JPH07118583A - Ink-jet printing composition - Google Patents

Abstract

PURPOSE:To provide an ink-jet printing compsn. capable of forming a film of printing having a light resistance, a moisture resistance, a heat resistance, an abrasion resistance, and such a high adhesion as not be transferred to a surface of other base material placed thereon. CONSTITUTION:An ink-jet printing compsn. comprises at least one resin selected from the group consisting of acrylic silicone resins, cellulose ester resins, cellulose ether resins, polyvinyl acetal resins, and fluororesins.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is capable of forming a printed film having excellent adhesion and moisture resistance on the surface of a substrate such as metal, glass, plastic, etc. The present invention relates to a jet printing ink composition in which a printed film does not transfer to the surface of a laminated base material.

[0002]

2. Description of the Related Art In recent years, dot printing and pattern printing have been widely performed on a surface of a substrate such as metal, glass, plastic, and paper by using an inkjet printing method. As a method for testing the quality of the adhesion of the film formed by this inkjet printing method, there is a test method in which dot printing or pattern printing is performed using a jet printer, and tape peeling of the base crosscut is performed. A coating having sufficient adhesion to the method has not been obtained so far. Further, when inkjet printing is performed on the base material and the base materials are overlapped with each other and a load is applied to the base material, there is a disadvantage that the dried print film is transferred to the surface of the overlapped base material. Furthermore, in order to improve the durability of the product having the pattern of the film formed by inkjet printing, the light resistance, moisture resistance, heat resistance and abrasion resistance of the printing film should be prevented, and the bleeding prevention to improve the printing quality. It is required to further improve the anti-repellency and the cissing resistance. On the other hand, in the conventional ink jet printing composition, a printing film which satisfies all of the above conditions is not obtained at present.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the problems of conventional ink jet printing compositions, and provides light resistance, moisture resistance, heat resistance, abrasion resistance, anti-bleeding property, and overlaying a base material. Another object of the present invention is to provide a composition for inkjet printing, which forms a printed film having high adhesion so that the printed film does not transfer to the surface of another substrate.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that an acrylic silicone resin, a cellulose ester resin, a cellulose ether resin, a polyvinyl acetal resin and a fluororesin are used. By using as a binder in combination with at least one resin selected from the group consisting of
The present invention has been accomplished by finding that an ink jet printing composition that forms a print film having particularly high adhesion can be obtained. Therefore, the present invention provides at least one selected from the group consisting of (a) acrylic silicone resin, (b) (i) cellulose ester resin, (ii) cellulose ether resin, (iii) polyvinyl acetal resin, and (iv) fluororesin.
An ink jet printing composition comprising a resin of a kind is provided. More specifically, the present invention is
A room temperature curable ink jet printing composition containing a colorant, a solvent, an electric conductivity adjuster, a surfactant, etc., if necessary, wherein (a) an acrylic silicone resin and (b) (i) a cellulose ester. Resin, (ii) Cellulose ether resin (i
ii) An ink-jet printing composition comprising a binder containing a polyvinyl acetal resin and (iv) at least one resin selected from the group consisting of fluororesins. Hereinafter, the present invention will be described in detail.

The acrylic silicone resin used in the present invention includes a block polymer or a graft polymer prepared by reacting an acrylic acid polymer with an organopolysiloxane. As the organopolysiloxane, a linear polymer having an OH functional group is preferable, and examples thereof include compounds represented by the following formula. _{HO-Si (CH 3) 2} -O- (Si (CH 3) 2 -O) n -Si (CH 3) 2 -OH ( wherein,
n is 10 to 5000) In addition, up to 80 mol% of the methyl group in the above formula may be substituted with an ethyl group, a vinyl group or a phenyl group,
Particularly preferred is an organopolysiloxane in which 50 mol% or more is substituted with a methyl group.

The acrylic acid-based polymer has a molecular weight of 500 to 80,000, preferably 1,000 to 15,000, obtained by polymerizing a monomer such as an α, β-unsaturated acid or its ester. It is a polymer or a copolymer. Examples of the α, β-unsaturated acid or ester thereof include acrylic acid, methacrylic acid and their methyl esters, ethyl esters, butyl esters, stearyl esters, 2-ethylhexyl esters, 2-hydroxyethyl esters, 3-hydroxypropyl ester and the like. Further, the comonomer which is polymerized with the α, β-unsaturated acid or its ester is maleic acid, itaconic acid, fumaric acid, styrene, α
-Methylstyrene, vinyl acetate, vinyl propionate and the like. When the acrylic acid-based polymer is a copolymer, the proportion of acrylic acid, methacrylic acid or their esters is preferably 10 to 75 mol%, particularly 25 to 60 mol%. The acrylic acid-based polymer onto which the organopolysiloxane is grafted has a molecular weight of 500 to 80,000, preferably 1,000 to 1, produced from the α, β-unsaturated acid, its ester and the comonomer.
5,000 polymers and copolymers can be used. When the acrylic acid-based polymer is a copolymer, the ratio of acrylic acid, methacrylic acid or their esters is 10
˜75 mol%, especially 25 to 60 mol%.

