JPH11181345A - Composition for ink jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can form a printed film showing good adhesion to a polyolefin-based resin substrate by making the composition contain a chlorinated polyolefin-based resin, an epoxy group-containing resin which is liquid at ambient temperatures and a silicone-acrylate-based resin. SOLUTION: The composition contains preferably 100 parts by weight (hereinafter parts) of a chlorinated polyolefin-based resin having a chlorine content of 10-60 wt.%, a weight average molecular weight of 1,000-100,000, preferably 3,000-50,000, preferably 1-500 parts of a resin which has not less than one epoxy groups and is liquid at ambient temperatures (for example; a bisphenol A type epoxy resin), preferably 1-100 parts of a silicon acrylic-based resin and, if necessary, preferably 50-1,000 parts of a resin soluble in said resin which has not less than one epoxy groups and is liquid at ambient temperatures (for example; an acrylic resin). Even when a substrate made of the same polyolefin-based resin is laminated on the printed film formed of the composition, said printed film is not transferred to the laminated substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for ink-jet printing, and more particularly to a composition capable of forming a printed film having excellent adhesion to the surface of a polyolefin-based resin base material. The present invention relates to a composition for ink jet printing which can form a print film which is not transferred to the overlapped substrate even when the same polyolefin resin substrate is overlapped.

[0002]

2. Description of the Related Art Since polyolefin resins do not have highly reactive functional groups, it is generally difficult to apply adhesion or coating to polyolefin resin substrates.
In order to improve this point, some attempts have been made to improve the adhesion of the coating film by modifying the surface of the resin by a physical treatment method such as an acid treatment, a corona discharge treatment, and a plasma treatment. . However, in these cases, the process becomes complicated or a huge capital investment is required. Further, even if such complicated processes and capital investment are implemented, it is hard to say that an effect commensurate with them is always obtained.

[0003] In addition, when ink-jet printing is performed on the surface of a polyolefin resin substrate, and the substrate is placed on the printed film after drying, when a load is applied, the printed film is deposited on the surface of the laminated substrate. There was a disadvantage that it was transferred. There is a need to remedy this drawback, and various ink jet printing compositions have been proposed as a solution.

[0004]

However, at present, a print film which sufficiently satisfies the above-mentioned properties has not been obtained with the conventional ink jet printing composition. An object of the present invention is to solve the above problems of the conventional ink jet printing composition, that is, a polyolefin resin, for example, propylene homopolymer, ethylene-
A propylene copolymer, a molded product having an ethylene-propylene-butene copolymer as a main component, a film, a printed film having excellent adhesion to a fiber product, etc. can be formed,
Another object of the present invention is to provide an ink jet printing composition capable of forming a printed film that is not transferred to the surface of the superposed substrate even when the same substrate is stacked on the printed film.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the inkjet printing composition containing a chlorinated polyolefin resin has at least one epoxy group. The present inventors have found that the above problems can be solved by adding a resin and a silicone acrylic resin which are liquid at ordinary temperature, and have reached the present invention.

That is, the composition for ink jet printing of the present invention is characterized by containing a chlorinated polyolefin resin, a resin which is liquid at room temperature having at least one epoxy group, and a silicone acrylic resin. Further, the ink jet printing composition of the present invention is characterized by containing, as an additional component other than the above components, a resin having at least one epoxy group and being compatible with a liquid resin at normal temperature and at room temperature.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the composition for ink jet printing of the present invention will be described in detail. Examples of the chlorinated polyolefin resin used in the present invention include, for example, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, and chlorinated polyolefin compounds obtained by modifying these with an acrylic polymer having an ethylenically unsaturated bond or urethane. And preferably has a chlorine content of 10
-60% by weight, weight average molecular weight of 1,000-100,
000, more preferably in the range of 3,000 to 50,000. The chlorinated polyolefin resin mainly contributes to the adhesion to the polyolefin resin substrate.

The liquid resin at room temperature having at least one epoxy group used in the present invention includes allyl glycidyl ether, phenyl glycidyl ether, diglycidyl ether of bisphenol A, epoxidized vegetable oil, epoxidized low fatty acid and esters thereof, An epoxy group-containing compound of cyclohexane is exemplified. A room temperature liquid resin having at least one epoxy group imparts flexibility to the printed film, and is particularly effective when the printed film is formed on a stressed surface such as a film surface.
In addition, it has an effect as a storage stabilizer of the chlorinated polyolefin resin. In order to achieve these effects, a liquid resin having at least one epoxy group at room temperature and having a temperature of 1 to 500 parts by weight per 100 parts by weight of the chlorinated polyolefin resin is used.
It is preferred to mix in parts by weight.

