JP6358464B2 - INKJET RECORDING METHOD AND METHOD FOR PRODUCING INKJET RECORDED PRODUCT - Google Patents

Description

  The present invention relates to an inkjet recording method and inkjet recorded matter using tarpaulin and water-based ink.

Inkjet printers have advantages such as low noise, low running cost, and easy color printing, and are therefore widely used as digital signal output devices in general households.
More recently, the spread of inkjet printing methods that can easily record digital images on a print medium by computer processing, such as the printing industry, advertising industry, sign and display industry, various event industries, amusement industry, architecture / interior, etc. It is increasingly used as a precision printed matter with high visual catch and advertising effect in various fields such as the design industry.

  In particular, the demand for outdoor applications has advanced remarkably. For example, there is an increasing demand for the development of outdoor advertising signs, building and building curing sheets, internally-lighted tents, safety signs, etc. In these industrial materials fields, A so-called tarpaulin base material obtained by coating a polyester fiber fabric with a thermoplastic resin is used for reasons such as film material strength, outdoor durability, flameproofing, and general-purpose cost.

  When inkjet recording is performed on non-porous media such as tarpaulin, the ink to be used so far is, for example, a solvent-based inkjet ink using an organic solvent as a vehicle, or an ultraviolet curable type mainly composed of a polymerizable monomer. Inkjet inks have been widely used.

  However, solvent-based ink-jet inks are not preferred from the viewpoint of environmental impact because they evaporate a large amount of solvent in the atmosphere, and UV curable ink-jet inks may have skin sensitivity depending on the monomers used. Since the expensive ultraviolet irradiation device needs to be incorporated in the printer body, the field of application is limited.

Against this background, recently, water-based inkjet recording inks that have a low environmental burden and can be directly printed on a non-porous substrate have been developed (see Patent Documents 1 and 2).
However, these water-based inks are disclosures of inks for non-porous substrates in general, and no special consideration has been given to tarpaulins.

Further, Patent Documents 3 and 4 are disclosed as water-based inks for tarpaulins, but these patent documents focus only on drying and fixing properties, and do not particularly mention image quality.
Further, in Patent Documents 3 and 4, only a tarpaulin coated with a polyvinyl chloride resin is studied. By the way, since polyvinyl chloride resin products are problematic in that toxic hydrogen chloride gas is generated due to thermal decomposition during disposal and incineration, tarpaulins coated with acrylic resin are also increasing in the market. . Patent Documents 3 and 4 do not discuss tarpaulins coated with acrylic resin at all.
Therefore, no investigation has been made on an ink jet recording method using a tarpaulin and an aqueous ink jet ink that is optimal for it.

  The present invention has been made in view of the current situation, and an object of the present invention is to provide an ink jet recording method using tarpaulin and water-based ink that can provide high image quality and high fastness.

The above problem is solved by the following invention 1).
1) In an inkjet recording method in which printing is performed using water-based ink on tarpaulin, the peak absorbance of 1720 ± 5 cm ⁻¹ / 2960 ± 5 cm ⁻¹ in the infrared absorption spectrum obtained by the ATR method on the surface of the tarpaulin. The absorbance ratio represented by the peak absorbance is 2.50 to 5.50, and the water-based ink contains at least water, a water-soluble organic solvent, a pigment, and two or more kinds of resins. An ink jet recording method, wherein at least one of the resins is a urethane resin.

  According to the present invention, an ink jet recording method can be obtained which uses water-based ink on tarpaulin to give a printed matter with high image quality and high fastness.

It is the schematic which shows an example of a serial type inkjet recording device. It is a schematic block diagram explaining the whole structure of the mechanism part of the inkjet recording device shown in FIG. It is an infrared absorption spectrum of Tarpaulin A (Vel Adwise VS-T) used in the examples. It is an infrared absorption spectrum of Tarpaulin B (NIJ-WTM manufactured by Nichie) used in the examples. It is an infrared absorption spectrum of Tarpaulin C (LT15GS made by Lucio) used in the examples. It is an infrared absorption spectrum of Tarpaulin D (Valex 7504 manufactured by Lucio) used in the examples. It is an infrared absorption spectrum of Tarpaulin E (LUMIJET-W002 manufactured by IKC) used in Examples.

Hereinafter, the present invention 1) will be described in detail. In addition, since the following 2) -7) are also included in embodiment of this invention 1), these are also demonstrated collectively.
2) The inkjet recording method according to 1), wherein the urethane resin is a polycarbonate-based urethane resin.
3) The water-soluble organic solvent was selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. The inkjet recording method according to 1) or 2) above, which contains at least one kind.
4) An ink jet recorded product formed using the ink jet recording method described in any one of 1) to 3).

