JPH10226155A - Hot melt type ink-jet recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot melt type (solid) ink-jet recording paper which has good adhesion to solid ink, translucency required for an electric decoration signboard, and paper feeding/delivery properties. SOLUTION: A hot melt type ink-jet recording paper which receives molten hot melt type ink which is solid at room temperature and ejected into air for recording has structure in which a hot melt type ink receiving layer is formed on the surface of a support which is a translucent porous stretched film containing white inorganic fine powder through a primer coating layer of a specified composition, and the light transmittance of the paper is 30-70%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an illuminated signboard using internal illumination, aesthetics, and the like, because of the absence of graphic or character bleeding, the excellent adhesion of printing ink to recording paper, and its translucency. The present invention relates to a translucent hot-melt ink jet recording paper used for posters having excellent transparency.

[0002]

2. Description of the Related Art Conventionally, aqueous ink compositions have been widely used as ink compositions for ink jet recording paper. However, there are the drawbacks that the ink dries slowly and that the print tends to bleed. For the purpose of remedying such drawbacks, using a hot-melt type ink composition made of wax or the like that is solid at room temperature, it is liquefied by heating, is sprayed onto paper with some energy applied, and is cooled and solidified on paper. A hot-melt ink jet recording paper for forming recording dots has been proposed (US Pat. No. 4,751, 51).
528, U.S. Pat. No. 4,758,396,
U.S. Pat. No. 4,931,095, JP-A-3-50
No. 1470, No. 5-202327, No. 5-31110
No. 1, No. 7-133451, No. 7-70490, No. 8-3493, No. 8-3495, No. 8-3499
Nos. 8-67841, 8-67842, and JP-A-7-503498).

The features of this hot-melt type (solid) ink jet recording system include plain paper, recycled paper, Japanese paper, OH
High-density color prints can be made regardless of the type of paper such as film for P (overhead project), coated paper, corrugated cardboard, and trace paper; print quality can be as good as a laser printer; ink can be printed even if the printed paper gets wet with water Are not exuded, and a large screen printing of a poster or CAD and a large drawing can be performed as compared with the laser printer method. On the other hand, it has been pointed out that if the printed (printed) surface is strongly rubbed, the print is peeled off, or if the printed matter is folded, the printed portion of the folded portion is peeled off.

[0004]

DISCLOSURE OF THE INVENTION The present invention is a hot-melt type (solid) which is excellent in adhesion of solid ink, has translucency required for an electric signboard, and has good paper supply / discharge properties. The purpose is to provide inkjet recording paper.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a hot-melt ink-jet recording sheet which heats and melts a solid-state hot-melt ink at normal temperature to receive and fly the molten ink. A translucent microporous film made of a stretched resin film containing a white inorganic fine powder is used as a support (I), and a primer coating layer (II) having the following composition is placed on the surface of the support (I) via a support. A hot melt ink receiving layer (III) is provided, and the opacity of the recording paper is 30 to 70%.

The primer coating layer (II) comprises: (a) a tertiary nitrogen atom of a polymer obtained by copolymerizing the following monomers (i), (ii) and (iii) with a cationizing agent; A quaternized nitrogen-containing acryl-based resin which is a quaternized amphoteric compound: 100 parts by weight,

Embedded image (Iii) Other hydrophobic vinyl monomers 0 to 80% by weight [where R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. ]

(B) Ethyleneimine adducts of polyethyleneimine, poly (ethyleneimine-urea) and polyaminepolyamide, or alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified products thereof A polyimine compound selected from the group consisting of a body: 20 to 300 parts by weight; (c) an epichlorohydrin adduct of polyamine polyamide: 20 to 300 parts by weight; It was obtained.

[0008]

The presence of the primer layer (II) on the recording paper makes it difficult for the received solid ink to peel off from the support (I). In particular, when the surface layer of the support of the recording paper contains an inorganic fine powder, the inorganic fine powder projecting from the surface layer exhibits an anchoring effect, and is formed on the surface layer by stretching. The primer penetrates into the fine cracks, which also exerts an anchoring effect, thereby strengthening the adhesion of the solid ink.

Further, since the support made of a stretched film has fine voids (voids), even if the hot melt ink heated to 50 to 150 ° C. adheres to the recording paper, the voids have a heat insulating property. Therefore, the support does not thermally shrink, and no wrinkles are generated on the recording paper due to the heat shrinkage. In addition, by using solid ink, the printed material can be clearly recognized for both transmitted light and reflected light when used for an illuminated signboard, and when used for a poster, because of the appropriate translucency of the paper. It is soft and has excellent aesthetics.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The hot melt type ink jet recording paper of the present invention will be described in more detail below. (I) Support: The support (I) provided with the primer coating layer (II) is a stretched film of a thermoplastic resin containing an inorganic fine powder and is translucent. This stretched film has a porosity of 5 to 20 represented by the following formula inside the film.
%, Preferably 5 to 15%.

[0011]

(Equation 1)

A translucent film satisfying such physical properties can be adjusted by the type of the white inorganic fine powder, the type of the pigment and the thermoplastic resin, the stretching temperature, the stretching ratio, and the structure of the layer. For example, a biaxially stretched film of a thermoplastic resin film containing 5 to 40% by weight of a white inorganic fine powder is used as a base material layer (A). A uniaxially stretched thermoplastic resin film containing 0.3 to 5% by weight of a pigment and 10 to 60% by weight of a white inorganic fine powder selected from calcium carbonate, calcined clay, silica and zeolite is used as a front and back layer (B, B). ′).