Examples of the cellulose ester resin used in the present invention include cellulose diacetate, cellulose triacetate, nitrocellulose, cellulose nitrate, cellulose propionate and cellulose acetate butyrate. The molecular weight of this cellulose ester resin is 500-80,000, especially 500-1.
5,000 is preferred. Examples of the cellulose ether resin used in the present invention include methyl cellulose, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose and the like. The molecular weight of this cellulose ether resin is 1,000 to 50,000, especially 1,000.
-15,000 is preferable.

Typical examples of the polyvinyl acetal resin used in the present invention include polyvinyl butyral, polyvinyl acetoacetal and polyvinyl formal. The molecular weight of this polyvinyl acetal resin is 100
0 to 50,000 is preferable, and 1,000 to 15,000 is particularly preferable. Suitable fluororesins for use in the present invention include the fluorocopolymers described in JP-A-57-34107. That is, a suitable copolymer that can be used in the present invention is a copolymer containing fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as essential components, and has a weight average molecular weight of about 10,000 to 100,000.
The ones are suitable. The fluoroolefin in the present invention is preferably a perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene. Further, as the alkyl vinyl ether, those containing a linear or branched alkyl group having 2 to 8 carbon atoms, particularly those having 2 to 4 carbon atoms are preferable. The fluoroolefin and the alkyl vinyl ether can be used alone or as a mixture of two or more kinds.

Acrylic silicon resin in the present invention
The compounding ratio of (a) and at least one resin (b) selected from the group consisting of cellulose ester resin, cellulose ether resin, polyvinyl acetal resin and (iv) fluororesin is 100 parts by weight of resin (b). On the other hand, the acrylic silicone resin (a) is preferably 1 to 70 parts by weight, particularly preferably 1 to 10 parts by weight. Within this range, the inkjet printing composition of the present invention can form a print film that is excellent in adhesion and moisture resistance, and that does not transfer to the surface of the laminated base material even when the base material is overlaid on the print film. When two or more kinds of cellulose ester resin, cellulose ether resin, polyvinyl acetal resin and fluororesin are used, they can be used in any combination and have a total weight of 1 to 10.
It is used so that it becomes the weight part.

The colorant used in the present invention is not particularly limited as long as it is compatible with other ink components and soluble in the solvent. A typical example is Solvent.
Black 22, 27, 28, 29, Solvent Red 83 1, 125, 132, Solvent Blue 47, 48, Solvent
There are dyes such as Yellow 88 and 89, and inorganic or organic pigments such as titanium oxide, carbon black, zinc sulfide, oil smoke, yellow lead, red iron oxide, phthalocyanine blue, phthalocyanine green, brilliant carmine 6B, and lake red C. When using insoluble dyes and pigments, in order to prevent nozzle clogging, a particle size of 3 μm or less,
It is particularly preferably 1 μm or less.

In the present invention, the solvent is used for appropriately adjusting the viscosity of the ink. Therefore, if it is compatible with other components, it can be used without particular limitation. Representative examples of the solvent used in the present invention include ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, and ethers such as cellosolve and butyl cellosolve. Inkjet printing composition of the present invention, the resin (a) and (b), in addition to the colorant and solvent, if necessary, lithium nitrate, lithium nitrite, ammonium nitrite, ammonium formate, ammonium acetate, halogen. A conductivity adjusting agent such as lithium bromide and sodium thiocyanate, a surfactant and the like can be added. In the composition for inkjet printing of the present invention, the compounding amount of the binder comprising the resins (a) and (b) in combination is preferably 1 to 30% by weight, particularly 1 to 15% by weight in the composition. The blending amount of the colorant can be arbitrarily determined depending on the type of the colorant used and the like, but 1 to 15% by weight, particularly 5 to 10% by weight in the composition is suitable. The amount of the solvent blended is determined in consideration of the viscosity and surface tension of the ink composition, but usually 60 to 95% by weight of the composition is suitable, and the conductivity adjusting agent is 0.1 to 10% by weight. It is appropriate that the amount of the surfactant is 0.1 to 10% by weight.

