JP3101127B2 - Pressure-sensitive recording sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive recording sheet. The present invention is particularly applicable to a predetermined partial area of 620-700n.
The present invention relates to a pressure-sensitive recording sheet capable of forming a color image having an absorption maximum in a wavelength region of m.

[0002]

2. Description of the Related Art A microcapsule layer comprising microcapsules containing an electron-donating color former (hereinafter sometimes referred to as "color former"), and an electron-accepting color developer (hereinafter "color developer"). ), And pressurize this to break the microcapsules,
A pressure-sensitive recording sheet utilizing formation of a color image by reacting a color former and a color developer has been known for a long time and has been widely used.

In recent years, barcodes have been used in a wide variety of fields as part of product management and the like. Bar code reading is generally performed using a red L having a wavelength of 620 to 700 nm.
This is performed using a bar code reader using an ED (light emitting diode) light source or a laser beam. Until now, most barcodes were printed, but recently it has been required to use a pressure-sensitive recording sheet to read a barcode coloring image formed on a developer layer of a copied sheet. It became so.

In order to read a bar code using a red optical reader having a wavelength of 620 to 700 nm as described above, the color image of the bar code formed on the color developer layer by pressure-sensitive recording must have the above-mentioned wavelength. It is necessary that the region has an absorption maximum. After reacting with a color developer as a color former of a pressure-sensitive recording sheet used for that purpose,
It is necessary to use an electron-donating color former that forms a color image having an absorption maximum in the wavelength region of 700 nm.

A generally used pressure-sensitive recording sheet is intended to easily make a copy. If a color image that can be identified by the naked eye is formed on a developer layer of a middle sheet or a lower sheet, the pressure-sensitive recording sheet is generally used. It is enough. Therefore, in a general pressure-sensitive recording sheet, an inexpensive color former that forms a color image having an absorption maximum in a visible light region on a shorter wavelength side than 600 nm is used as a color former. This makes it easy to easily use the recording sheet.

When an electron-donating color former which forms a color image having an absorption maximum in the wavelength range of 620 to 700 nm is used as a color former in the microcapsule layer of the pressure-sensitive recording sheet, It is possible to form a color image that can be read by a bar code reader. However, such color formers are expensive,
Use of a microcapsule containing such a color former on the entire surface of the microcapsule layer of the pressure-sensitive recording sheet unnecessarily increases the cost of the pressure-sensitive recording sheet, and restricts the use of the pressure-sensitive recording sheet. Not a target.

Further, since the purpose can be sufficiently achieved if the barcode coloring image is formed on a specific portion of a part of the pressure-sensitive recording sheet, 620-70 is formed on the entire surface of the pressure-sensitive recording sheet.
It is not necessary to form a layer of microcapsules containing a color former that forms a color image having an absorption maximum in the wavelength region of 0 nm. Furthermore, since the area where the barcode coloring image is formed differs depending on the user of the pressure-sensitive recording sheet, the area where the barcode coloring image is formed can be easily formed in any size at any place according to the user's request. Preferably, it can be provided.

In order to meet such a demand, a color former which forms a color image having an absorption maximum in a wavelength range of 620 to 700 nm is included on a microcapsule layer of a generally used pressure-sensitive recording sheet. It is conceivable to form a layer of the microcapsules. However, when the ink liquid containing the microcapsules containing the color former is printed by offset printing that is simple and suitable for mass production, and the layer of the microcapsules containing the above color former is formed, the microcapsule is printed during the offset printing. Since the capsule is destroyed, the function as a pressure-sensitive recording sheet is lost.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to form a color image having an absorption maximum in a wavelength range of 620 to 700 nm in a predetermined partial region, which can be easily manufactured by a simple operation. The object of the present invention is to provide a pressure-sensitive recording sheet capable of performing the following.

[0010]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
A microcapsule-containing layer containing an electron-donating color former and a solvent that forms a color-developed image having an absorption maximum in the visible light region on the shorter wavelength side than 620 nm is provided, and a part of the surface of the microcapsule-containing layer is provided. A pressure-sensitive ink comprising a microcapsule provided with an ink layer containing an electron-donating color forming agent that forms a color image having an absorption maximum in a wavelength range of 620 to 700 nm. On the recording sheet.

The preferred embodiment of the present invention is as follows.

[0012] (1) Ru Tei is contained in the ink layer an electron-donating color former is a bar code forming color former above pressure-sensitive recording sheets. (1a) The ink layer is on the microcapsule-containing layer
The above-mentioned feeling formed by offset printing
Pressure recording sheet.

(2) The ink layer has a thickness of 620 to 700 n
The above-described pressure-sensitive recording sheet, which is provided by printing an ink containing an electron-donating color-forming agent that forms a color image having an absorption maximum in a wavelength region of m.