The image fastness that becomes a problem when water-based ink is printed on a non-porous substrate can be evaluated mainly from the following two viewpoints.
(1) Abrasion resistance showing resistance to image quality degradation when a force is applied to the image in the direction along the print surface. (2) A sticky substance such as a tape is stuck on the printed matter and perpendicular to the print surface. Adhesion showing resistance to image quality degradation when force is applied in the direction

A urethane resin forms a highly glossy, flexible and tough coating film composed of a hard segment and a soft segment, and therefore can be suitably used for printing on a non-porous substrate from the viewpoint of scratch resistance.
However, investigations by the inventors have revealed that adhesion to some tarpaulins is poor.
Then, when the surface composition of the tarpaulin used as the substrate was examined, in the infrared absorption spectrum obtained by the ATR method, the absorbance represented by [peak absorbance at 1720 ± 5 cm ⁻¹ / peak absorbance at 2960 ± 5 cm ⁻¹ ]. It has been found that adhesion is ensured when the ratio is 2.50 to 5.50.

In the infrared absorption spectrum, a peak near 1720 cm ⁻¹ is derived from a carbonyl group, and a peak near 2960 cm ⁻¹ is a peak derived from a methylene group. For this reason, the intensity ratio of this peak can be used as an index of the polarity / nonpolar intensity of the media surface, and the intermolecular force of the urethane resin works most effectively from 2.50 to 5.50. This is probably because of this.
Further, although the reason is not clear, the inventors have found that when two or more kinds of resins are mixed with water-based ink, the color developability on tarpaulin is improved and the image density is greatly improved, and the present invention has been achieved.

  Polycarbonate urethane resins are excellent in water resistance, heat resistance, wear resistance, and weather resistance due to the high cohesive strength of carbonate groups. For this reason, when the urethane resin contained in the ink is a polycarbonate-based urethane resin, the printed material is preferable because the scratch resistance of the printed material becomes stronger, and the printed material is used in harsh environments such as outdoor use. Can be obtained.

  The water-soluble organic solvent is selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. When at least one kind is contained, higher gloss is easily obtained, which is preferable.

Hereinafter, the components of the ink of the present invention will be described.
<Urethane resin>
In the present invention, it is necessary to use at least one urethane resin in the ink, and the urethane resin can be used without particular limitation with respect to a urethane resin obtained by reacting a polyol and a polyisocyanate.
Examples of the polyol that can be used as the polyol include polyether polyol, polycarbonate polyol, and polyester polyol.
From the viewpoint of obtaining particularly excellent image fastness, a polycarbonate-based urethane resin using a polycarbonate polyol as the polyol is particularly preferable. Particularly preferred polycarbonate urethane has a structure derived from an aliphatic or alicyclic diisocyanate, and is preferred from the viewpoint of obtaining excellent weather resistance.
In the present invention, the two or more types of resins are different types of resins having at least different resin skeletons. In the urethane resin, resins having different polyol components or different polyol components such as ester-based, ether-based, and carbonate-based resins are different resins. Those with the same skeleton but different molecular weight are the same resin.
Of the two or more types of resins, the one type of urethane resin that is essential in the ink is preferably a polycarbonate-type urethane resin, and the combination of two or more types of resins includes polycarbonate-type urethane resins and other urethane resins. A combination is most preferred.

(Polyether polyol)
As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  As the polyether polyol, it is preferable to use polyoxytetramethylene glycol or polyoxypropylene glycol from the viewpoint of obtaining a binder for ink jet printing ink capable of imparting very excellent scratch resistance.

(Polycarbonate polyol)
As said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, and what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedi Methanol, hydroquinone, resorcin, bisph Relatively low molecular weight dihydroxy compounds such as Nord-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexa Polyester polyols such as methylene succinate and polycaprolactone can be used.

(Polyester polyol)
Examples of the polyester polyol include those obtained by an esterification reaction of a low molecular weight polyol and a polycarboxylic acid, polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymers of these. Polymerized polyester or the like can be used.
Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

(Polyisocyanate)
Examples of the polyisocyanate used in producing the urethane resin include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate are used alone or in combination of two or more. be able to.
In addition, since the ink of the present invention is intended for outdoor use such as posters and signboards, it requires a coating film with extremely high long-term weather resistance. From this viewpoint, aliphatic or alicyclic diisocyanate Is preferably used.

