating composition of each example was applied to the recording support using manual drawdown with a wire round rod. The slurry was placed on the paper and the circular wire rod was pulled across the surface of the paper by hand to spread the slurry coating. After coating the support, the support was placed in a drying oven until the coating reached ambient humidity. Example 1 The following CF formulation was prepared and a 12 lb. voice.
East. Boise East Coast
t) Applied as above at 6.7 g/m2.

A. Standard CF coating
dry wet
Ansilex 20.02
40.04 Hydral 7
10-B 65.46 10
0.70 Tamol 850
1.30 4.34
H2O-
29.51 HRJ-2
456 16.42
30.30 PG 290
22.0 73.3
3 12
5.20 278.22 B. Speed-enhancing CF coating of the present invention
dry wet
Ansilex 20.02
40.04 Hydral 7
10-B 65.46 10
0.7 Tamol 850
1.30 4.34
H2O-
26.6 HRJ-101
76 16.42
33.21 PG 290
22.0 73.33
125.
20 288.22
45
% solids The CF coating described above was combined against standard microcapsule CB paper and imaged using a standard calendar tester at approximately 21.1°C (70°F) and 0°C (32°F). It was done. % of images generated in this way
Reflectance was determined using a Photovolt at 30 seconds, 5 minutes, 20 minutes and 24 hours after image generation. The lower the % reflectance, the darker the image. The results obtained are shown in Table 1 below.

[0039]

[Table 1] ――――――――――――――――――――――――
――――――――――
% reflectance
Approximately 21.1°C (70°F)
30 seconds
5 minutes 20 minutes
24 hours――――――――――――――――
―――――――――――――――― Standard CF coating 64.6 54.
9 53.1 5
2.5 (HRJ-2456) Speed-up CF coating 54.9
54.2 53.4
52.9 (HRJ-10176)
――――――――――――――――――――――――
――――――――――
0°
C (32°F)
5 seconds 5 minutes
20 minutes 24 hours――――――――
――――――――――――――――――――――――
- Standard CF coating 90.5
79.1 58.7
57.0 (HRJ-2456) Speed-up CF coating 80.5
59.9 54.7
55.7 (HRJ-10176)
――――――――――――――――――――――――
――――――――――Table 1 shows the temperature at room temperature and 0°C (32°C).
Both Figures F) show that the speed increasing coating of the present invention (HRJ-10176 resin) provides faster image generation than the standard CF coating (HRJ-2456 resin). However, as can be seen from Table 1, its faster image generation is 0
It is further accentuated at 32°F (°C). 0°C (32°F)
), it can be seen that a non-carbon paper using the resin of the present invention requires 5 minutes to produce an image with a % reflectance of 59.9. On the other hand, using a standard CF coating, its % reflectance is 79.1 after 5 minutes and it takes 20 minutes to produce an image with a % reflectance of 58.7. Example 2 Low cost pigment composition
dry wet
Exsilon 58.86
102.14 M-60
32.3
49.59 Water
-35.08
Colloid 230
1.61 3.98 Ammonia 26°Be −
0.67 resin
17.85 35.61
PG 380 1
3.91 49.85 Sunr
enz 700m 0.44
1.06
125.00 278.0
The following compounds were used as "resins" in the above compositions.

1) HRJ-2456 (control) 2) HRJ
-10176 (manufactured sample) 3) HRJ-10802 The three compositions described above were tested at approximately 20°C (68°F) and 0.
It was tested and its % reflectance was determined using a low pressure calender tester at 32°F. The results are shown in Table 2 below.
As shown in

[0041]

[Table 2] ――――――――――――――――――――――――
――――――――――
% reflectance approximately 20°
C (68°F) CF
30 seconds 5 minutes 20
Minutes 24 hours――――――――――――
――――――――――――――――――――――
HRJ-2456 72.2
55.4 53.
2 53.1 HRJ-10
176 60.2
55.2 54.1
53.2 HRJ-10802
57.3 53.0
52.5 51.
1 ――――――――――――――――――――――
――――――――――――
% reflectance
0°C (32°F)
30 seconds 5 minutes
20 minutes 24 hours――――――――
――――――――――――――――――――――――
--HRJ-2456
92.1 81.3
59.9 57.8 HR
J-10176 81.3
60.3 55.1
56.0 HRJ-10802
80.9 5
9.8 53.1
52.9 ――――――――――――――――――
――――――――――――――――From Table 2, both HRJ-10176 and HRJ-10802 according to the present invention are compared to conventional HRJ-2456 at room temperature and 0°C (32°F).
It can be seen that this results in even faster image generation. Example 1
Its faster image generation, such as
), for example, the HRJ-2456 formulation has a
It takes 20 minutes to achieve a reflectance of 59.9, while HRJ-10802 has a % reflectance of 59.8 after 5 minutes. Example 3 HRJ-10176 resin manufacturing test HRJ-10176 manufacturing sample (55 gal dr.
um) was used for laboratory testing (HRJ
-2456 sample and HRJ-10176 laboratory sample).