White inorganic fine powder The white inorganic fine powder used for the substrate layer (A) includes:
Heavy calcium carbonate, diatomaceous earth, calcined clay, clay, silica, talc, zeolite, titanium oxide, barium sulfate, zinc oxide and the like having an average particle size of 0.03 to 16 microns can be used. The combination of the white inorganic fine powder used for the front and back layers is as described above. In particular, the combination of titanium oxide and calcium carbonate or calcined clay is economical,
Good in terms of weather resistance.

Thermoplastic resin The thermoplastic resin for the film material includes propylene homopolymer, propylene / ethylene copolymer, propylene / propylene copolymer.
Butene-1 copolymer, propylene / ethylene / butene
Propylene-based resins such as 1 copolymer and propylene / 4-methylpentene-1 copolymer;
70 g / cm ³ high-density polyethylene, olefin resins such as poly (4-methylpentene-1); polyesters such as polyethylene terephthalate, polybutylene terephthalate; polyamides such as nylon 6, nylon 6,6; polyphenylene sulfide; A thermoplastic resin having a melting point of 132 ° C. or more such as polycarbonate can be used. The copolymer may be a random copolymer or a block copolymer.

These thermoplastic resins having a melting point of 132 ° C. or more include low-density polyethylene, linear low-density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylate copolymer, and ethylene / methacrylic acid copolymer. Stretching can be facilitated by blending 3 to 15% by weight of a low melting point resin having a melting point of 80 to 126 ° C. such as a metal salt (Li, Na, K, Zn, Al, etc.), polystyrene, petroleum resin and the like.

The stretching is performed using a difference in peripheral speed between rolls, a tenter, a mandrel and the like. The stretching ratio is 3.5 to 3.5 in the machine direction.
7 times and 3.5 to 12 times in the horizontal direction. The stretching temperature is determined by the opacity (JIS P-813) of the resulting translucent film.
8) is 30 to 70%, for example, when the thermoplastic resin is a propylene homopolymer, the longitudinal stretching is performed at a temperature 5 to 15 ° C. lower than the melting point of the resin, Stretching is performed at a temperature 2 to 15 ° C. higher than the melting point of the resin.

The translucent film may be a single-layer biaxially stretched film, but from the viewpoint of the waist strength and the surface strength of the front and back layers, the base layer is a biaxially stretched film and the front and back layers are a uniaxially stretched film. Is preferred. The thickness of the translucent film is 4
0 to 300 μm, preferably 60 to 200 μm, and in the case of a laminated structure, the thickness of the base material layer is 40 to
Preferably, it occupies 80%.

The physical properties of the translucent film are such that the opacity is 25 to 67%, preferably 35 to 66%. When the opacity exceeds the above range, the hot melt ink image viewed with transmitted light is felt dark and unclear, and it is difficult to see characters and pictures on an illuminated signboard, a poster, and the like. Conversely, if the opacity is less than the above range,
Hot-melt ink images viewed with reflected light from illuminated signboards and posters are unclear.

(II) Primer coating layer: Support (I)
The primer coating layer (II) for improving the adhesiveness between the ink and the solid ink receiving layer (III) and improving the paper feeding / discharging properties of the ink jet recording paper comprises: (a) the following monomer (i): (Ii) A tertiary nitrogen-containing acrylic resin, which is an amphoteric compound obtained by copolymerizing (iii) and (iii) with a tertiary nitrogen atom quaternized with a cationizing agent:

Embedded image (Iii) Other hydrophobic vinyl monomers 0 to 20% by weight [where R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. ]

(B) Ethyleneimine adduct of polyethyleneimine, poly (ethyleneimine-urea) and polyaminepolyamide, or an alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified product thereof A polyimine compound selected from the group consisting of a body: 20 to 300 parts by weight; (c) an epichlorohydrin adduct of a polyamine polyamide: 20 to 300 parts by weight; Is applied to the front surface or the front and back surfaces and dried.

The quaternary nitrogen-containing acrylic resin as the component (a) is a primer component that contributes to antistatic properties, and the one described in JP-B-2-2910 is used. Examples of the monomer (ii) include ethyl acrylate, propyl acrylate, butyl acrylate, capryl acrylate, and stearyl methacrylate. As the hydrophobic vinyl monomer (iii), styrene, vinyl chloride and the like can be used.

The polyimine compound as the component (b) is a primer component for enhancing the adhesive force, and is, for example, a polyethyleneimine represented by the following general formula (1) and an ethyleneimine adduct of a polyamine polyamide, or a polyethyleneimine adduct thereof. Alkyl-modified, alkenyl-modified, benzyl-modified,
Alternatively, a polyimine compound selected from the group consisting of modified aliphatic cyclic hydrocarbons and poly (ethyleneimine-urea) can be mentioned (Japanese Patent Publication No. 2-2910, JP-A-1-141736).

[0023]

Embedded image [In the formula, R ^{5 to} R ⁸ are each independently H, having 1 carbon atom.
Represents an alkyl group or alkenyl group, an aliphatic cyclic hydrocarbon group or a benzyl group, m is 0 to 300,
n, p and q each represent a numerical value of 1 to 300. ]

The polyamine polyamide / epichlorohydrin adduct of the component (c) is also a primer for strengthening the adhesive force, such as a polyamide comprising a saturated dibasic carboxylic acid having 3 to 10 carbon atoms and a polyalkylene polyamine. It is a water-soluble, cationic thermosetting resin obtained by reacting with epichlorohydrin. The details of such a thermosetting resin are described in JP-B-35-3547.