(Production method)
The urethane resin used in the ink of the present invention is contained as urethane resin fine particles, and the urethane resin fine particles can be obtained by a conventionally commonly used production method, and examples thereof include the following methods.
First, an isocyanate-terminated urethane prepolymer is produced by reacting the polyol and the polyisocyanate in an equivalent ratio in which an isocyanate group becomes excessive in the absence of a solvent or in the presence of an organic solvent.
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with the following neutralizing agent as necessary, then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. By doing so, urethane resin fine particles can be obtained.

  Usable organic solvents include, for example, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, acetates such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, dimethylformamide, N-methylpyrrolidone, Amides such as N-ethylpyrrolidone can be mentioned. These may be used alone or in combination of two or more.

Examples of the chain extender include polyamines and other active hydrogen atom-containing compounds.
Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamine, polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine, hydrazines such as hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, adipic acid dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide.

  Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. , Glycols such as methylene glycol, glycerin and sorbitol, phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water. These may be used alone or in combination of two or more as long as the storage stability of the ink does not deteriorate.

In the ink of the present invention, it is usually preferable to add urethane resin fine particles in the form of a resin emulsion dispersed in an aqueous medium.
The resin solid content in the resin emulsion is preferably 20% by mass or more, and when it is 20% by mass or more, it is preferable because the prescription design for making an ink becomes easy.

When dispersing fine resin particles in an aqueous medium, a forced emulsification type using a dispersant can be used. However, since the dispersant may remain in the coating film and lower the strength, anionic properties may be present in the molecular structure. A so-called self-emulsifying type having the above is preferred.
In that case, it is preferable from the viewpoint of water dispersibility that an anionic group is contained in the range of 5 to 100 mgKOH / g, and 5 to 50 mgKOH / mg gives excellent scratch resistance and chemical resistance. This is particularly preferable.
Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among them, it is preferable to use a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like in order to maintain good water dispersion stability, and these anionic groups are introduced into the resin. For these, monomers having these anionic groups may be used.

  Examples of basic compounds that can be used for neutralization of the anionic group include organic bases such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, and metal base compounds including Na, K, Li, and Ca. Etc.

When the forced emulsification method is used, either a nonionic surfactant or an anionic surfactant can be used, but a nonionic surfactant is preferable because water resistance is improved.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, sorbitan fatty acid ester , Polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, polyalkylene glycol (meth) acrylate and the like. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.

  As an anionic surfactant, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, methyl taurate, sulfosuccinate, ether sulfonate, ether carboxylate, Fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides and the like are preferable, and polyoxyethylene alkyl ether sulfates, sulfosuccinates and the like are preferable.

  The addition amount of surfactant is 0.1-30 mass% with respect to resin, Preferably it is 5-20 mass%. If it is in the range of 0.1 to 30% by mass, the film-forming property of the resin emulsion is not hindered, so that an ink having excellent adhesion and water resistance can be obtained, and the printed matter is less likely to cause blocking.

Further, the particle diameter of the resin fine particles is preferably 10 to 1,000 nm, more preferably 10 to 200 nm, and further preferably 10 to 100 nm, particularly considering use in an ink jet recording apparatus.
By using the resin fine particles having a volume average particle size of 10 to 1,000 nm, the contact area between the water-soluble organic solvent and the resin fine particle surface is increased, the film forming property of the resin fine particles is enhanced, and the continuous coating of tough resin Therefore, it is possible to obtain a printed matter with high strength.
Here, the volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  In the present invention, the ink contains two or more kinds of resins, and the total content of all resins is preferably in the range of 1 to 10% by mass in the total mass of the ink in terms of fixability and ink stability. The range of 10% by mass is more preferable because the smoothness of the ink layer is further improved, high glossiness can be obtained, and the fixability to the substrate is also improved.

<Resin other than urethane resin>
In the present invention, it is essential that the ink contains two or more types of resins, and all of the two or more types of resins may be different types of urethane resins, but may contain resins other than urethane resins. Absent.
There is no restriction | limiting in particular as kind of resin other than such urethane resin, According to the objective, it can select suitably, For example, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin Styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, acrylic silicone resin, polyolefin resin, and the like.