Comparison-HRJ-2456 material
dry wet
Jun Ansilex
20.02 40.04
Hydrol 710B
65.46 100.70
Tamol 850
1.30 4.34
water
-29.01
HRJ-2456
16.42 30.80
PG 290 2
2.00 73.33
125.2
0 278.22 45% solids-
Coated on 12 lb. Boyce Pond 76 g/m2 Control Lab Sample HRJ-10176 Material
drying
Moisture
Ansilex 20.02
40.04 Hy
drol 710B 65.46
100.70 Tamol
850 1.30
4.34 Water
−
29.01 Laboratory batch HRJ-10176 16.42
30.80 PG 290
22.00 7
3.33
125.20 278.22
45% solids - 12 lbs. voice lbs. 7.7
Coated on g/m2 Manufacturing sample HRJ-10176 Material
dry wet
Jun Ansilex
20.02 40.04
Hydrol 710B
65.46 100.70
Tamol 850
1.30 4.34
water
-29.01
Manufacture HRJ-10176 1
6.42 30.80
PG 290 22.
00 73.33
125.20
278.22 Coated on 45% solids - 12 lb voice pond 7.7 g/m2 These three resin compositions were imaged at room temperature using microcapsule coated CB paper. The results obtained are shown in Table 3 below.

[0043]

[Table 3] ――――――――――――――――――――――――
――――――――――
% reflectance
CF 30
seconds 5 minutes 20 minutes――――――――――――――――――――――
----------- HRJ-2456 (control)
72.30 53.50
52.20 HRJ-10176 (Laboratory)
55.20 52.00 52.
20 HRJ-10176 (Manufacturing) 5
5.40 54.50 53.50-
――――――――――――――――――――――――
――――――――As shown in the above results, HRJ-101
The manufacturing material of 76 is similar to that of the laboratory sample;
Both show improved results over HRJ-2456.

Although Applicants do not wish to be limited by any chemical theory contained in the present invention, it is our understanding that the resins of the present invention (
It has been postulated that the improved results achieved over the prior art (HRJ-2456) by e.g. Salicylic acid can act as a facilitator to help the dye react with the resin.

[0045]

As explained above, since the non-carbon copying composition of the present invention uses HRJ-10176 or HRJ-10802 in place of the conventional resin dispersion HRJ-2456, when it comes into contact with the dye precursor, Fast image generation and high density images can be achieved below room temperature.

Claims (3)

[Claims] 1. A coating composition for use in a non-carbon reproduction system comprising a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment. approximately 4.4°C (40°F)
) Compositions capable of providing accelerated image generation of non-carbon systems at temperatures of: 2. A recording support; a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a resin dispersion which is a pigment. one image-forming component; an auxiliary image-forming component that is encapsulated in microcapsules and is capable of reacting with said first image-forming component to generate a colored reaction product; said first image-forming component and said auxiliary image-forming component are in parallel contact with each other; A non-carbon reproduction system arranged such that the application of pressure in selected areas on the non-carbon system produces a colored image in corresponding areas on the recording support at a temperature of about 4.4°C ( A non-carbon reproduction system capable of providing enhanced image generation at temperatures below 40°F. 3. A recording support; a transmission support; a phenol/aldehyde condensation product resin produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment. one image-forming component; and an auxiliary image-forming component that is microencapsulated and capable of reacting with the first image-forming component to generate a colored reaction product; the first image-forming component and the auxiliary image-forming component are in parallel contact with each other. a non-carbon copying system arranged such that application of selected areas of pressure on the non-carbon system forms a colored image on corresponding areas of the recording support at a temperature of about 4.4°C; A non-carbon reproduction system that provides enhanced image generation below (40°F).