Specific examples of the above-mentioned saturated dibasic carboxylic acids having 3 to 10 carbon atoms include dicarboxylic acids having 4 to 8 carbon atoms,
In particular, adipic acid is mentioned. Further, specific examples of the polyalkylene polyamine include polyethylene polyamines, particularly ethylene diamine, diethylene triamine, and triethylene tetramine, and among them, diethylene triamine.

In addition to these components, sodium carbonate, sodium sulfate, sodium sulfite, sodium thiosulfate, barium hydroxide, sodium metasilicate, sodium pyrophosphate (Na ₄ P ₂ O ₇ .10H ₂ O), sodium tripolyphosphate _{(Na 5 P 3 O 10 ·} 6H 2 O), primary phosphate, sodium _{(NaH 2 PO 4 · 2H 2} O), potassium alum (KAl (S
O ₄ ) ₂・ 12H ₂ O), ammonium alum (Al (N
An inorganic compound such as H ₄ ) (SO ₄ ) ₂ · 12H ₂ O) can be blended.

These components (a), (b) and (c) usually have an aqueous solution (coating agent) having a solid content of generally 0.1 to 10% by weight, preferably 0.1 to 5% by weight. Used as The coating amount on the propylene resin film as the support (I) is generally 0.005 to 1 in terms of solid content.
0 g / m ^2, preferably in the range from 0.02 to 5 g / m ^2. As a method for applying the primer, an ordinary application method such as a roll, a blade, an air knife, and a size press can be adopted.

The proportions of the components (a), (b) and (c) are such that the polyimine compound (b) is 20 to 300 parts by weight, preferably 100 parts by weight of the nitrogen-containing acrylic resin (a). Is 20 to 100 parts by weight, and the epichlorohydrin adduct of the polyamine polyamide of (c) is 20 to 100 parts by weight.
It is in the range of 300 parts by weight, preferably 35 to 200 parts by weight. By maintaining these compositions, the antistatic property of the hot melt type ink jet recording paper is maintained, and the ink receiving layer (II) is interposed via the primer coating layer (II).
The adhesion between I) and the support (I) is high.

(III) Ink receiving layer: The ink receiving layer is made of styrene / maleic anhydride copolymer, styrene / alkyl acrylate copolymer, polyvinyl alcohol, ethylene / vinyl alcohol copolymer containing silanol group, polyvinyl Pyrrolidone, ethylene / vinyl acetate copolymer, methyl ethyl cellulose, sodium polyacrylate, starch, polyethylene polyamine, polyester, polyacrylamide, vinyl pyrrolidone / vinyl acetate copolymer, cation-modified polyurethane resin, tertiary nitrogen-containing acrylic resin (Japanese Patent Application Laid-Open No. Sho 62-148292) as a binder, and synthetic silica, alumina hydrosol, talc, calcium carbonate, clay, titanium oxide, zinc oxide, or hollow to improve ink adhesion to the resin. Type Ramin resin filler which was blended with plastic pigments such as hollow polystyrene filler, further ink setting agent necessary, an ultraviolet absorber, in which the surfactant or the like is blended. The binder resin is 8 to 60% by weight, preferably 10 to 40% by weight, and the pigment is 92 to 40% by weight, preferably 90 to 40% by weight.
It is used in the range of 60% by weight.

Pigments are preferably used in combination of two or more in order to improve solid printing.
Oil absorption measured according to No. 1 is 60 to 100 ml / 100
g, for example, calcium carbonate, metatitanic acid, etc. in a pigment at 30 to 60% by weight, and an oil absorption (JIS K-
5101) is 15 ml / 100 g or more, 60 ml / 10
Less than 0 g, such as talc, clay, titanium oxide,
It is preferable to use a mixture of zinc oxide and the like with 70 to 40% by weight in the pigment.

Examples of the ink setting agent include a tertiary ammonium salt of polyethyleneimine, an acrylic copolymer containing a quaternary ammonium group as a copolymerization component, and an epichlorohydrin adduct of polyamine polyamide. The ink receiving layer is formed on the support by applying a coating agent containing the above components to the primer coating layer (II) formed on the surface of the support (I) in an amount of 5 to 50 g / m ² , preferably 5 to 50 g / m ² . ~ 30g
/ M ² (solid content) and dried. If necessary, the surface of the dried coating layer is subjected to a super calender treatment to smooth the coating layer (ink receiving layer).

Physical properties: The opacity of the hot melt type ink jet recording paper is 30 to 70%, preferably 40 to 7
0%. When the opacity exceeds the above range, the hot melt ink image viewed with transmitted light is felt dark and unclear, and it is difficult to see characters and pictures on an illuminated signboard, a poster, and the like. On the other hand, when the opacity is less than the above range, the hot melt ink image viewed from reflected light of an illuminated signboard or poster is unclear. In addition, by using solid ink, the printed material can be clearly recognized for both transmitted light and reflected light when used for an illuminated signboard, and when used for a poster, because of the appropriate translucency of the paper. Is soft and
Excellent aesthetics.