As resin fine particles of resins other than the urethane resin, those appropriately synthesized may be used, or commercially available products may be used.
Examples of the commercially available resin fine particles include microgel E-1002, E-5002 (styrene-acrylic resin fine particles, manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic resin fine particles, manufactured by Dainippon Ink & Chemicals, Inc.). ), Boncoat 5454 (styrene-acrylic resin fine particles, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin fine particles, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin fine particles, Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin fine particles, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin fine particles, manufactured by Toyo Ink Manufacturing Co., Ltd.), # 3070 (Methyl methacrylate polymer Fat particles, Mikuni Color Ltd.) Au Lauren AE-202 (polyolefin resin emulsion, manufactured by Nippon Paper Industries Co., Ltd.), Elitel KT-8803 (polyester resin emulsion, manufactured by Unitika Ltd.) and the like.
Further, the preferred forms of the addition of these resins into the ink, the average particle diameter of the particles, the dispersion method, the acid value, and the like are the same as those for the urethane resin described above.

  The addition amount of two or more kinds of resins added in the present invention is [addition amount of one type of urethane resin essential to the ink / addition amount of resin other than one type of urethane resin essential to the ink. ] Is preferably 100/1 to 5/1, more preferably 50/1 to 10/1 in terms of the mass ratio of the solid content. When used in this range, it is desirable because the image density on tarpaulin is improved. In addition, when two or more types of different types of urethane resins are contained as two or more types of resins, one type of urethane resin that is essential for the ink is any urethane resin of two or more types of urethane resins. Although it may be, it is preferable that it is a polycarbonate-type urethane resin.

Next, other components of the ink of the present invention will be described.
The ink component of the present invention comprises at least water, a pigment, a water-soluble organic solvent, and may contain other surfactants, antiseptic / antifungal agents, rust preventives, pH adjusters and the like as necessary. .

<Pigment>
As pigments, inorganic pigments are manufactured by known methods such as contact method, furnace method, thermal method in addition to titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow. Carbon black can be used.

Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black, etc. .
Of these pigments, those having good affinity with the solvent are preferably used.

The amount of the pigment added as the coloring material in the ink composition is preferably about 0.1 to 10% by mass, more preferably about 1 to 10% by mass.
In general, when the pigment concentration is increased, the image density is increased and the image quality is improved. However, the reliability such as fixing property, ejection stability, and clogging tends to be adversely affected.

  Specific examples of pigments preferably used in the present invention include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11). And metal pigments such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).

  Further, for color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, CI pigment orange 5, 13, 16, 17, 36, 43, 51, CI pigment red 1, 2, 3, 5, 17, 22 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B) ), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Kinaku) Don Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, CI Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16 19, 23, 38, CI pigment blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 15: 4, 16, 17: 1, 56, 60, 63, CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

In addition, a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the surface of the pigment (for example, carbon) can be used.
Further, a pigment may be included in a microcapsule so that the pigment can be dispersed in water.
This can be paraphrased as resin fine particles containing pigment particles.
In this case, it is not necessary for all pigments blended in the ink to be enclosed or adsorbed in the resin fine particles, and the pigments may be dispersed in the ink as long as the effects of the present invention are not impaired.

The particle diameter of the pigment is not particularly limited, but it is preferable in the present invention to use a pigment ink having a particle diameter of 20 to 150 nm in terms of the maximum frequency in terms of the maximum number. When the particle size is 150 nm or less, not only the pigment dispersion stability as the ink composition is improved, but also the ejection stability is excellent, and the image quality such as the image density is increased, which is preferable.
If the particle size is less than 20 nm, the storage stability of the ink composition and the jetting characteristics of the printer are stable, but it is economical to disperse to such a fine particle size because the dispersion operation and classification operation are complicated. is not.

In the case of dispersing a pigment using a dispersant, any conventionally known dispersant can be used.
Examples thereof include a polymer dispersant and a water-soluble surfactant.

<Water-soluble organic solvent>
Next, the water-soluble organic solvent will be described. In the present invention, the type of solvent used is not particularly limited.
Specifically, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3- Methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1, Polyhydric alcohols such as 3-hexanediol, 2-ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Diechi Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methyl Amides such as formamide and N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine and triethylamine, dimethyl sulfoxide, sulfo Emissions, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and ethylene carbonate and the like.
These may be used alone or in combination of two or more.
Among these, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol are used from the viewpoint of promoting resin film formation and preventing particle aggregation. 2,3-butanediol is particularly preferable, and high gloss is easily obtained.

The total amount of the water-soluble organic solvent contained in the entire ink is preferably in the range of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.
When the total amount of the water-soluble organic solvent is 20% by mass or more, the ink is difficult to dry and ink ejection stability is improved.
Further, when the total amount of the water-soluble organic solvent is 70% by mass or less, the viscosity of the ink can be kept low, so that the ink can be easily discharged.

