JP2917042B2 - Light and heat sensitive recording material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a light- and heat-sensitive recording material that can be used in a printer as an output of a copying machine, a computer, and the like, and particularly relates to a porous material synthesized by an interfacial polymerization method. The present invention relates to a light and heat sensitive recording material capable of continuous gradation recording using high quality microcapsules.

[Summary of the Invention]

The present invention provides a porous microcapsule obtained by synthesizing a porous microcapsule containing a dye or pigment, a polymerizable monomer, and a photopolymerization initiator as main components on one surface of a support by an interfacial polymerization method and dispersing in a binder. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light- and heat-sensitive recording material having a structure provided with a layer, capable of performing continuous tone recording on a recording material such as paper by heat transfer, and capable of recording high-quality multicolor images.

A photopolymerization initiator having a photosensitive wavelength of λ1 and a cyan dye or pigment are combined and encapsulated in a porous microcapsule synthesized by an interfacial polymerization method together with a polymerizable monomer. A magenta dye or pigment is combined, and a photopolymerization initiator having a photosensitive wavelength of λ3 and a yellow dye or pigment are combined (λ1, λ2, λ3 are all different wavelengths, and
at least two kinds of those encapsulated in the porous microcapsules synthesized by the interfacial polymerization method together with the polymerizable monomer are dispersed in the porous microcapsule layer. By irradiating light corresponding to the photosensitive wavelength of the polymerization initiator, a latent image is drawn, and the image is heated and transferred to a recording medium by a heat roller, infrared rays, or the like, so that a continuous tone is possible and a high-quality multicolor recording image is obtained. The purpose is to get.

[Conventional technology]

As a conventional heat-sensitive recording material, a thermochromic dye is generally applied to a support such as paper, and the material is colored by heat from a thermal head or the like for recording. In addition, as a recording material to which microcapsules are applied, carbonless paper is typical, and the resolution depends on the pressing area of a pressing object such as a ballpoint pen.

Further, as recording materials using light energy and microcapsules, JP-A-58-88739 and JP-A-58-1
No. 7432 discloses a photosensitive pressure-sensitive recording sheet that creates a latent image of an image by light and destroys the microcapsule at high pressure, the inclusions of the microcapsule are released, and the dye reacts with the developer to form a color. Was getting. Further, JP-A-60-214990 discloses that an image is fixed and recorded by curing a photocurable resin in an uncolored microcapsule with light energy after image formation by heat.

[Problems to be solved by the invention]

In the conventional photosensitive pressure-sensitive recording sheet, there is a problem in that the microcapsules are destroyed at a high pressure, so that image unevenness occurs due to pressure unevenness of a pressurized portion, the apparatus becomes large, and high-speed recording cannot be performed. . Further, in the fixing type using light energy, there is a problem that a high-resolution image cannot be obtained because the resolution of an image depends on a heating element which is a heat energy source.

[Means for solving the problem]

In order to solve the above problems, in the present invention, PET
(Polyethylene terephthalate) At least two or more types of porous microcapsules, each containing a compound of the following combination as a main component and synthesized by an interfacial polymerization method, are mixed on one side of a support such as a film and dispersed in a binder. This is a photosensitive and heat-sensitive recording material having a configuration provided with a porous microcapsule layer and capable of recording a multicolor image on a recording medium such as paper by heat transfer.

・ Cyan dye or pigment, photopolymerization initiator and polymerizable monomer having a photosensitive wavelength at λ1 ・ Magenta dye or pigment, photopolymerization initiator and polymerizable monomer having a photosensitive wavelength at λ2 ・ Yellow dye or pigment, λ3 The polymerization degree of the polymerizable monomer in the porous microcapsule changes by irradiating the photosensitive wavelength of the photopolymerization initiator with light according to the image to the photosensitive heat-sensitive recording material. At the time of heat transfer, the transmission amount of the dye or pigment released from the porous microcapsules is controlled in accordance with the degree of polymerization, so that continuous gradation expression is possible and multicolor image recording is possible.

Further, in a recording material using a conventional microcapsule, a dye precursor such as a leuco material must be used, so that the recording material must be processed by applying a color developer. However, in the present invention, since the dye or pigment is encapsulated in the microcapsules, the recording medium is PP
It is possible to record an image on a recording medium that is not particularly processed, such as C paper.

[Action]

The photosensitive heat-sensitive recording material of the present invention is irradiated with light corresponding to an image signal from a CRT or the like to form a latent image corresponding to the image signal on the polymerizable monomer in the porous microcapsules, and heat roller or thermal head or infrared light is used. Dye or pigment in an amount corresponding to the image signal is transmitted from the porous microcapsules and transferred to the recording medium by heat from the microcapsules, thereby achieving continuous tone and high quality multicolor image recording.