(3) The pressure-sensitive recording sheet as described above, wherein the ink layer is provided by printing a photocurable ink.

In general, a pressure-sensitive recording sheet has a microcapsule layer (hereinafter sometimes referred to as a “microcapsule layer”) composed of microcapsules containing a color former as a support (generally, wood pulp paper, synthetic paper, etc.). The upper paper formed on one side of the above, or the middle paper in which a microcapsule layer is formed on one side of the support and the color developer layer is formed on the opposite side, and the middle paper or the color developer layer is supported. Generally, the lower paper formed on one side of the body is used in combination with the microcapsule layer and the color developer layer so as to be in contact with each other.

In the pressure-sensitive recording sheet of the present invention, a layer containing a color former (color former-containing layer) is formed on a part of the surface of the microcapsule layer containing a specific color former as described above.
It is characterized by being formed by providing an ink layer containing a specific color former.

The microcapsule layer of the coloring agent-containing layer in the pressure-sensitive recording sheet of the present invention can be formed in the same manner as the microcapsule layer of a conventional pressure-sensitive recording sheet. For example, a microcapsule layer is formed by dissolving a color former in a suitable solvent to form a microcapsule, preparing a coating liquid for forming a microcapsule layer together with a binder, a capsule protective agent, etc., applying the solution on a support, and drying. I do.

The color former contained in the microcapsule layer may be a triphenylmethanephthalide-based compound, as long as it is a color former that forms a color image having an absorption maximum in a visible light region shorter than 620 nm. Use various compounds such as fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. be able to.

Among these color formers, examples of blue color formers which form a blue color image (having an absorption maximum in a wavelength region of 580 to 620 nm) by reaction with a developer include crystal violet lactone and 3,6-bis-
Diphenylaminofluoran, 3- [4- (diethylamino) -2-ethoxyphenyl] -3- (2-methyl-
1-octyl-3-indolyl) -phthalide, 3- [4
-(Diethylamino) -2-ethoxyphenyl] -3-
(2-methyl-1-octyl-3-indolyl) -4-
Azaphthalide, 3- [4- (diethylamino) -2-ethoxyphenyl] -3- (2-methyl-1-ethyl-3
-Indolyl) -4-azaphthalide, 3- [1,1-bis (4-diethylaminophenyl) ethylene-2-yl] -6-dimethylaminophthalide and the like.

A red color image (48 due to the reaction with the developer)
Examples of the red-coloring color forming agent which has an absorption maximum in a wavelength region of 0 to 570 nm) include 2-chloro-3-methyl-6-diethylaminofluoran, 1,2-benzo-6-diethylaminofluoran, 1,2-benzo-6
-N-ethyl-N-isoamylaminofluoran, 2-
Methyl-6-N-ethyl-N-tolylaminofluoran, 2-chloro-6-diethylaminofluoran, 1,
2-benzo-6-dibutylaminofluoran, 3,3-
Bis (1-octyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, rhodamine-β-
(Γ-nitroanilino) lactam and the like.

A green color image (59) is formed by the reaction with the developer.
Examples of the green color-forming agent for producing a compound having an absorption maximum in a wavelength region of 5 to 620 nm) include 2-dibenzylamino-6-diethylaminofluoran and 2-anilino-6.
-N-ethyl-N-hexylaminofluoran, 2-octylamino-6-diethylaminofluoran, 2-
(N-methyl) anilino-6-N-ethyl-N-tolylaminofluoran, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide and the like can be mentioned.

An orange colored image (45) is formed by the reaction with the developer.
Examples of the orange-coloring color forming agent which has an absorption maximum in a wavelength region of 0 to 520 nm) include 2-methyl-6-diethylaminofluoran, 3-chloro-6-N-cyclohexylaminofluoran, and 2-t -Butyl-6-diethylaminofluoran, 1,3-dimethyl-6-diethylaminofluoran and the like.