<Surfactant>
A surfactant may be added to the ink of the present invention to ensure wettability to the recording medium.
The addition amount of the surfactant in the ink is preferably 0.1 to 5% by mass. When it is 0.1% by mass or more, wettability to a non-porous substrate can be secured, so that the image quality is improved, and when it is 5% by mass or less, the ink is less likely to foam, and thus excellent ejection stability. Is obtained.

  The surfactant to be used is not particularly limited as long as the above addition amount conditions are satisfied, and any of amphoteric surfactants, nonionic surfactants, anionic surfactants, and the like can be used. However, due to the relationship between the dispersion stability of colorants and image quality, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol are desirable. Further, depending on the formulation, it is possible to use a fluorine-based surfactant or a silicone-based surfactant in combination or independently.

<Other additives>
As ink constituents other than those described above, additives such as antiseptic / antifungal agents, rust preventives, and pH adjusters may be used as necessary.
Examples of antiseptic / antifungal agents include 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and the like.
Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite and the like.

  As the pH adjuster, any substance can be used as long as it can adjust the pH to a desired value without adversely affecting the ink. Examples include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate, quaternary ammonium hydroxides and diethanolamine. And amines such as triethanolamine, ammonium hydroxide, quaternary phosphonium hydroxide and the like.

The ink of the present invention is prepared by dispersing or dissolving the above-described constituents in an aqueous medium, and further stirring and mixing as necessary.
The stirring and mixing can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser or the like.

The ink of the present invention can be used favorably in any printer equipped with an ink jet head of the following method, but can be particularly suitably used for a piezo type.
A so-called piezo type in which a piezoelectric element is used as pressure generating means for pressurizing ink in the ink flow path, and a diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. (See Japanese Patent Laid-Open No. 2-51734)
A so-called thermal type that generates bubbles by heating ink in the ink flow path using a heating resistor (see Japanese Patent Laid-Open No. 61-59911)
An ink droplet is formed by changing the inner volume of the ink flow path by deforming the vibration plate by an electrostatic force generated between the vibration plate and the electrode, with the vibration plate and the electrode forming the wall surface of the ink flow path facing each other. Electrostatic discharge type (see JP-A-6-71882)

The tarpaulin in the present invention refers to what is commonly called “tarporin”, that is, a laminate obtained by bonding a thermoplastic resin layer to both surfaces of a polyester fiber base fabric.
Further, the tarpaulin used as a substrate in the recording method of the present invention has a surface composition with an absorbance represented by [peak absorbance at 1720 ± 5 cm ⁻¹ / peak absorbance at 2960 ± 5 cm ⁻¹ ] in the infrared absorption spectrum. The ratio needs to be 2.50 to 5.50, and the infrared absorption spectrum of the tarpaulin surface can be easily measured by the ATR method (total reflection measurement method).
From the viewpoint of obtaining stronger adhesion, the absorbance ratio is preferably 2.60 to 5.35.

  According to the recording method of the present invention, a printed matter having high image quality and high fastness can be obtained by combining the tarpaulin and water-based ink. It is more desirable to heat the recording medium after printing in order to form an image with higher image quality and higher abrasion resistance and adhesion, and to be able to cope with high-speed printing conditions.

As a device used for heating, many known devices can be used. For example, devices such as forced air heating, radiation heating, conduction heating, high frequency drying, and microwave drying may be used, and these may be used alone or in combination of two or more.
The heating temperature can be changed according to the type and amount of the water-soluble organic solvent contained in the ink and the minimum film-forming temperature of the resin emulsion to be added, and further changed depending on the type of the substrate to be printed. Can do.

The heating temperature is preferably high from the viewpoints of drying property and film-forming temperature. However, if the heating temperature is too high, the substrate to be printed is damaged, or non-ejection occurs due to warming up to the ink head. This is not preferable because there is a possibility that the
As a heating temperature range, 40-120 degreeC is preferable, More preferably, it is 50-90 degreeC.

  Here, an ink jet recording apparatus capable of recording using the ink of the present invention will be described with reference to the drawings. Inkjet recording apparatuses include a serial type (shuttle type) scanned by a carriage and a line type equipped with a line type head. FIG. 1 is a schematic diagram showing an example of a serial type inkjet recording apparatus.

  The ink jet recording apparatus includes an apparatus main body 101, a paper feed tray 102 mounted on the apparatus main body 101, a paper discharge tray 103, and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 200. Reference numeral 111 denotes an upper cover, and reference numeral 112 denotes a front surface of the front cover.