〔Example〕

This will be described below with reference to the drawings. FIG. 1 shows a schematic view of a porous microcapsule of the present invention. The porous microcapsule 1 is synthesized by an interfacial polymerization method, and the porous microcapsule coating 2 is a porous film having many pores 3, and the inclusions in the porous microcapsule 1 are released by heat stimulation. Is what you can do. Photopolymerization initiator 5 in the porous microcapsule 1
Has an absorption wavelength as a photosensitive wavelength, generates a photopolymerization initiating species by light of the photosensitive wavelength, polymerizes the polymerizable monomer 6, and cures the polymerizable monomer 6. In addition, since the degree of polymerization can be controlled by the energy of light having a photosensitive wavelength, the amount of inclusions released from the porous microcapsules 1 can be controlled by heat depending on the degree of polymerization.

FIG. 2 is a schematic view showing the light and heat sensitive recording material of the present invention. Photopolymerization initiators 5a, 5b, 5c having different photosensitive wavelengths, a polymerizable monomer 6, and dyes or pigments 4a, 4b, 4c are respectively included on a support 9 such as a PET film and synthesized by an interfacial polymerization method. Porous microcapsules 7a, 7b,
The structure is such that a porous microcapsule layer 10 in which 7c is dispersed in a binder 8 is provided.

FIG. 3 is a schematic view showing an exposed state of the light and heat sensitive recording material of FIG. Λ1, λ according to the image signal from the CRT etc.
2. When the light 12a, 12b, 12c having the wavelength of λ3 is irradiated, the polymerizable monomer 6 in the porous microcapsules 7a, 7b, 7c according to the respective wavelengths depends on the energy of the light of the respective wavelength. It can cure and form a latent image.

FIG. 4 is a schematic view showing a heat transfer state of the light and heat sensitive recording material. Light is emitted by applying heat from a heating element 15 such as a thermal head to the porous microcapsule layer 10 of the light and heat sensitive recording material 11 on which a latent image of an image is formed as shown in FIG. Porous microcapsule coating 2 of porous microcapsules that have not been cured
The dyes or pigments 4a, 4b, and 4c are transmitted from the substrate, and transfer portions 14a, 14b, and 14c of each color according to an image signal can be obtained, and a multicolor image can be recorded.

Examples of the constituent material of the porous microcapsule film using the interfacial polymerization method in the present invention include polyamide, polyester, polyurea, and polyurethane as the porous film.

As a constituent compound of these porous microcapsule coatings, polyvalent carboxylic acid chlorides include malonyl dichloride, succinic dichloride, glutar dichloride, adipoyl chloride, sebacoyl chloride, fumaryl chloride, itaconyl chloride, terephthalic acid chloride, phthaloyl chloride And compounds such as isophthaloyl chloride, 1,3 naphthoic acid chloride, and 4,4'-biphenyl-dicarboxylic acid chloride. Further, as the carboxylic anhydride, compounds such as maleic anhydride, benzoic anhydride, and pyromellitic dianhydride, which are dehydration condensates of carboxylic acid bimolecular or dicarboxylic acid, can be used. Polyamines include 1,2-diaminopropane, 1,3
-Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,2-diaminocyclohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- Diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 1,2-diamino-2-
Methylpropane, 3,3'-diamino-N-methyldipropylamine, 1,8-methanediamine, 4,4'-ethylene-
Di-m-toluidine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4-diaminotoluene, 2,6 -Diaminotoluene, 3,4-diaminotoluene, 2,6-diamino-4
-Nitrotoluene, 1,2-dianilinoethane, 4,4'-methylenedianiline, 2,7-diaminofluorene, 3,7-diamino-2-methoxyfluorene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 3,4-diaminobenzophenone, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-
Diaminoanthraquinone, 3,5-diamino-1,2,4-triazole, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 4,5-diaminopyridine, 4,5-diamino Pyrimidine, 4,6-diamino-2-mercaptopyrimidine, 5,6-diamino-1,3-dimethyluracil hydrate, diaminomaleonitrile, 9,10-diaminophenanthrene, dimethylenetriamine, 2,4,6- Triaminopyrimidine, 4,5,6-triaminopyrimidine,
Trian Teren etc. are mentioned. Examples of the polyvalent isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, and naphthalene-1,4.
-Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'dimethoxy-4,4'-biphenyldiisocyanate, 3,3'-dimethyldiphenylmethane
4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, ethylidine Diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate,
4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1,4- (isocyanatomethyl) cyclohexane, p-4,4 ', 4 "-tri Phenylmethane triisocyanate, toluene-2,4,6-triisocyanate, polymethylene polyphenylisocyanate, 4,4'-dimethyldiphenylmethane-2,2'3,3'-
In addition to tetraisocyanate, compounds having the following structures can also be used.

Examples of the polyhydric alcohol include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3
-Butanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol,
3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol,
2-ethyl-1,3-hexanediol, 2,5-dimethyl-
2,5-hexanediol, 1,8-octanediol, 1,2,
6-hexanetriol and the like.