Further, the composition for ink jet printing of the present invention is required to have characteristics adapted to the ink jet printing method. Therefore, the viscosity of the composition is 1 to 10 centipoise (20 ° C.) and the surface tension is 20 to 60 dynes / cm, the specific resistance is 200 to 3,000 Ωcm, and the specific gravity is preferably 0.8 to 1.2. When the ink composition of the present invention is prepared, the components are mixed and stirred, and then filtered and purified with a filter having a pore size of about 1/10 or less with respect to the nozzle diameter of the jet printer used. The inkjet printing composition of the present invention can be used in conventional jet printers. This jet printer includes, for example, a charge control system, an ink-on-demand system, and a system in which a thermal head ejects ink. Inkjet printed ink is
A dried film is formed by drying at several 100 ° C. The object to be printed using the composition of the present invention is not particularly limited as long as it does not deform or deteriorate under the conditions of drying the printed composition. For example, the surface of a base material such as metal, glass and plastic, paper coated with resin on the surface, transparent sheet for overhead projects, etc.

[0013]

EFFECTS OF THE INVENTION According to the present invention, as compared with the conventional ink jet printing composition, the adhesion of the printed film, the moisture resistance, the light resistance, the heat resistance and the abrasion resistance, the bleeding prevention property and the repellency prevention property at the time of printing, etc. An ink jet printing composition that is excellent in the properties and capable of forming a printing film that does not transfer to the surface of the laminated base material even when superposed on another base material was obtained.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples. In addition, "part" and "%" in the examples are based on weight. [Examples 1 to 8 and Comparative Examples 1 to 8] After uniformly mixing the components shown in Tables 1 and 2, the mixture was filtered and purified with a membrane filter having a pore size of 1.0 µ to correspond to each Example and each Comparative Example. A composition for inkjet printing was prepared. Each composition obtained was jetted in a predetermined image with a jet printer to form a printing film on a stainless plate, a glass plate, or a polyethylene terephthalate film, and the adhesion, transfer resistance, and light resistance of the printing film were formed. Resistance, moisture resistance, heat resistance, dot bleeding / repelling, and abrasion resistance tests.

As is clear from Tables 3 to 6, the composition of the present invention forms a printed film having excellent adhesion, moisture resistance, transfer resistance, abrasion resistance, and the like, and prevents bleeding and repellency. It was excellent in storage stability and storage stability. On the other hand, Comparative Examples 1 and 2 containing only the cellulose ester resin and Comparative Example 3 containing only the cellulose ether resin have poor transfer resistance and poor adhesion to metallic glass and polyethylene terephthalate. The wear resistance was poor. Comparative Example 4 of polyvinyl acetal resin alone
Had poor transfer resistance, moisture resistance, anti-bleeding property, anti-repellency property and abrasion resistance, and poor adhesion to metallic glass and polyethylene terephthalate. Further, Comparative Examples 5, 6, and 7 in which the silicon acrylic resin alone is used,
In each case, the transfer resistance was good, but the adhesion, the bleeding prevention property and the cissing prevention property were poor.

[0016]

[Table 1]Table 1 ────────────────────────────────────Example 1 2 3 4 5 6 7 8 Cellulose ester resin * 1) 4 4 2 Cellulose ester resin * 2) 4 4 Cellulose ether resin * 3) 4 compound Polyvinyl acetal resin * 4) 5 2 Silicon acrylic resin * 5) 0.1 0.1 0.2 agent Silicon acrylic resin * 6) 0.1 0.1 0.1 0.1 Silicon acrylic resin * 7) 0.1Fluororesin * 8) 0.1 12 Arrival Solvent Black 27 8 5 colors Solvent Black 29 10 10 8 10 8 4 10Agent Melted methyl ethyl ketone 85.9 80 82 44 85.7 44 86.9 77.8 Agent Ethanol 5.9 5.7 43 43 Add lithium nitrate 0.2 0.2Agent

[0017]

[Table 2] Table 2 ─────────────────────────────────── Comparative Examples 1 2 3 4 5 6 7 8 Cellulose ester resin * 1) 4 binder Cellulose ester resin * 2) 4 Cellulose ether resin * 3) 4 compound Polyvinyl acetal resin * 4) 5 Silicon acrylic resin * 5) 3 agents Silicon acrylic resin * 6) 3 Silicon acrylic resin * 7) 3 Fluorocarbon resin * 8) 3 12 pieces Solvent Black 27 10 10 colors Solvent Black 29 10 10 10 10 10 10 Agent soluble methyl ethyl ketone 80 80 80 80 80 80 80 78 Agent Ethanol 6 5.8 6 6 6.8 7 7 Addition Lithium nitrate 0.2 0.2 vulcanizing agent

[0018]

[Table 3] Table 3 ─────────────────────────────────── Example No. 1 2 3 4 4 Adhesion * 9) 10 0 10 0 10 0 98 10 0 10 0 10 0 10 0 96 99 99 96 100 100 100 100 100 100 100 100 100 100 100 100 Test transfer resistance * 10) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Light resistance * 11) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Item Moisture resistance * 12) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance * 13) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Eye dot bleeding ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ・ Repelling * 14) Abrasion resistance * 15) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Storage stability 60 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ * 16) 50 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 20 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ −5 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ※ test items, for each example and Comparative example Genus, were evaluated for glass and PET, in that order ◎, ○, △, indicated by ×. The same applies to Tables 4 to 6.