In the apparatus main body 101, as shown in FIG. 2, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates (not shown). Then, the scanning is moved by a main scanning motor (not shown).
The carriage 133 has a plurality of ink ejection openings of a recording head 134 including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
Further, the carriage 133 is equipped with sub tanks 135 for each color for supplying each color ink to the recording head 134. The sub tank 135 is supplied with water-based ink according to the present invention from the ink cartridge 200 loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown) and is replenished.

On the other hand, as a sheet feeding unit for feeding the substrate 142 loaded on the substrate loading unit (pressure plate) 141 of the sheet feeding tray 102, the substrate 142 is separated and fed one by one from the substrate loading unit 141. Opposite the half-moon roller [paper feed roller 143] and the paper feed roller 143, a separation pad 144 made of a material having a large friction coefficient is provided, and this separation pad 144 is urged toward the paper feed roller 143 side. The base material 142 is the tarpaulin according to the present invention.
As a transport unit for transporting the base material 142 fed from the paper feed unit on the lower side of the recording head 134, a transport belt 151 for electrostatically attracting and transporting the base material 142, and a paper feed unit On the conveyor belt 151, the counter roller 152 for transporting the base material 142 fed through the guide 145 with the transport belt 151 being sandwiched between the counter roller 152 and the base material 142 fed substantially vertically upward is changed by about 90 °. And a leading end pressure roller 155 urged toward the conveyor belt 151 by a pressing member 154, and charging as charging means for charging the surface of the conveyor belt 151. A roller 156 is provided.

  The conveyor belt 151 is an endless belt, is stretched between a heater-type conveyor roller 157 and a tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a non-porous substrate adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE). And a back layer (medium resistance layer, earth layer) which is made of the same material as the surface layer and is subjected to resistance control by carbon. A heater-type guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the base material 142 recorded by the recording head 134, a separation claw 171 for separating the base material 142 from the transport belt 151, a paper discharge roller 172, and a paper discharge roller 173, After the substrate 142 is dried with hot air by the fan heater 174, it is output to the sheet discharge tray 103 below the sheet discharge roller 172.

A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the base material 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the base material 142 is separated and fed one by one from the paper feed unit, and the base material 142 fed substantially vertically upward is guided by the guide 145, It is sandwiched between and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °. At this time, the conveyance belt 151 is charged by the charging roller 156, and the base material 142 is electrostatically attracted to the conveyance belt 151 and conveyed.
Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped base material 142 to record one line, and the base material 142 is conveyed by a predetermined amount. After that, the next line is recorded. Upon receiving a recording end signal or a signal that the rear end of the base material 142 reaches the recording area, the recording operation is finished, and the base material 142 is discharged onto the paper discharge tray 103.
The ink jet recording product of the present invention is obtained by the above ink jet recording method.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “part” is “part by mass”, and “%” is “% by mass” except for those in the evaluation criteria.

<Preparation of polycarbonate urethane resin emulsion 1>
In a reaction vessel into which a stirrer, a reflux condenser and a thermometer were inserted, 1500 g of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), 220 g of 2,2-dimethylolpropionic acid (DMPA) and N-methyl 1347 g of pyrrolidone (NMP) was charged under a nitrogen stream and heated to 60 ° C. to dissolve DMPA. Subsequently, 1445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out a urethanization reaction for 5 hours to obtain an isocyanate-terminated urethane prepolymer.

  The reaction mixture was cooled to 80 ° C., 4340 g was extracted from the mixture in which 149 g of triethylamine was added and mixed, and added to a mixed solution of 5400 g of water and 15 g of triethylamine with vigorous stirring. Next, 1500 g of ice was added, 626 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid content concentration became 30%. -Based urethane resin emulsion 1] was obtained.

  It was 35 nm when the volume average particle diameter of the obtained [polycarbonate-type urethane resin emulsion 1] was measured using the particle size analyzer (Microtrac MODEL UPA9340, Nikkiso Co., Ltd. product).

<Preparation of polycarbonate urethane resin emulsion 2>
[Polycarbonate-based urethane resin emulsion 2] was obtained in the same manner as in the preparation of [Polycarbonate-based urethane resin emulsion 1] except that 4,4′-dicyclohexylmethane diisocyanate was changed to isophorone diisocyanate.
It was 24 nm when the volume average particle diameter of the obtained polycarbonate-type urethane resin emulsion 2 was measured using the particle size analyzer (Microtrac MODEL UPA9340, Nikkiso Co., Ltd. product).