The silicone acrylic 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 a compound represented by the following chemical formula. _{HO-Si (R) 2 -O-} [Si (R) 2 -O] in _n -Si (R) ₂ -OH (wherein, R is a mixture of either a methyl group, a hydrogen element and a methyl group Or a part of the methyl group is substituted with an ethyl group, a vinyl group or a phenyl group, and n is an integer of 10 to 5,000). In the above chemical formula, 50 to 100 mol% of R is a methyl group,
An organopolysiloxane in which 0 to 50 mol% is a hydrogen element is preferable, and up to 80 mol% of a methyl group thereof may be substituted with an ethyl group, a vinyl group or a phenyl group.

The acrylic polymer is a polymer having a molecular weight of from 500 to 80,000, preferably from 1,000 to 15,000, obtained by polymerizing a monomer such as an α, β-unsaturated acid or an ester thereof. Or it is a copolymer. Examples of the α, β-unsaturated acids or esters thereof include acrylic acid, methacrylic acid, and methyl, ethyl, butyl, stearyl, 2-ethylhexyl, 2-hydroxyethyl, and 3-hydroxypropyl esters thereof. Esters and the like can be mentioned.

The comonomer which can be copolymerized with the α, β-unsaturated acid or ester thereof includes maleic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, vinyl acetate, vinyl propionate and the like. Can be mentioned. When the acrylic acid or acrylic acid ester-based polymer is a copolymer, the proportion of acrylic acid, methacrylic acid or its ester in the total copolymer is usually 10 to 75 mol%. , Preferably 2
5 to 60 mol%. Silicone acrylic resin
This has the effect of preventing transfer to the substrate surface when the polyolefin-based resin substrate is overlaid on the printed film, and has the effect of enhancing the adhesion. In order to achieve this effect, a silicone acrylic resin is replaced with a chlorinated polyolefin resin 10.
It is preferable to mix in an amount of 1 to 100 parts by weight with respect to 0 parts by weight.

Additional components other than the above-mentioned components of the ink-jet printing composition, that is, epoxidized resin which is a component other than chlorinated polyolefin resin, resin at room temperature having at least one epoxy group, and silicone acrylic resin. Examples of the resin that is compatible with a liquid resin at normal temperature having at least one resin include an acrylic resin, a phenol resin, a maleic resin, a toluenesulfonamide formaldehyde resin, a modified epoxy resin, a xylene resin, a melamine resin, and a cellulose ester resin. Is desirable.

The above-mentioned resin having at least one epoxy group and being compatible with a liquid resin at normal temperature enhances the flexibility of the whole printed film and contributes to the adhesion to the polyolefin resin substrate. In order to achieve these effects, a resin that has at least one epoxy group and is compatible with a liquid resin at room temperature is mixed in an amount of 50 to 1000 parts by weight based on 100 parts by weight of the chlorinated polyolefin resin. Is preferred. The composition for inkjet printing of the present invention may contain additives such as a colorant, a solvent, and a conductivity adjuster, a surfactant, an ultraviolet absorber, a quencher, a dispersant, and a preservative, if necessary. it can.

As the above-mentioned coloring agent which can be used in the present invention, various ones can be mentioned, but those which are compatible with the above-mentioned ink jet printing composition and are soluble in a solvent are preferable. Representative colorants that can be used in the present invention include C.I. I. Solvent Bl
ack22, C.I. I. Solvent Black2
7, C.I. I. Solvent Black 28, C.I.
I. Solvent Black 29, C.I. I. Sol
vent Red 83-1, C.I. I. Solvent
Red 125, C.I. I. Solvent Red13
2, C.I. I. Solvent Blue 47, C.I. I.
Solvent Blue 48, C.I. I. Solven
t Blue 70, C.I. I. Solvent Yellow
ow88, C.I. I. Solvent Yellow 8
9, C.I. I. Basic Violet 1, C.I. I. B
asic Violet 3, C.I. I. Basic Re
d1, C.I. I. Basic Red 8, C.I. I. Bas
and inorganic or organic pigments such as ic Black 2, basic dyes, titanium oxide, carbon black, zinc sulfide, oily smoke, graphite, red iron oxide, phthalocyanine blue, phthalocyanine green, brilliant carmine 6B, and lake red C. However, when an insoluble dye or pigment is used, the particle size is usually preferably 3 μm or less, particularly preferably 1 μm or less, in order to prevent nozzle clogging. The amount of the coloring agent is 100
A suitable amount is usually 50 to 1000 parts by weight, preferably 80 to 800 parts by weight, per part by weight.