Hot-melt type ink: A hot-melt type ink is a solid at a temperature of 5 to 30 ° C., and melts at a temperature of 50 to 150 ° C., preferably 70 to 135 ° C. In the industry, it is also called solid ink or phase change ink. Generally, polyester, polyamide, polyvinyl acetate, polysilicon, cumarone resin, paraffin wax, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer Metal salts of polymers (K, Zn, Na, Al
Etc.), ethylene-acrylic acid alkyl ester copolymer (alkyl group having 1 to 4 carbon atoms), one or two or more heat-meltable solid substances having a melting point of 50 to 150 ° C, such as fatty acid derivatives. And 0.1 to 15% by weight, preferably 1 to 8% by weight of an oil-soluble dye. Further, if necessary, a surfactant, a plasticizer, a rust inhibitor, an ultraviolet absorber, an organic solvent, an antioxidant, a viscosity lowering inhibitor and the like are blended (see the above-mentioned patent publications). The content of the heat-fusible solid substance in the ink is in the range of 30 to 99% by weight.

As the fatty acid derivative, for example, at least one selected from stearic acid, arachinic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melicic acid can be used in combination. . Fatty acid amides include lauric amide, stearic amide, oleic amide, erucamide,
At least one selected from ricinoleic acid amide, stearic acid ester amide, palmitic acid amide, behenic acid amide, brassic acid amide, or the like can be used as a mixture. N, N'-2-hydroxystearic acid amide as N-substituted fatty acid amide;
N'-ethylenebisoleic acid amide, N, N'-xylenebisstearic acid amide, stearic acid monomethylolamide, N-oleylstearic acid amide, N-stearylstearic acid amide, N-oleylpalmitic acid amide, N-stearyl Erucamide, N, N'-
At least one selected from dioleyl adipamide, N, N'-dioleylsebacic amide, N, N'-distearyl isophthalic amide and the like can be used in combination. As the glyceride, hardened castor oil, castor oil with partial water addition, extremely hardened oil of soybean oil, extremely hardened oil of rapeseed oil, extremely hardened oil of vegetable, and the like can be used as a mixture. .

Oil-soluble dye (Solvent Dye)
Specifically, there are the following. <Magenta dye> MS Magenta VP, MS
Magenta HM-1450, MS Magen
ta HSo-147 (manufactured by Mitsui Toatsu Co., Ltd .: trade name),
AIZENSOT Red-1, AIZEN SOT
Red-2, AIZEN SOTRed-3, AIZE
N SOT Pink-1, SPIRON Red G
EH SPECIAL (all made by Hodogaya Chemical Co., Ltd .: trade name), RESOLIN Red FB 200%, MA
CROLEX Red VioletR, MACROL
EX ROT5B (Bayer Japan: trade name), KAYASET Red B, KAYSETR
ed 130, KAYSETRed 802 (Nippon Kayaku Co., Ltd .: trade name), PHLOXIN, ROSEBE
NGAL, ACID Red (above: manufactured by Daiwa Kasei Co., Ltd.), HSR-31, DIARESEN Red K
(Mitsubishi Chemical Corporation: trade name), Oil Red (BA
SF Japan Co., Ltd .: trade name).

<Cyan dye> MS Cyan HM-
1238, MS Cyan HSo-16, Cyan
HSo-144, MS Cyan VPG (Mitsui Toatsu Co., Ltd .: trade name), AIZEN SOT Blue-4
(Trade name, manufactured by Hodogaya Chemical Co., Ltd.), RESOLEN BR.
Blue BGLN 200%, MACROLEXBl
ue RR, CERES Blue GN, SIRIU
S SUPRATURQ. Blue Z-BGL, SI
RIUS SUPRA TURQ. BlueBF-LL
330% (Bayer Japan: product name), KA
YASETBlue FR, KAYASET Blue
N, KAYASET Blue 814, Turq. B
lue GL-5 200, Light Blue B
GL-5 200 (Nippon Kayaku Co., Ltd .: trade name), DA
IWA Blue 7000, Oleosol Fas
t Blue GL (product name: manufactured by Daiwa Kasei Co., Ltd.),
DIARESIN Blue P (Mitsubishi Chemical Corporation: trade name), SUDAN Blue 670, NEOPEN B
lue 808, ZAPON Blue 806 (above B
ASF Japan Ltd .: trade name).

<Yellow Dye> MS Yellow
HSm-41, Yellow KX-7, Yellow
EX-27 (Mitsui Toatsu Co., Ltd .: trade name), AISE
NSOT Yellow-1, AIZEN SOT Y
yellow-3, AIZEN SOT Yellow-
6, MACROLEX (trade name, manufactured by Hodogaya Chemical Co., Ltd.)
Yellow 6G, MACROLEX FLUO
R. Yellow 10GN (above, manufactured by Bayer Japan: trade name), KAYASET YellowSF-
G, KAYASET Yellow2G, KAYASE
T Yellow AG, KAYASET Yellow
ow EG (all manufactured by Nippon Kayaku Co., Ltd .: trade name), DAIW
A Yellow 330HB (manufactured by Daiwa Kasei: trade name), HSY-68 (manufactured by Mitsubishi Chemical Corporation: trade name), SUD
AN Yellow 146, NEOPEN Yellow
ow 075 (manufactured by BASF Japan: trade name) and the like.

<Black Dye> MS Black V
PC (manufactured by Mitsui Toatsu): AIZEN SOT
Black-1, AIZEN SOT Black-5
(The above is made by Hodogaya Chemical Co., Ltd .: trade name), RESOLIN B
rack GSN 200%, RESOLIN Bla
ckBS (above, manufactured by Bayer Japan: trade name), KA
YASET Black AN (manufactured by Nippon Kayaku Co., Ltd .: trade name), DAIWA Black MSC (manufactured by Daiwa Kasei Co., Ltd .: trade name), HSB-202 (manufactured by Mitsubishi Chemical Corporation: trade name), NEPTUNE Black X60, NEOP
EN BlackX58 (from BASF Japan:
Product name).