<Preparation of polyether urethane resin emulsion>
In the preparation of [Polycarbonate-based urethane resin emulsion 1], the same procedure as in [Polycarbonate-based urethane resin emulsion 1] was used except that polyether polyol (Hiflex D2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of polycarbonate diol. [Polyether-based urethane resin emulsion] was obtained.
It was 13 nm when the volume average particle diameter of the obtained [polyether-based urethane resin emulsion] was measured using a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.).

<Preparation of polyester urethane resin emulsion>
In the preparation of the [polycarbonate urethane resin emulsion 1], a polyester polyol (Polylite OD-X-2420 manufactured by DIC) was used instead of the polycarbonate diol. A [polyester urethane resin emulsion] was obtained.
It was 54 nm when the volume average particle diameter of the obtained [polyester urethane resin emulsion] was measured using a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.).

<Preparation of acrylic resin emulsion>
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring.
Maintaining the internal temperature at 70 ° C., adding 4 g of potassium persulfate as a polymerization initiator, dissolving, and previously stirring 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 365 g of styrene, 545 g of butyl acrylate, and 10 g of methacrylic acid The emulsion prepared in addition to the chemical conversion was continuously dropped into the reaction solution over 4 hours.
After completion of the dropwise addition, aging was performed for 3 hours.
The obtained aqueous emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 30% by mass and pH 8.
It was 88 nm when the volume average particle diameter of the obtained [acrylic resin emulsion] was measured using a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.).

<Preparation of black pigment dispersion>
The following prescription mixture was premixed and then circulated and dispersed for 7 hours in a disk type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mm diameter zirconia ball used) to obtain a black pigment dispersion.
Carbon black pigment (Monarch 800 manufactured by Cabot Corporation) 15 parts Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 2 parts Ion-exchanged water 83 parts

<Preparation of cyan pigment dispersion>
A cyan pigment dispersion was obtained in the same manner as in the preparation of the black pigment dispersion, except that Pigment Blue 15: 4 was used as the pigment to be used.
<Preparation of magenta pigment dispersion>
A magenta pigment dispersion was obtained in the same manner as in the preparation of the black pigment dispersion, except that Pigment Red 122 was used as the pigment to be used.
<Preparation of yellow pigment dispersion>
A yellow pigment dispersion was obtained in the same manner as in the preparation of the black pigment dispersion, except that Pigment Yellow 74 was used as the pigment to be used.

<Preparation of ink>
The ink was prepared by mixing and stirring with the formulation described in Table 2 and filtering with a 0.2 μm polypropylene filter.
The surfactant in the table is Softanol EP-5035 (manufactured by Nippon Shokubai Co., Ltd.), and the polyolefin resin emulsion and the polyester resin emulsion are commercially available, respectively. Aurolen AE-202 (polyolefin manufactured by Nippon Paper Industries Co., Ltd.) Resin emulsion) and Elitel KT-8803 (polyester resin emulsion manufactured by Unitika) were used.
Moreover, when the volume average particle diameter of the polyolefin resin emulsion and the polyester resin emulsion was measured using a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.), they were 140 nm and 115 nm, respectively.

[Examples 1-11, Comparative Examples 1-8]
Using the prepared ink, printing on various tarpaulins and the evaluation described below were performed.
The types of ink and tarpaulin used and the evaluation results are shown in Table 3.
The types of tarpaulins used in Table 3 are as follows, and the numbers in parentheses indicate the absorbance ratio represented by [peak absorbance at 1720 ± 5 cm ⁻¹ / peak absorbance at 2960 ± 5 cm ⁻¹ ]. It is a value measured by the ATR method using an infrared spectroscopic analyzer Spectrum Two manufactured by PerkinElmer. The measurement was performed with a single reflection using a diamond prism.
Tarpaulin A: VS-T (4.71) manufactured by Bell Adwise
Tarpaulin B: NIJ-WTM (5.34) manufactured by Nichie
Tarpaulin C: LT15GS (2.61) manufactured by Lucio
Tarpaulin D: VALEX 7504 (5.58) manufactured by Lucio
Tarpaulin E: LUMIJET-W002 (2.27) manufactured by IKC

Infrared absorption spectra of tarpaulins A to E measured by the ATR method for each substrate are shown in FIGS. Moreover, the light absorbency which can be read from the spectrum of each base material and its ratio are shown below.

In consideration of the use in outdoor applications, the evaluation criteria for substrate adhesion and scratch resistance were considerably stricter than when printing on general paper.
From these evaluation results, it can be seen that the ink of the present invention is suitable for outdoor use.