A black color image (56) is formed by the reaction with the developer.
Examples of the black color-forming agent for producing a colorant having a maximum absorption in a wavelength region of 0 to 600 nm) include 2-anilino-3-
Methyl-6-N-methyl-N-isopropylaminofluoran, 2-anilino-3-methyl-6-N-methyl-
N-pentylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl- 6-dibutylaminofluoran, 2-anilino-3-chloro-6-
Dimethylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluoran,
2-anilino-3-methyl-6-N-methyl-N-isoamylaminofluoran, 2-anilino-3-chloro-
6-diethylaminofluoran, 2-anilino-3-chloro-6-N-methyl-N-ethylaminofluoran,
2-anilino-3-chloro-6-N-methyl-N-isopropylaminofluoran, 2-anilino-3-chloro-6-N-3-methyl-6-dimethylaminofluoran, 2- (p-methylanilino ) -3-Methyl-6-diethylaminofluoran, 2- (p-methylanilino)
-3-methyl-6-N-methyl-N-ethylaminofluoran, 2- (p-methylanilino) -3-methyl-6
-N-methyl-N-isopropylaminofluoran, 2
-(P-methylanilino) -3-methyl-6-N-methyl-N-pentylaminofluoran, 2- (p-methylanilino) -3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2 -(P-methylanilino) -3-methyl-6-N-ethyl-N-pentylaminofluoran, 2- (p-methylanilino) -3-chloro-6-dimethylaminofluoran, 2- (p-methylanilino) -3-chloro-6-diethylaminofluoran, 2- (p-methylanilino) -3-chloro-6-N
-Methyl-N-ethylaminofluoran, 2-p-chloroanilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-6-dioctylaminofluoran, 2-anilino-3-methyl- 6-N-methyl-N-dodecylaminofluoran, 2-anilino-3
-Methoxy-6-dibutylaminofluoran, 2-o-
Chloroanilino-6-dibutylaminofluoran, 2-
p-chloroanilino-3-ethyl-6-N-ethyl-N
-Isoamylaminofluoran, 2-o-chloroanilino-6-p-butylanilinofluoran, 2-anilino-3-pentadecyl-6-diethylaminofluoran,
2-anilino-3-ethyl-6-dibutylaminofluoran, 2-o-toluidino-3-methyl-6-diisopropylaminofluoran, 2-anilino-3-methyl-
6-N-isobutyl-N-ethylaminofluoran, 2
-Anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3
-Chloro-6-N-ethyl-N-isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-
N-γ-ethoxypropylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-γ-ethoxypropylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N- γ-propoxypropylaminofluoran, and the like.

One of the above color formers may be used alone, or two or more of them may be used in combination.

As the solvent, natural or synthetic oils can be used alone or as a mixture. Examples of such solvents include vegetable oil, kerosene, paraffin, naphthenic oil,
Examples include alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diarylalkane, phthalic acid ester, and the like.

The microcapsules containing the color former can be produced by any method known per se, for example, methods such as interfacial polymerization, internal polymerization, phase separation, external polymerization, and coacervation. it can. In addition, a water-soluble binder, a latex-based binder, or the like can be used as the binder, and cellulose powder, starch particles, talc, or the like can be used as the capsule protective agent. The formation of the microcapsule layer on the support can also be performed by a method known per se.

The final coating amount of the color former in the microcapsule layer is 0.03 to 0.30 g / m ² , preferably 0.03 to 0.30 g / m ² .
5 to 0.20 g / m ² is appropriate.

The ink layer of the pressure-sensitive recording sheet of the present invention contains a color former which forms a color image having an absorption maximum in the wavelength region of 620 to 700 nm by reaction with the color developer as described above. , Are locally provided on the microcapsule layer. The color former contained in the ink layer has a high P in the wavelength range of 620 to 700 nm due to the reaction with the color developer.
A device capable of forming a color image having a CS value (Print Contrast Signal) (an index indicating the appropriateness of optical reading),
In particular, it is preferable to be able to form a barcode color image that can be read reliably by a barcode reader using light having a wavelength of 620 to 700 nm.

The compound preferably used as a color former to be contained in the ink layer having such characteristics is a compound represented by the following general formula (A) or a compound represented by the following general formula (B). Examples thereof include compounds and compounds represented by the following general formula (C).

[0030]

Embedded image

(Wherein, R ^A1 , R ^A2 , R ^A3 and R ^A4 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; R ^A1 and R ^A2 or R ^A3 and R ^A4 may combine to form a ring together with the nitrogen atom to which they are attached, R ^A5 represents a hydrogen atom or an alkyl group, R ^A6 ,
R ^A7 , R ^A8 and R ^A9 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted amino group or an alicyclic amino group, and X and Y each independently represent a hydrogen atom, an alkyl group or Represents an alkoxy group).

[0032]

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(Wherein, R ^B1 , R ^B2 , R ^B3 and R ^B4 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; R ^B1 and R ^B2 or R ^B3 and R ^B4 may combine to form a ring together with the nitrogen atom to which they are attached, R ^B5 and R ^B6 each independently represent an alkyl group, and Z ^B is , The following formula:

[0034]

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Represents a divalent group having

[0036]

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(Wherein R ^C1 and R ^C2 are each independently
Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and R ^C1 and R ^C2 are bonded to form a ring with the nitrogen atom to which they are bonded; R ^C3 , R ^C4 , R ^C5 and R ^C6 each independently represent a hydrogen atom or an alkyl group, and R ^C7 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or Represents a substituted or unsubstituted aryl group, wherein Z ^C has the following formula:

[0038]

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Represents a divalent group having

In the above general formula (A), the substituted or unsubstituted alkyl group represented by R ^{A1 to} R ^A4 includes one having 1 carbon atom such as methyl, ethyl, propyl, butyl, hexyl and octyl. ~ 8 linear or branched alkyl groups,
And a substituted alkyl group in which a substituent such as chlorine atom, methoxy, phenoxy and the like is bonded to these alkyl groups.