Hot melt type ink jet recording apparatus:
Numerous patents have been filed for the hot-melt type ink jet recording apparatus, and they have been put into practical use (Japanese Patent Publication No. 3-501470, Japanese Patent Application Laid-Open No. 2-298951, Japanese Patent Application Laid-Open No. 5-202327, Japanese Patent Application Laid-Open No. 7-133451). issue,
No. 8-11300, US Pat. No. 5,455,501, US Pat. No. 5,170,187, US Pat.
No. 71527, British Patent No. 3,221,471, JP-A-62-135375, JP-A-7-2570
No.13, No.7-186518, Special Publication No.3-50417
Publications such as No. 0). A commercially available hot melt drop demand printer SI-
480, a solid inkjet color printer JOLT manufactured by Hitachi Koki Co., Ltd., and a Phaser 300JS manufactured by Sony Tektronix Co., Ltd., and the like.

FIG. 1 shows an example of a hot melt type ink jet color printer. In the figure, 1 is a color printer device, 2 is an ink pack, 3 is an ink cassette, 4 is an ink loader, 5 is a solid ink, 6 is a print head, 7
Is a paper cassette, 8 is a recording paper, 9 is a head carriage, 10 is a paper pick roller, 11 is a paper feed motor, 12 is a paper feed belt, 13 is a printed paper, 14 is a paper receiver, 15 is a control board, and 16 is a head. It is a feed motor. FIG. 2 shows a partial cross-sectional view of the nozzle of the print head 6. In the figure, 17 is a heater for controlling the ink temperature, 18
Is a nozzle for ejecting color inks of cyan, magenta, yellow, etc., 19 is a nozzle, 20 is an orifice, 21 is a foot (PZT displacement transmission mechanism), and 22 is a PZT (piezo ceramic) actuator.

In the nozzle of FIG. 2, the print head 18 'for black ink and the print head 19' for cyan, magenta, and yellow are respectively overlapped below and above,
The heads 18 'and 19' are heated by the ink temperature control heater 17 at the bottom, and the solid ink is melted to a viscosity of about 10%.
The liquid ink of mPa · S is supplied to the pressure chamber 31. Using a PZT (piezoceramic) actuator 21, a small displacement is applied to the diaphragm of the pressurizing chamber 31, and a small amount of ink is sucked into the ink chamber and the liquid is ejected from the nozzles 18 and 19 as droplets onto the paper via the orifice 20.

The printing using the printer 1 is performed by pulling out the ink jet recording paper 8 stored in a paper cassette 7 on the front of the printer one by one by a paper pick roller 10 and rotating the paper feed belt rotated by a motor 11. The paper is sucked by the paper 12 and printed while passing through the front surface of the print head 6, and the paper 13 printed on the paper receiver 14 by the paper feed belt so that the printing surface faces down is stacked.

To replenish the ink, the ink pellets contained in the ink pack 2 are put into the ink cassette 3 from above the ink cassette 3. The print head 6 can be moved right and left by a head carriage 9, and the print head 6 (17 ′, 1 ′)
8 '), a nozzle set 19 in which 16 nozzles each for cyan, magenta, and yellow are arranged in a line, and a black (black) nozzle set 18 are mounted.

FIG. 3 is a perspective view in which a part of the signboard is cut away. In the figure, the illuminated signboard (E) is a recording paper (A)
The shop name, place, telephone number, product (menu), design, etc. are printed (B) on the surface of the gravure, screen, offset, etc., and fixed to the frame (C). , Light bulbs, mercury lamps, xenon lamps and other light sources (D)
It is formed by irradiating more light rays and transmitting the light from the printed recording paper (E) for the illuminated signboard.

Printing: The hot melt type ink jet recording paper of the present invention has water resistance by itself and can be used outdoors. Further, the support of the recording paper is a stretched film, has a high stiffness, and the primer coating layer has an antistatic property, so that the paper feeding and discharging operation is good. Furthermore, since the primer coating layer (II) having a special composition is present, the adhesion between the ink receiving layer (III) and the support (I) is excellent, so that the adhesion of the printing ink is strong and the printing surface is Rubbing with a finger or folding the printed paper does not peel off the print. In addition, printed matter using solid ink can be clearly recognized in both transmitted light and reflected light because of the appropriate translucency and whiteness of the paper, and because of its translucency, the underlying document Also, the drawings are legible.

[0046]

The present invention will be described in more detail with reference to the following examples. Production Example of Support: (Example 1) (1) A mixture of 89% by weight of a propylene homopolymer having an MFR of 0.8 g / 10 minutes, 8% by weight of high-density polyethylene, and 3% by weight of calcium carbonate powder having a particle size of 1.5 μm. (A) was melt-kneaded by an extruder, extruded into a sheet from a die, and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 155 ° C., it was stretched 5 times in the machine direction.

(2) 45% by weight of calcined clay having an average particle size of 1.2 μm and 50.5% by weight of propylene homopolymer (C) having a MFR of 4.0 g / 10 minutes and polypropylene of 50.5% by weight of MFR 4.0 g / 10 minutes. 0.8 μm diameter titanium oxide
A composition (B) obtained by mixing 0% by weight and 3.5% by weight of high-density polyethylene is melt-kneaded in separate extruders, laminated in a die, and co-extruded into a 5-fold stretched sheet of (1). Then, the five-layer laminate was heated to 185 ° C. and then stretched 7.5 times in the transverse direction to obtain a five-layer film.