<Image density evaluation>
The prepared ink was filled in an ink jet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), a solid image was printed on the target tarpaulin, and then dried at 80 ° C. for 1 hour.
The density of the solid image portion was measured four times with X-Rite 938 (manufactured by X-Rite) and judged from the average value.

<Base material adhesion evaluation>
The prepared ink was filled in an inkjet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), a solid image was printed on the target tarpaulin, and dried at 80 ° C. for 1 hour.
Evaluated by counting the number of remaining squares of 100 1 mm test squares by a cross-cut peel test (based on JIS-K5600) using a cloth adhesive tape (123LW-50 made by Nichiban) for the solid part of the image did.

<Abrasion resistance evaluation>
The prepared ink was filled in an inkjet printer (IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), a solid image was printed on the target tarpaulin, and then dried at 80 ° C. for 1 hour.
The solid part was rubbed with dry cotton (Kanakin No. 3) under a load of 400 g, and the rub resistance was determined according to the following criteria.
A: The image does not change even after rubbing 51 times or more.
B: Some scratches remain after rubbing 50 times, but the image density is not affected.
C: The image density is lowered while rubbing 31 to 50 times.
D: Image density decreases during rubbing 11 to 30 times.
E: Image density is lowered by rubbing 10 times or less.

Examples 1 to 7 are particularly preferred examples of the present invention, in which a high concentration is obtained, and adhesion to a substrate and high scratch resistance are obtained. Gloss and scratch resistance can be obtained.
Examples 8 and 9 are examples that contain a urethane resin but are not polycarbonate-based. Compared to those using a polycarbonate-based resin, the printed materials can be obtained with excellent scratch resistance.
Examples 10 and 11 are examples in which the type of the water-soluble organic solvent does not use those described in claim 3. Compared with Examples 1 and 2, the resin film-forming property is slightly inferior, so the concentration decreases. Also, the scratch resistance is slightly inferior.

Comparative Examples 1 and 2 are examples in which the absorbance ratio of the surface of the tarpaulin does not satisfy the range of claim 1 and the substrate adhesion is greatly inferior.
Comparative Examples 3 and 4 are examples in which only one type of urethane resin is included, and the image density is greatly inferior.
Comparative Example 5 is an example containing only an acrylic resin. Similar to Comparative Examples 3 and 4, the image density is inferior, and since no urethane resin is contained, adhesion and scratch resistance cannot be obtained.
Comparative Examples 6 and 7 are examples in which two types of resins are included, but no urethane resin is included, and adhesion and scratch resistance are still not obtained, which is problematic in practical use.
Comparative Example 8 is an example that does not contain a resin in the first place, and the performance was inferior in all items.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front face 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Substrate loading part 142 Base material 143 Paper feed Roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Holding member 155 Tip pressure roller 156 Charging roller 157 Conveying roller 158 Densation roller 161 Guide member 171 Separating claw 172 Discharging roller 173 Discharging roller 174 Fan heater 181 Double-sided paper feed unit 182 Manual paper feed unit 200 Ink cartridge

JP 2005-220352 A JP 2011-094082 A JP2012-46671 JP2012-241135

Claims (4)

In the ink jet recording method in which printing is performed on a tarpaulin using water-based ink, [the peak absorbance at 1720 ± 5 cm ⁻¹ / the peak absorbance at 2960 ± 5 cm ⁻¹ ] in the infrared absorption spectrum obtained by the ATR method on the surface of the tarpaulin. The water-based ink contains at least water, a water-soluble organic solvent, a pigment, two or more types of resins, and at least one of the two or more types of resins. An ink jet recording method, wherein one type is a urethane resin.   The inkjet recording method according to claim 1, wherein the urethane resin is a polycarbonate-based urethane resin.   The water-soluble organic solvent is at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. The inkjet recording method according to claim 1, wherein the inkjet recording method comprises seeds. In the method for producing an ink jet recorded matter by producing an ink jet recorded matter by performing printing using a water-based ink on the tarpaulin, the tarpaulin has [1720 ± 5 cm in the infrared absorption spectrum obtained by the ATR method on the surface of the tarpaulin. ^-1 Peak absorbance / 2960 ± 5 cm ^-1 Using a tarpaulin having an absorbance ratio of 2.50 to 5.50, the water-based ink contains at least water, a water-soluble organic solvent, a pigment, and two or more resins. A method for producing an ink jet recorded product, comprising using a water-based ink in which at least one of the two or more types of resins is a urethane resin.

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