As the binder, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, styrene-
Butadiene latex or the like can be used.

Since the polymerizable monomer is a main component in the porous microcapsules and is also used as a solvent for dissolving or dispersing a dye or a pigment or a photopolymerization initiator, the polymerizable monomer is a liquid at ordinary temperature, The ability to smoothly release the dye or pigment from the porous microcapsules when heat is applied to the microcapsules is required. Also,
Since the size of the porous microcapsules is determined by emulsifying the encapsulated liquid in water, one of the important factors is that the polymerizable monomer as the solvent of the encapsulated liquid is insoluble in water. . If the effective polymerizable monomer is solid at room temperature, it can be used in combination with another polymerizable monomer that is liquid at room temperature. Although it does not show polymerizability, it is also possible to use a solid polymerizable monomer dissolved in water-insoluble oils (such as diisopropylnaphthalene) at room temperature, but in this case, it is completely polymerized. However, there is a problem that the dye or pigment exudes from the porous microcapsules without being completely cured. As an effective polymerizable monomer, a monomer having two or more ethylenically unsaturated groups or a polymer having an ethylenically unsaturated terminal or side chain can be used. The compounds contained therein include acrylate or methacrylate terminated polyesters, acrylate or methacrylate terminated epoxy resins, and polyhydric alcohol acrylates or methacrylates. Specifically, the compounds contained therein include:
Diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol di Methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipe Data erythritol hexa methacrylate, ethyl carbitol acrylate, ethyl carbitol methacrylate, phenoxyethyl acrylate, addition as described below, such acrylates such as phenoxyethyl methacrylate.

Here, A: acrylic acid, M: dihydric alcohol, N: dibasic acid, X: polyhydric alcohol, Y: polyhydric basic acid.

As the photopolymerization initiator, quinone, acyloin, diazoanthrone, diazonium salt, diazophenanthrone,
Disulfide, aromatic azide, aromatic ketone, aromatic azosulfonate, aromatic carbazide and the like can be used.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1: Synthesis of magenta color capsule) 1.4 parts by weight of a magenta dye was dispersed in 30 parts by weight of a polymerizable monomer, trimethylolpropane triacrylate (TMPTA: manufactured by Wako Pure Chemical Industries) using a ball mill for 24 hours. . Separately, 5 parts by weight of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the capsule membrane monomer 1 in TMPT.
Dissolved in 20 parts by weight of A. To this, the dispersion liquid in which the dye was dispersed by a ball mill was completely mixed, and 0.1 part by weight of a complex compound of safranine and triphenyl-n-butylboron (photosensitive wavelength: 500 nm) was added as a photopolymerization initiator to N, N −
It was mixed with a solution dissolved in 1 part by weight of dimethylformamide (DMF), and sufficiently stirred to obtain a capsule inclusion. Further, this liquid was mixed with a 3% (W / W) aqueous solution of a styrene-maleic anhydride copolymer (manufactured by Aldrich) and emulsified and dispersed using a homogenizer. The emulsified dispersion was continuously stirred with a mechanical stirrer while being cooled with ice water. When the temperature of the emulsified dispersion was completely equal to that of ice water, an aqueous solution in which 2.93 parts by weight of diethylenetriamine was dissolved as capsule monomer 2 was added. Interfacial polymerization was performed for about 4 hours to obtain a capsule dispersion solution, and porous microcapsules were separated by filtration to obtain magenta capsules.

(Example 2: Synthesis of cyan capsule) 0.1 parts by weight of a complex compound of methylene blue and trifel-n-butylboron (photosensitive wavelength: 650 nm) was used as the photopolymerization initiator by using the same amount of the cyan dye in Example 1. After that, a cyan capsule was synthesized in the same manner.

(Example 3: Synthesis of yellow capsule) In Example 1, 2 parts by weight of the yellow dye was used.
A combination of 1.0 parts by weight of benzophenone and 0.4 parts by weight of Michler's ketone (photosensitive wavelength: 400 n
m) used. Thereafter, a yellow capsule was synthesized in the same manner.

(Example 4: Preparation of photosensitive and heat-sensitive recording material) The porous microcapsules of each color thus synthesized were placed in an aqueous solution of 5% (W / W) styrene-maleic anhydride copolymer in the same amount and the same amount as the total amount of capsules. The dispersion is referred to as a capsule dispersion. A bar coater (produced by Yoshimitsu Seiki:
The composition was coated using a bar coater # 10) and dried sufficiently at room temperature to obtain a light and heat sensitive recording material.