[0019]

[Table 4] Table 4 ─────────────────────────────────── Example No. 5 6 7 8 Trial Adhesion * 9) 10 0 10 0 10 0 96 98 97 10 0 10 0 99 10 0 10 0 10 0 100 100 100 100 100 100 100 100 100 100 100 100 Test transfer resistance * 10) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Light resistance * 11) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Item Moisture resistance * 12) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance * 13) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Eye dot bleeding ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ・ Repelling * 14) Abrasion resistance * 15) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Storage stability 60 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ * 16) 50 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 20 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ −5 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[0020]

[Table 5] Table 5 ─────────────────────────────────── Comparative Example No. 1 2 3 4 4 Adhesion * 9) 0 70 60 0 70 70 0 60 55 0 70 80 100 100 100 100 100 100 100 100 100 100 100 100 Test transfer resistance * 10) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Light resistance * 11) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Item Moisture resistance * 12) ○ ○ ○ ○ ○ ○ ○ ○ ○ × × × Heat resistance * 13) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Dot bleeding ○ ○ ○ ○ ○ ○ ○ ○ ○ × × × ・ Repelling * 14) Abrasion resistance * 15) △ ○ ○ △ ○ ○ △ ○ ○ △ △ △ Storage stability 60 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ * 16) 50 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 20 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ −5 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[0021]

[Table 6] Table 6 ─────────────────────────────────── Comparative Example No. 5 6 7 8 Adhesion * 9) 94 93 30 95 90 40 30 90 90 20 60 15 100 100 100 100 100 100 100 100 100 100 100 100 Test transfer resistance * 10) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ Light resistance * 11) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Item Moisture resistance * 12) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance * 13) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Eye dot bleeding × × × × × × × × × ○ ○ ○ ・ Repelling * 14) Abrasion resistance * 15) ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ △ Storage stability 60 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ * 16) 50 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 20 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ −5 ℃ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

* 1) Cellulose acetyl butyrate resin * 2) Cellulose acetate resin * 3) Ethyl cellulose ether resin * 4) Polyvinyl butyral resin * 5) Methyl methacrylate / dimethyl polysiloxane * 6) Ethyl methacrylate / dimethyl polysiloxane * 7) Acrylic acid alkyl ester, methacrylic acid alkyl ester, dimethyl siloxane * 8) Chlorotrifluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxyalkyl vinyl ether

* 9) According to JIS K5401, 1
A 100-mm square substrate test was conducted, the peeled state was confirmed with cellophane tape, and the number of adhesions in 100 was displayed. * 10) A polyethylene terephthalate plate was overlaid on the printed matter, pressed with a force of 50 kg / cm ² , and allowed to stand for 24 hours, and then the presence or absence of transfer to the polyethylene terephthalate plate was examined. ◎: No transfer at all ○: Transfer is observed in part * 11) UV intensity is 23 mW / cm in 360 nm spectrum
After exposure to the fade meter of No. ² for 300 hours, obtain the ΔE value with the preliminary sample. ΔE ≦ 1

* 12) Leave in water at 60 ° C for 50 hours,
Immediately after taking out and after performing room temperature drying for 5 hours, an adhesion and abrasion resistance test was performed. There should be no change. * 13) After leaving for 50 hours in a 120 ° C constant temperature bath, after obtaining the ΔE value with the preliminary sample, conduct an adhesion and abrasion resistance test. There should be no change. * 14) Visually check for bleeding and repelling of dots immediately after dot printing. There must be no bleeding or repellency. * 15) Rub the printed area 100 times with a rubbing tester with a load of 750 kg / cm ² and check if the printed film is peeled off. ◯: No abnormality Δ: Peeling of print film is observed in part. * 16) 1 at 60 ℃, 50 ℃, 20 ℃, and -5 ℃.
After allowing to stand for one month, the viscosity was measured with an Ostwald viscometer.
The difference from the initial viscosity must be within 0.5 centipons.

Claims (1)

[Claims] 1. An (a) acrylic silicone resin, (b)
An inkjet printing composition comprising (i) a cellulose ester resin, (ii) a cellulose ether resin, (iii) a polyvinyl acetal resin, and (iv) at least one resin selected from the group consisting of fluororesins.