In the general formula (A), the substituted or unsubstituted aralkyl groups represented by R ^{A1 to} R ^A4 include:
7-1 carbon atoms such as benzyl, phenethyl, cumyl, etc.
Preferred are aralkyl groups 2 and substituted aralkyl groups in which substituents such as chlorine atom, methoxy, phenoxy and the like are bonded to these aralkyl groups.

In the above general formula (A), the substituted or unsubstituted aryl groups represented by R ^{A1 to} R ^A4 include aryl groups having 6 to 10 carbon atoms such as phenyl, naphthyl and the like. And a substituted aryl group in which a substituent such as methoxy, phenoxy and the like is bonded to the aryl group.

In the general formula (A), examples of the ring formed by R ^A1 and R ^A2 or R ^A3 and R ^A4 together with the nitrogen atom to which they are bonded include a 1-pyrrolidino group, It is preferably a 5- to 6-membered heterocyclic ring such as a piperidino group.

In the above general formula (A), the alkyl group represented by R ^A5 is a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl and the like. preferable.

In the general formula (A), the halogen atom represented by R ^{A6 to} R ^A9 is preferably a chlorine atom or a fluorine atom. As the alkyl group represented by R ^{A6 to} R ^A9 , a linear or branched alkyl group having 1 to 8 carbon atoms as described for R ^A1 is preferable. As the alkoxy group, methoxy, ethoxy, propoxy, An alkoxy group having 1 to 8 carbon atoms such as butoxy, hexyloxy, octyloxy and the like is preferable. As the substituted amino group, two alkyl groups having 1 to 4 carbon atoms such as dimethylamino, diethylamino and dibutylamino are preferable. The dialkylamino group is preferable, and the alicyclic amino group is preferably a group such as pyrrolidino and piperidino.

In the above formula (A), the alkyl group and the alkoxy group represented by X or Y are preferably those described above for R ^A6 .

In the above general formula (B), the substituted or unsubstituted alkyl group, substituted or unsubstituted aralkyl group and substituted or unsubstituted aryl group represented by R ^{B1 to} R ^B4 are represented by the general formula: Those similar to those described for R ^{A1 in} (A) are preferable. ^Examples of the ring formed by bonding R ^B1 and R ^B2 or R ^B3 and R ^B4 together with the nitrogen atom to which they are bonded include those described for R ^A1 and R ^{A2 in} the general formula (A). Similar ones are preferred. As the alkyl group represented by R ^B5 or R ^B6 , those similar to those described for R ^{A5 in} formula (A) are preferable.

In the general formula (C), the substituted or unsubstituted alkyl group, substituted or unsubstituted aralkyl group and substituted or unsubstituted aryl group represented by R ^C1 , R ^C2 and R ^C7 are Preferred are the same as those described for R ^{A1 in} formula (A). As the ring formed by bonding R ^C1 and R ^C2 together with the nitrogen atom to which they are bonded, the same ring as described for R ^A1 and R ^{A2 in} formula (A) is preferable. Also, R
^{As the} alkyl group represented by ^{C3 to} R ^C6 , a compound represented by the general formula (A)
The same as those described for R ^{A5 in the} above are preferred.

Preferred specific examples of the compound represented by formula (A) are shown in Table A below. In Table A, R ^A1
R ^A9 , X and Y represent symbols in the general formula (A).

[0050]

[Table 1]

Preferred specific examples of the compound represented by formula (B) are shown in Table B below. In Table B, R ^B1-
R ^B6 and Z ^B represent the symbols in formula (B).

[0052]

[Table 2]

Preferred specific examples of the compound represented by formula (C) are shown in Table C below. In Table C, R ^C1 to
R ^C7 and Z ^C represent the symbols in formula (C).

[0054]

[Table 3]

The above-mentioned ink layer reacts with a developer to form 620.
It can be provided at any position, size, and number of regions where it is desired to generate a color image having an absorption maximum in a wavelength region of ７００700 nm (for example, to form a color image of a barcode). The formation of the ink layer can be easily performed by printing (preferably, offset printing) the ink containing the color former as described above on the microcapsule layer.