(3) The surface of the five-layer laminated film is subjected to corona discharge treatment to obtain (C) / (B) / (A) / (B) /
(C) The thickness of each film is 5/30/80/30/5
A laminate with a micron five-layer structure was obtained. This wall thickness is 150
The micron five-layer laminate film had 64% opacity and 93% whiteness.

Example 2 (1) A mixture (A) of 92% by weight of a propylene homopolymer and 8% by weight of a high-density polyethylene was melt-kneaded with an extruder and then sheeted from a die. To obtain a non-stretched sheet. After heating this sheet to 155 ° C.,
It was stretched twice. (2) As high as 56% by weight of a propylene homopolymer having an MFR of 4.0 g / 10 minutes, 40% by weight of calcium carbonate having an average particle size of 1.5 μm and 0.5% by weight of anatase-type titanium oxide having an average particle size of 0.8 μm. And melt kneading with a composition (B) mixed with 3.5% by weight of polyethylene by a separate extruder;
Coextrusion was performed in a die on both sides of the 5-fold stretched sheet of (1) so that (B) was on the outside.
After heating to 85 ° C., the film was stretched 7.5 times in the transverse direction to obtain a three-layer laminated film.

(3) The surface of the three-layer laminated film is subjected to a corona discharge treatment to form a three-layer laminated film having a (B) / (A) / (B) film thickness of 20/50/20 microns. I got something. The physical properties of the three-layer laminated film having a thickness of 100 microns were 39% in opacity and 86% in whiteness.

(Example 3) (1) A mixture of 81% by weight of a propylene homopolymer having an MFR of 1.0 g / 10 minutes, 3% by weight of high-density polyethylene, and 16% by weight of calcium carbonate having an average particle size of 1.5 μm (A) Was melt-kneaded by an extruder, extruded into a sheet from a die, and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 140 ° C.,
It was stretched twice. (2) A mixture (B) of 54% by weight of a propylene homopolymer having an MFR of 4.0 g / 10 minutes and 46% by weight of calcium carbonate having an average particle size of 1.5 μm was melt-kneaded in separate extruders, and (1) The sheet was co-extruded and laminated in a die so that (B) was on the outside on both sides of the 5-fold stretched sheet, and then the laminate was heated to 160 ° C. and then stretched 7.5 times in the transverse direction. A three-layer laminated film was obtained.

(3) The surface of this three-layer laminated film is subjected to a corona discharge treatment to form a three-layer laminated film having a thickness of (B) / (A) / (B) of 25/60/25 microns. I got something. The physical properties of the three-layer laminated film having a thickness of 110 microns were 94% opacity and 96% whiteness.

Production Example of Primer Coating Agent: (Example 4) A coating agent having the following composition was used. (A) 0.5% by weight of a terpolymer of the following unit:

Embedded image 28 _{mole% -CH 2 -CH 2 -COOC 2 H} 4 56 _{mole% -CH 2 -CH 2 -COOC 18 H} 37 16 mol%

(B) Butyl-modified polyethyleneimine 0.3% by weight (c) 0.5% by weight of epichlorohydrin adduct of water-soluble polyamine polyamide (“WS-570: trade name” manufactured by Nippon PMC Co., Ltd.) ) Water residue

Example 5 A coating composition having the following composition was used. (A) quaternary copolymer of the following unit: 1.5% by weight

Embedded image 34 mol% -CH ₂ -CH ₂ -COOC ₄ H ₉ 46 mol%

[0056]

Embedded image 8 mol%

[0057]

Embedded image 12 mol%

(B) 0.2% by weight of butylated modified polyethyleneimine obtained by the following method: Nippon Shokubai Co., Ltd. was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet. ) Polyethyleneimine “Epomin P-1000” (trade name; degree of polymerization 1)
600), 25 parts by weight of a 25% by weight aqueous solution, 10 parts of n-butyl chloride and 10 parts of isopropyl alcohol were added, and the mixture was stirred under a nitrogen stream, and subjected to a denaturation reaction at a temperature of 80 ° C. for 20 hours to give a concentration of 20.8% by weight. A butyl-modified polyethyleneimine aqueous solution was obtained.

(B ′) Ethyleneimine adduct of polyamine polyamide (Polymin SN manufactured by BASF) 0.3% by weight (c) Epichlorohydrin adduct of water-soluble polyamine polyamide (WS-570) 0.5% by weight ( d) water residue

(Example 6) A coating agent having the following composition was used. (A) 0.5 parts by weight of a quaternary nitrogen-containing acrylic resin as the component (a) in Example 4 (b) 0.1 parts by weight of a cyclopentylated modified ethyleneimine-based polymer obtained by the following method Stirrer, reflux In a four-necked flask equipped with a cooler, a thermometer, and a nitrogen gas inlet, polyethyleneimine “Epomin P-1000” manufactured by Nippon Shokubai Co., Ltd. (trade name; degree of polymerization: 1)
600), 25 parts by weight of a 25% by weight aqueous solution, 13 parts of cyclopentyl chloride and 10 parts of isopropyl alcohol were added thereto, and the mixture was stirred under a nitrogen stream and subjected to a denaturation reaction at a temperature of 80 ° C. for 20 hours to give a cyclopentyl concentration of 20.8% by weight. A modified polyethyleneimine aqueous solution was obtained.