(Example 6: Evaluation of photosensitive thermosensitive recording medium) A xenon short arc lamp (UYX-300, manufactured by Ushio Inc.) was used as a light source for evaluating the characteristics of the prepared photosensitive thermosensitive recording material. For the purpose of limitation, a latent image of an image is formed by irradiating each photosensitive wavelength of the photopolymerization initiator to the photosensitive thermosensitive recording material using an interference filter (manufactured by MELLES GRIOT), and a thermal head printing device (manufactured by Okura Electric: TH-M)
The image obtained by transferring to PPC paper using 1) was used.

As a result, an image corresponding to the light irradiation time was formed on the recording paper, and continuous tone recording was possible. Also, selective color development by light was possible, and a multicolor image could be formed. Since the polymerizable monomer was cured by light irradiation and the dye was not colored in the portions where color development was unnecessary, a good image could be obtained without background fogging.

〔The invention's effect〕

As described above, the present invention synthesizes porous microcapsules containing a dye or pigment, a polymerizable monomer, and a photopolymerization initiator on a support such as a PET film by an interfacial polymerization method and dispersed in a binder. As a configuration with a porous microcapsule layer, multicolor image recording with continuous tone and high image quality with little background fogging, good whiteness in the white part, continuous tone and high image quality is recorded on plain paper by heat transfer to the recording medium It is possible to provide a light- and heat-sensitive recording material which can be used.

[Brief description of the drawings]

FIG. 1 is a schematic view of a porous microcapsule used in the light and heat sensitive recording material of the present invention, FIG. 2 is a schematic view of the light and heat sensitive recording material of the present invention, and FIG. It is a schematic diagram showing an exposure state. FIG. 4 is a schematic view showing a heat transfer state of the light and heat sensitive recording material. DESCRIPTION OF SYMBOLS 1 ... Porous microcapsule 2 ... Porous microcapsule film 3 ... Porous part 4 ... Dye or pigment 4a ... Cyan dye or pigment 4b ... Magenta dye or pigment 4c ... Yellow dye or Pigment 5 Photopolymerization initiator 5a Photopolymerization initiator of λ1 photosensitivity 5b Photopolymerization initiator of λ2 photosensitivity 5c Photopolymerization initiator of λ3 photosensitivity 6 Photopolymerizable monomer 7a Photosensitive with λ1 Porous microcapsules 7b... Porous microcapsules sensitive to λ2 7c... Porous microcapsules sensitive to λ3 8... Binder 9... Support 10... Porous microcapsule layer 11. Material 12a: Irradiated light λ1 12b: Irradiated light λ2 12c: Irradiated light λ3 13a: Porous microcapsules cured by λ1 13b: Porous microcapsules cured by λ2 13c: Porous cured by λ3 Microcapsules 14a Cyan transfer part 14b Magenta transfer part 14c Yellow transfer part 15 Heating element

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-81679 (JP, A) JP-A-63-65436 (JP, A) JP-A-58-211488 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03F 7/004 G03F 7/028

Claims (6)

(57) [Claims] 1. A dye or pigment on one side of a support,
A polymerizable monomer capable of being crosslinked and cured by light energy and a photopolymerization initiator capable of initiating polymerization of the polymerizable monomer by irradiating light having a photosensitive wavelength as a main component, and A microcapsule layer in which at least two types of porous microcapsules having a porous microcapsule film formed by interfacial polymerization of an isocyanate and a polyvalent amine are provided in a binder is provided. A light and heat sensitive recording material capable of recording a color image. 2. The porous microcapsule, wherein the capsule film forming the outer shape is a porous film having a large number of pores, and the porous film of the porous microcapsule is applied by applying heat from the outside. 2. The light- and heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording material has a function of allowing the inclusions to pass through the fine pores and being released to the outside of the porous microcapsules. 3. The photopolymerization initiator, which itself undergoes a chemical change by light energy to generate a polymerization initiation species, or a sensitizer which causes a chemical change by light energy, and a sensitizer which causes a chemical change by light energy. 2. The light- and heat-sensitive recording material according to claim 1, comprising a polymerization initiating species generator which reacts with a sensitizer to generate a polymerization initiating species. 4. The photopolymerization initiator has a photosensitive wavelength of 580 nm to 780 nm.
nm polymerization initiator, photosensitive polymerization wavelength 460nm ~ 620nm red polymerization initiator, photosensitive wavelength 380nm ~ 520nm selected from yellow polymerization initiator, the lack of polymerization initiator photosensitive wavelength is separated by 50nm or more. The light- and heat-sensitive recording material according to claim 1, wherein: 5. The light- and heat-sensitive recording material according to claim 1, wherein the polymerizable monomer is a compound which is crosslinked and cured by light energy. 6. The binder has a function of fixing the porous microcapsules in the porous microcapsule layer and preventing the microcapsules from being detached from the support, and rapidly reduces the viscosity when heat is applied. 2. The light and heat sensitive recording material according to claim 1, wherein the inclusions released from the porous microcapsules can be transferred to the recording medium.