The ink containing a color former for forming the ink layer (sometimes referred to as “color former ink”) may be a vehicle type or a photo-curable type.
The photo-curing type is preferable because drying after printing is quick.

The vehicle-type colorant ink is constituted in the same manner as a conventional vehicle-type printing ink (particularly preferably, a vehicle-type ink for offset printing) except that it contains a selected specific colorant. It can be prepared similarly. For example, a vehicle-type coloring agent ink can be prepared by mixing a specific coloring agent, a white pigment such as titanium oxide, calcium carbonate, and alumina, a vehicle such as vegetable oil and mineral oil, a resin, and the like. The vehicle-type coloring agent ink does not need to be particularly added with a coloring pigment, but may contain a coloring pigment to such an extent that the coloring image is not adversely affected, if necessary.

The above vegetable oils include linseed oil, tung oil,
Drying oils such as EB oil are preferred. As mineral oil, volatile oil,
Kerosene, machine oil, petrolatum, paraffin wax and the like are used. As the above resin, a natural resin such as shellac and rosin, a modified phenol resin, a modified alkyd resin, nitrocellulose and the like are used. Further, ketones, esters, alcohols, ethers, terpenes, and the like may be added to the color forming ink as needed.

The photocurable colorant ink is a conventional photocurable printing ink (particularly preferably a photocurable ink for offset printing) except that it contains a selected specific colorant.
And can be similarly prepared. That is, the photocurable colorant ink contains a photocurable compound and a photopolymerization initiator instead of the vehicle of the vehicle type colorant ink.

Examples of the photocurable compound include, for example,
(1) Aliphatic, alicyclic, araliphatic or aromatic 2-6
(2) aliphatic, alicyclic, araliphatic or aromatic polyhydric alcohols having an alkylene oxide added thereto, Polyhydric alcohol polyacrylate or polymethacrylate, (3) polyacryloyloxyalkyl phosphate or polymethacryloyloxyalkyl phosphate, (4) polyester polyacrylate or polyester polymethacrylate, (5) epoxy polyacrylate or epoxy polymethacrylate (6) polyurethane polyacrylate or polyurethane polymethacrylate, (7) polyamide polyacrylate or polyamide polymethacrylate, (8) polysiloxane polyacrylate or policy. It may be mentioned hexane polymethacrylate or the like.

Examples of the photopolymerization initiator include benzoin alkyl ethers, acetophenones, benzyl ketals, benzophenones, and thioxanthones. Of these, acetophenones are particularly preferred, and specific examples thereof include 2-methyl-1- [4-
(Methylthio) -phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and the like.

The final coating amount of the color former in the ink layer is 0.1.
1 to 1.2 g / m ² , preferably 0.2 to 0.6 g / m ^2
2 is appropriate.

The photocurable color former ink does not need to be particularly added with a coloring pigment, but may contain a coloring pigment which does not adversely affect the color image if necessary.

The color developing agent contained in the color developing layer to be brought into contact with the color forming agent containing layer of the pressure-sensitive recording sheet of the present invention includes:
Acid clay, activated clay, attapulgite, zeolite,
Examples include clay substances such as bentonite and kaolin, metal salts of aromatic carboxylic acids, and phenol formaldehyde resins. Above all, metal salts of aromatic carboxylic acids are preferred. Preferred specific examples of the aromatic carboxylic acid metal salt include 3,5-di-t-butylsalicylic acid,
5-di-t-octyl salicylic acid, 3,5-di-t-nonyl salicylic acid, 3,5-di-t-dodecyl salicylic acid, 3-methyl-5-t-dodecyl salicylic acid, 3-t
-Dodecylsalicylic acid, 5-t-dodecylsalicylic acid,
5-cyclohexylsalicylic acid, 3,5-bis (α, α
-Dimethylbenzyl) salicylic acid, 3-methyl-5-
(Α-methylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5-methylsalicylic acid, 3- (α,
α-dimethylbenzyl) -6-methylsalicylic acid, 3-
(Α-methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl)
-6-ethylsalicylic acid, 3-phenyl-5- (α, α
Zinc salt, nickel salt, aluminum salt, calcium salt such as -dimethylbenzyl) salicylic acid, carboxy-modified terpene phenol resin, salicylic acid resin which is a reaction product of 3,5-bis (α-methylbenzyl) salicylic acid and benzyl chloride, and the like. And the like.

The above-mentioned metal salts of aromatic carboxylic acids can be used by mechanically dispersing them in an aqueous system or by dissolving them in an organic solvent.

When the metal salt of an aromatic carboxylic acid is mechanically dispersed, it can be treated with a ball mill, an art writer, a sand grinder, or the like, to obtain a dispersion.