(B ′) Ethylene imine adduct of polyamine polyamide (Polymin SN, trade name of BASF) 0.3 part by weight (c) Polyamine polyamide / epichlorohydrin adduct (WS-570) 0.5 part by weight (d) Water residue

Production Example of Ink-Receiving Layer Coating Agent (Example 7) A coating agent having the following solid components was used. The coating agent is dispersed in water, and the solid component concentration is adjusted to 5% with water.
It was adjusted to 5% by weight. The following pigments and resin binders were used. Diatomaceous earth: Oil absorption 42 ml / 100 g: 30 parts by weight Light calcium carbonate: Oil absorption 63 ml / 100 g: 40 parts by weight Silica: Oil absorption 263 ml / 100 g: 15 parts Clay: Oil absorption 46 ml / 100 g : 15 parts by weight Binder: Acrylic ester resin emulsion "Bonlon S-282" (trade name) of Mitsui Toatsu Co., Ltd.: 10 parts by weight

Example 1 On the front and back surfaces of the film of Example 1,
Each of the primer coating layers of Example 4 was 0.2 g / m 2 in a solid amount.
^It was applied so as to be ² and dried at 65 ° C. On one surface of the dried primer layer, an ink receiving layer coating composition having the composition shown in Example 7 was applied in an amount such that the solid content became 10 g / m ² ,
After drying at 100 ° C, ink receiving layer / primer coating layer /
Inkjet recording paper having the structure of synthetic paper / primer coating layer was obtained.

A phase change ink jet type color printer “Phaser 300” manufactured by Sony Techtronics Co., Ltd. is applied to this ink jet recording paper.
Using JS "(product name), the company's black ink (016-1123-00), cyan ink (016-1124-00), magenta ink (016-1125-00) and yellow ink as hot melt inks (0
16-1126-00), the ink melting temperature (7
(8 to 85 ° C.), and inkjet printing was performed. The obtained recording paper and its printed matter were evaluated.
Table 1 shows the results.

(Evaluation) (1) Solid printability: yellow, magenta, cyan,
Regarding the solid portion developed with the black color ink, the uniformity of the image quality of the transmitted light and the reflected light by the fluorescent lamp was observed, and evaluated visually as follows. : Uniform with no solid portion missing. ×: There are considerable white spots on the solid portion, which is a practical problem.

(2) Readability of illuminated signboard: The printed matter was fixed to the frame shown in FIG. 3, and two 20-W white fluorescent lamps were arranged 5 cm from the back of the printed matter. Readability was evaluated. : The print surface is bright and the image is clear. ×: The printing surface is dark and the image is unclear.

(3) Adhesiveness of ink: Nichiban Co., Ltd. adhesive tape trade name "Cellotape LP-2"
Paste 4 ”and press lightly with a gauze in the shape of a bead.
Rubbing was repeated and the tape was quickly peeled off to evaluate ink adhesion. The adhesion of the ink was evaluated as follows. ；: The ink does not peel at all (no problem in practical use). X: The peeled portion was 25% or more.

(4) Presence / absence of peeled portion of printing at the time of folding: The printed recording paper was folded in eight, and opened to check whether or not the printing ink of the fold portion was peeled. ○ ・ ・ ・ No peeling. ×: There is peeling.

(5) Presence or absence of heat shrinkage during printing of recording paper:
A sample having a heat shrinkage of 2% or more was evaluated as poor (x), and a sample having a heat shrinkage of less than 2% and having no problem was evaluated as good (o). (6) Paper feeding / discharging property: The number of paper jams when hot-melt ink jet printing is performed on 10 recording papers consecutively.・ ・ ・: No paper jam. ×: Paper jam.

(Comparative Example 1) A recording paper was manufactured and evaluated in the same manner as in Example 1 except that an ink receiving layer was directly provided on a film without providing a primer coating layer. Table 1 shows the results. (Examples 2 to 4, Comparative Example 2) Except for changing the film and the primer coating agent as shown in Table 1, both the coating amount of the primer coating agent and the coating amount of the ink receiving layer were the same as in Example 1. Ink jet recording paper was manufactured and evaluated. Table 1 shows the results.

[0071]

[Table 1]

[0072]

According to the present invention, it is possible to provide a translucent hot-melt type ink jet recording sheet having good ink adhesion and excellent paper supply / discharge properties. Since the printed paper has excellent water resistance, it is useful as an electric sign or an outdoor poster.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a hot-melt type ink jet printer.

FIG. 2 is a schematic sectional view of a nozzle portion of a print head.