Examples of the organic solvent for dissolving the aromatic carboxylic acid metal salt include diisopropylnaphthalene, 1-phenyl-1-xylylethane, 1-phenyl-1-isopropylphenylethane, 1-phenyl-1-ethylphenylethane, toluene, Examples thereof include xylene, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, methylene chloride, butanol, paraffin, and kerosene.

A solution obtained by dissolving a metal salt of an aromatic carboxylic acid in the above organic solvent is added to water containing a dispersant in an amount of 5 to 120% by weight, preferably 50 to 100% by weight, and emulsified and dispersed. Subsequently, the organic solvent may be removed by heating the emulsified dispersion. The metal aromatic carboxylate is generally used by dissolving it in an organic solvent in an amount of 10 to 200% by weight.

As the dispersant, an ionic or nonionic surfactant or a water-soluble polymer compound can be used. Examples of the surfactant include an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkyl sulfonate, a dialkyl sulfosuccinate, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, and a polyhydric alcohol fatty acid partial ester. . Examples of the water-soluble polymer compound include polyvinyl alcohol, modified polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyvinyl ether, sodium polystyrene sulfonate, and maleic anhydride copolymer.

In the coating solution for forming the color developer layer, styrene-butadiene copolymer latex, vinyl acetate latex, acrylate latex, polyvinyl alcohol, polyacrylic acid, maleic anhydride are used as binders. A synthetic or natural polymer such as styrene-copolymer, starch, casein, gum arabic, gelatin, carboxymethylcellulose, methylcellulose and the like may be added.

The final amount of the developer applied to the support is as follows:
^{0.1g / m 2 ~3.0g / m 2} , preferably 0.2g
/ M ^{2 to} 1.0 g / m ² is appropriate.

In the pressure-sensitive recording sheet of the present invention, the colorant-containing layer is formed by providing an ink layer containing a specific colorant locally on the surface of the microcapsule layer as described above. Has the same configuration as a conventionally known pressure-sensitive recording sheet, and can be manufactured in the same manner. For example,
Forming a colorant-containing layer on one side of a support (generally paper) to form an upper sheet, or forming a colorant-containing layer on one side of the support and forming a developer layer on the opposite side, and forming an intermediate sheet And can be. The pressure-sensitive recording sheet of the present invention is a combination of an upper sheet and a middle sheet, a combination of middle sheets, and a combination of an upper sheet or a middle sheet and a lower sheet (one in which a developer layer is formed on one side of a support). In such cases, it is common to use the color former-containing layer and the color developer layer in contact with each other.

When pressure-sensitive recording is performed using the pressure-sensitive recording sheet of the present invention, the microcapsule layer contains the color developer layer corresponding to the area of the color former-containing layer where the ink layer is not provided. 6 in the color developer layer due to the reaction between the color former and the color developer
A color image having an absorption maximum is formed in a visible light region on the shorter wavelength side than 20 nm, and a color developer layer corresponding to a region where the ink layer of the color former-containing layer is formed includes an ink layer and a microcapsule layer. A color image having an absorption maximum in the wavelength region of 620 to 700 nm is formed by the reaction between the contained color former and the developer.

When a compound represented by the general formula (A), a compound represented by the general formula (B) and a compound represented by the general formula (C) are used as a color former to be contained in the ink layer, A color image having a remarkably high PCS value is formed in the color developer layer corresponding to the region of the color-former-containing layer where the ink layer is formed. The formation of such a color image having a high PCS value is extremely advantageous when forming a color image requiring accurate reading, for example, a barcode color image. That is, when a barcode is pressure-sensitively recorded in the area where the ink layer of the pressure-sensitive recording sheet of the present invention is provided, any red optical type in which the wavelength of the light used varies over a wide range of 620 to 700 nm. Even with the use of the reading device, it is possible to reliably read the formed barcode color image substantially without a reading error.

[0075]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of Microcapsule Solution Containing Coloring Agent 2-anilino-3-methyl-6-dibutylaminofluoran (colored image formed by reaction with a developing agent) was used as a coloring agent. Has an absorption maximum at 570 nm).
2.0 g of benzylamino-6-diethylaminofluoran (a color image formed by reaction with a color developer has an absorption maximum at 605 nm) is charged with diisopropylnaphthalene 80
g of isoparaffin and 20 g of isoparaffin. Carbodiimide-modified diphenylmethane diisocyanate (trade name "Millionate MTL", manufactured by Nippon Polyurethane Co., Ltd.) is used as a polyvalent isocyanate in the obtained oily liquid.
2. g, isocyanurate of hexamethylene diisocyanate (trade name "Coronate EH", manufactured by Nippon Polyurethane Co., Ltd.) and butylene oxide adduct of ethylenediamine (addition mole number of butylene oxide to ethylenediamine: 16.8 mol, molecular weight: 1267)
0 g was dissolved to prepare a primary solution.

Next, a secondary solution was prepared by dissolving 10 g of polyvinyl alcohol and 5 g of carboxymethyl cellulose in 140 g of water. While vigorously stirring the secondary solution,
The primary solution was poured into this to form an oil-in-water emulsion. When the size of the oil droplets reaches 7.0 μm, the stirring is weakened, and then 100 ml of water at 20 ° C. is added to the emulsion.
After the addition of g, the temperature of the system was gradually raised to 65 ° C. and maintained at this temperature for 90 minutes.

To the capsule solution thus obtained, 80 g of a 15% aqueous solution of polyvinyl alcohol, 30 g of a carboxy-modified SBR latex as a solid content and 60 g of starch particles (average particle size: 15 μm) were added. Then, water was added to adjust the solid content concentration to 20% by weight, to prepare a color former-containing microcapsule solution.

(2) Preparation of Coloring Agent Ink (1) Compound of compound number (A-2) shown in Table A above (a color image formed by reacting with a developer has an absorption maximum at 700 nm) 30 g, 10 g of di-trimethylolpropane tetraacrylate, 30 g of a propylene oxide adduct of neopentyl glycol diacrylate, and 0.1 g of N-nitrosophenylhydroxylamine ammonium salt.
1 g was heated to 120 ° C. and uniformly dissolved to prepare a varnish. To 50 g of this varnish was added 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone 3 g, 2-hydroxy-2-methyl-1-phenyl-1-propanone 3 g, polyethylene wax 3 g,
Mix 10g of titanium oxide and 5g of alumina white,
The mixture was ground with a three-roll mill, and finally, 10 g of a propylene oxide adduct of neopentyl glycol diacrylate was added to the resulting mixture to prepare a photocurable colorant ink (1).

(3) Preparation of pressure-sensitive recording sheet An air knife coater was applied so that the solid content of 3.5 g / m ² of the above color former-containing microcapsule solution was applied to the surface of 40 g / m ² base paper. , And dried to form a color former-containing microcapsule layer on the surface of the paper.

Next, the above-mentioned color former ink (1) was applied onto about half the area of the microcapsule layer by an offset printing machine at a speed of 120 m / min using a metal halide lamp with an output of 8 kW. A pressure-sensitive recording sheet (1) in which a microcapsule layer is provided on the entire surface of the paper, and an ink layer is provided on a part of the microcapsule layer, is printed so that an ink of 0.0 g / m ² is printed. That is,
The microcapsule layer and the ink layer were exposed in the color former-containing layer of the pressure-sensitive recording sheet).

(4) Preparation of developer dispersion zinc 3,5-bis (α-methylbenzyl) salicylate 1
5 parts by weight, calcium carbonate 120 parts by weight, activated clay 30
Parts by weight, 20 parts by weight of zinc oxide, 1 part by weight of sodium hexametaphosphate and 200 parts by weight of water were uniformly dispersed using a sand grinder so as to have an average particle size of 3 μm to prepare a developer dispersion.

(5) Preparation of a developer coating solution 10 parts by weight of the developer dispersion obtained above was added to 400 parts by weight.
% Polyvinyl alcohol (Kuraray Co., Ltd., PVA-
203) 10 parts by weight of aqueous solution (as solid content) and 10%
Polyvinyl alcohol (Kuraray Co., Ltd., PVA-1
17) 10 parts by weight of an aqueous solution (as a solid content) was added, and water was adjusted so that the solid content concentration became 20% to obtain a developer coating solution.

(6) Preparation of a developer sheet An air knife coater was used so that the above-mentioned developer coating solution was applied to a surface of 50 g / m ² base paper at a solid content of 5.0 g / m ^2. It was applied and dried to produce a developer sheet (1).

(7) Evaluation test of pressure-sensitive recording sheet Combining the pressure-sensitive recording sheet (1) obtained above and the developer sheet (1), measurement of PCS value and bar code reading test according to the following method. Was done.