FIG. 3 is a perspective view showing a part of an illuminated signboard without a part.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Color printer apparatus 2 Ink pack 3 Ink cassette 4 Ink loader 5 Solid ink 6 Print head 7 Paper cassette 8 Recording paper 9 Head carry 10 Paper pick roller 11 Paper feed motor 12 Paper feed belt 13 Printed paper 14 Paper receiving 15 Control base 16 Head feed motor 17 Ink temperature control heater 18 Black ink nozzle 18 'Black ink print head 19 Color ink nozzle such as cyan, magenta, yellow 19' Print head for color ink such as cyan, magenta, yellow 20 Orifice 21 Foot (PZT displacement transmission mechanism) 22 PZT actuator 31 Pressurizing chamber A Recording paper B Printing C frame D Light source E Illuminated signboard

[Procedure amendment]

[Submission date] April 2, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

[0046]

The present invention will be described in more detail with reference to the following examples. Production Example of Support: (Example 1) (1) A mixture of 89% by weight of a propylene homopolymer having an MFR of 0.8 g / 10 minutes, 8% by weight of high-density polyethylene, and 3% by weight of calcium carbonate powder having a particle size of 1.5 μm ( A) was melt-kneaded with an extruder, extruded from a die into a sheet, and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 155 ° C., it was stretched 5 times in the machine direction.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

(2) Propylene homopolymer (C) having an MFR of 4.0 g / 10 min and polypropylene of 50.5 wt% of MFR of 4.0 g / 10 min, and 45 wt% of calcined clay having an average particle size of 1.2 μm and particle size 0.8 μm titanium oxide 1.0
The composition (B) in which 3.5% by weight and 3.5% by weight of high-density polyethylene are mixed and melt-kneaded in separate extruders, laminated in a die, and co-extruded into a 5-fold stretched sheet of (1). The five-layer laminate was heated to 185 ° C. and then stretched 7.5 times in the horizontal direction to obtain a five-layer film.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

Example 2 (1) A mixture (A) of 92% by weight of a propylene homopolymer and 8% by weight of a high-density polyethylene was melt-kneaded with an extruder, and then formed into a sheet from a die. The sheet was extruded and cooled by a cooling device to obtain a non-stretched sheet. After heating this sheet to 155 ° C.,
It was stretched twice. (2) Calcium carbonate 4 having an average particle size of 1.5 μm was added to 56% by weight of a propylene homopolymer having an MFR of 4.0 g / 10 min.
A composition (B) in which 0% by weight, 0.5% by weight of anatase type titanium oxide having an average particle size of 0.8 μm and 3.5% by weight of high-density polyethylene are melt-kneaded in separate extruders,
Coextrusion was performed in a die on both sides of the 5-fold stretched sheet of (1) so that (B) was on the outside.
After heating to 85 ° C., the film was stretched 7.5 times in the transverse direction to obtain a three-layer laminated film.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

Example 3 (1) Mixture (A) of 81% by weight of propylene homopolymer, 3% by weight of high-density polyethylene, and 16% by weight of calcium carbonate having an average particle size of 1.5 μm was obtained by mixing (1) MFR of 1.0 g / 10 min. After melt-kneading with an extruder, the mixture was extruded into a sheet from a die and cooled by a cooling device to obtain a non-oriented sheet. After heating this sheet to 140 ° C.,
It was stretched twice. (2) 54% by weight of a propylene homopolymer having an MFR of 4.0 g / 10 min and calcium carbonate 4 having an average particle size of 1.5 μm
6% by weight of the mixture (B) is melt-kneaded by a separate extruder, and is co-extruded and laminated in a die on both sides of the 5-fold stretched sheet of (1) so that (B) is on the outside. After heating the laminate at 160 ° C., it was stretched 7.5 times in the transverse direction to obtain a three-layer laminate film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 9/00 C08J 9/00 // C08J 7/04 7/04 H

Claims (3)

[Claims] 1. A hot-melt ink-jet recording sheet which heats and melts a solid hot-melt ink at normal temperature to receive and record a flying molten ink, wherein the recording paper is a resin film containing a white inorganic fine powder. The support (I) is a translucent microporous film made of a stretched product of the above, and a hot-melt ink receiving layer is provided on the surface of the support (I) via a primer coating layer (II) having the following composition. A hot-melt ink jet recording sheet having a structure provided with (III), wherein the opacity of the recording sheet is 30 to 70%. Primer coating layer (I
I) is an amphoteric compound obtained by (a) quaternizing a tertiary nitrogen atom of a polymer obtained by copolymerizing the following monomers (i), (ii) and (iii) with a cationizing agent. , Quaternary nitrogen-containing acrylic resin: 100 parts by weight, (Iii) Other hydrophobic vinyl monomers 0 to 80% by weight [where R ¹ is H or CH ₃ , R ² is an alkyl group having 1 to 18 carbon atoms, R ³ and R ⁴ are each H is an alkyl group having 1 to 2 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms. (B) Polyethyleneimine, poly (ethyleneimine-urea) and ethyleneimine adducts of polyaminepolyamide, or alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified thereof. A polyimine compound selected from the group consisting of: 20 to 300 parts by weight; (c) an epichlorohydrin adduct of polyamine polyamide: 20 to 300 parts by weight; It was done. 2. The support (I) comprises an inorganic fine powder of 0 to 4
A biaxially stretched film of a thermoplastic resin film containing 0% by weight is used as a base layer, and a uniaxially stretched film of a thermoplastic film containing 8 to 65% by weight of an inorganic fine powder is formed on the front and back surfaces of the base layer. The opacity of the laminated stretched film is 25 to 67% and the whiteness is 8
The hot-melt ink jet recording paper according to claim 1, wherein the content is 0 to 100%. 3. A receiving layer of a hot melt ink (II)
I) contains 40 to 92% by weight of a pigment and 8 to 60% by weight of a resin binder, and the pigment has an oil absorption (JIS K-5101) in the pigment.
Is 60 to 100 ml / 100 g, and 30 to 60
Weight%, oil absorption 15ml / 100g or more, 60ml /
2. A hot-melt ink jet recording sheet according to claim 1, wherein a mixture containing less than 100 g of pigment in an amount of 70 to 40% by weight is used.