(A) Measurement of PCS value The colorant-containing layer of the pressure-sensitive recording sheet and the colorant layer of the colorant sheet are brought into contact with each other and overlapped with each other to correspond to the exposed surface of the microcapsule layer of the colorant-containing layer. A color pressure image is formed on the color developer layer by applying a load pressure of 300 kg / cm ^{2 to} both the region and the region corresponding to the exposed surface of the ink layer. After the developer sheet on which the color-formed image was formed was left in a dark place for 24 hours, the reflectance of the developer layer at 660 nm was measured using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). Measure. The PCS value is calculated from the measured reflectance by the following equation. PCS value = (reflectance of white background−reflectance of color image) / (reflectance of white background)

(B) Bar code reading test The color former-containing layer of the pressure-sensitive recording sheet and the color developer layer of the color developer sheet are brought into contact with each other and overlapped, and correspond to the exposed surface of the color capsule-containing layer of the microcapsule layer. Using a dot impact printer (8340SV, manufactured by Oki Electric Co., Ltd.), a barcode of NW-7 was printed on both the area and the area corresponding to the ink layer exposed surface, and the color of the developer sheet was developed. A color image of a bar code is formed on the agent layer. This barcode coloring image,
The reading test is performed using a pen-type barcode reader (manufactured by Datalogic, P50R-33, red LED, wavelength 660 nm).

Table 1 shows the results obtained in the above evaluation test.

Example 2 (1) Preparation of Coloring Agent Ink (2) Instead of 30 g of the compound of the compound number (A-2), the compound of the compound number (B-2) shown in Table B above (the (A color image formed by reaction with a colorant has an absorption maximum at 660 nm) (30 g) was used in the same manner as in the preparation of the colorant ink (1) of Example 1 except that 30 g of the colorant ink (2) was used. )
Was prepared.

(2) Preparation of pressure-sensitive recording sheet The procedure of Example 1 (3) was repeated except that the color former ink (2) prepared as described above was used instead of the color former ink (1). A pressure-sensitive recording sheet (2) having a microcapsule layer provided on the entire surface of the paper and an ink layer provided on a part of the microcapsule layer in the same manner as described above.

(3) Evaluation Test of Pressure-Sensitive Recording Sheet The pressure-sensitive recording sheet (2) obtained above and the developer sheet (1) produced in the same manner as in Example 1 were combined. According to the method described in Example 1, the measurement of the PCS value and the barcode reading test were performed. Table 1 shows the results.

Example 3 (1) Preparation of Coloring Agent Ink (3) The compound of compound number (C-8) shown in Table C above (a color image formed by reacting with the developer was 680 nm). A mixture of 20 g (having an absorption maximum), 20 g of a rosin-modified maleic resin and 12 g of linseed oil was heated to 140 ° C. and uniformly dissolved to prepare a varnish. 5 g of kerosene, 25 g of titanium oxide and 2 g of bentonite were added to this varnish, and the mixture was kneaded with a three-roll mill to prepare a color former ink (3).

(2) Preparation of pressure-sensitive recording sheet 3.5 microcapsules containing a color former prepared in the same manner as in Example 1 were applied to the surface of a 40 g / m ² base paper.
It was applied using an air knife coater so that a solid content of g / m ² was applied, and dried to form a color former-containing microcapsule layer on the surface of the paper.

Next, on the approximately half area of the microcapsule layer, the above color former ink (3) was printed with an offset printer at a speed of 80 m / min and 1.5 g / m ² of ink. Pressure-sensitive recording sheet (3) in which a microcapsule layer is provided on the entire surface of the paper and an ink layer is provided on a part of the microcapsule layer (that is, the pressure-sensitive recording sheet contains As for the layer, the microcapsule layer and the ink layer were exposed).

(3) Evaluation test of pressure-sensitive recording sheet The pressure-sensitive recording sheet (3) obtained above and the developer sheet (1) produced in the same manner as in Example 1 were combined and tested. According to the method described in Example 1, the measurement of the PCS value and the barcode reading test were performed. Table 1 shows the results.

As shown in Table 1, in each example,
The color image formed on the color developer layer in contact with the microcapsule layer of the pressure-sensitive recording sheet had a small PCS value and the bar code color image could not be read. The color image formed on the layer had a high PCS value, and a bar code color image was readable.

[0097]

According to the pressure-sensitive recording sheet of the present invention, a color image having a high PCS value having an absorption maximum in a wavelength region of 620 to 700 nm can be generated in a predetermined partial region. This is a pressure-sensitive recording sheet that has a remarkable effect that it can be reliably read without causing a reading error when a code color image is formed, and can be easily manufactured.

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 5/124

Claims (2)

(57) [Claims] 1. A microcapsule-containing layer containing a solvent and an electron-donating color forming agent that forms a color image having an absorption maximum in a visible light region shorter than 620 nm on a support. a portion of the surface of the microcapsule-containing layer, the micro-capsules electron donating color former to form a color image having an absorption maximum in the wavelength region of 620~700nm
A pressure-sensitive recording sheet comprising an ink layer that is contained without being included in a cell . 2. An ink layer is formed on a layer containing microcapsules.
The pressure-sensitive recording sheet according to claim 1, wherein the pressure-sensitive recording sheet is formed by offset printing .