In the present invention, a solvent is used to appropriately adjust the viscosity of the composition for ink jet printing.
Various solvents can be used without particular limitation as long as they are compatible with other components of the composition for inkjet printing. Representative examples of solvents that can be 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. Further, in order to improve the solubility of the chlorinated polyolefin-based resin, it is also possible to add an aromatic solvent such as toluene and xylene. The amount of the solvent in the ink-jet printing composition is determined in consideration of the viscosity, surface tension and the like of the ink-jet printing composition, but is usually 50 to 95% by weight of the ink-jet printing composition, preferably Is 70-9
A suitable amount is 0% by weight.

Examples of the above-mentioned conductivity adjusting agent that can be used in the present invention include lithium nitrate, lithium nitrite, ammonium sulfite, ammonium formate, ammonium acetate, lithium halide, sodium thiocyanate and the like. Further, the above-mentioned surfactants, ultraviolet absorbers, quenchers, dispersants, preservatives and the like which can be used in the present invention are those commonly used in ink jet printing compositions. The composition for ink jet printing of the present invention is characterized in that these additives are added to the ink composition for ink jet printing at 0.1%.
It can be contained in an amount of 1 to 5% by weight.

The composition for ink-jet printing of the present invention needs to have characteristics suitable for the ink-jet printing method. Therefore, the composition has a viscosity of 1 to 10 mPa.
S (20 ° C.), and the surface tension is desirably in the range of 20 to 70 mN / m. When preparing the composition for inkjet printing of the present invention, after mixing and stirring each component, the nozzle diameter of the jet printer to be used is, for example, about 1%.
The mixture is filtered and purified using a filter having a pore size of / 10 or less.

The composition for ink jet printing of the present invention comprises:
A conventionally known jet printer can be used. As such a jet printer, for example,
There are a load control system, an ink-on-demand system, and a system in which ink is ejected by a thermal head. The ink-jet printed ink forms a dry film by drying at room temperature to several hundred degrees Celsius.

The object to be printed using the ink jet printing composition of the present invention is not particularly limited as long as the printed ink jet printing composition is not deformed or deteriorated under drying conditions. For example, it can be printed on the surface of a base material such as metal, glass, plastic, especially a polyolefin resin, paper coated with a resin on the surface, particularly a polypropylene laminated paper, or a transparent sheet for an overhead project.
The composition for inkjet printing of the present invention can form a printed film having excellent adhesion to a substrate surface such as PP and PE as compared with a conventional composition for inkjet printing, and Even if a substrate is overlaid on the printed film, a printed film that is not transferred to the surface of the overlaid substrate can be formed.

[0020]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “parts” and “%” are based on weight. Examples 1 to 5 and Comparative Examples 1 to 4 The components shown in Table 1 were used in the amounts (parts) shown in Table 1 and uniformly mixed, and then purified by filtration through a membrane filter having a pore size of 1.0 μm. Inkjet printing compositions corresponding to the examples and the comparative examples were prepared.

The components used were as follows. -Chlorinated polyolefin resin having a chlorine content of 25% and Mw of about 30,000 (in Table 1, "chlorinated PO resin A"
Described). -Chlorinated polyolefin resin having a chlorine content of 40% and Mw of about 30,000 ("Chlorinated PO resin B" in Table 1)
Described). A bisphenol A type epoxy polymer having an epoxy equivalent of 180 to 190 (described in Table 1 as "epoxy resin A"). Monoglycidyl ether having an epoxy equivalent of 154 (described as “Epoxy resin B” in Table 1).

The main chain is MMA, and the side chain has dimethylpolysiloxane, Mw of about 15,000, NV = 5
0% resin (referred to as "silicone acrylic resin" in Table 1). -A toluenesulfonamide formaldehyde resin having an Mw of about 500. -Novolak type phenol resin having an Mw of about 2,000) In Table 1, it is described as "phenol resin"). A methyl methacrylate resin having an Mw of about 10,000 (described as “acrylic resin” in Table 1). A carbon epoxy graft type powder colorant having a carbon black content of 50% (referred to as "carbon graft polymer" in Table 1).

Each of the obtained ink-jet printing compositions is jetted onto a polypropylene film in a predetermined image by a jet printer to form a print film, and the print film is subjected to an adhesion test, a cellophane tape peel test, and the like. A transfer resistance test was performed. <Adhesion test>: After forming a print film on a polypropylene film with a jet printer, the film was crumpled to confirm the presence or absence of peeling of the dot film, and evaluated according to the following criteria. ：: No abnormality ○: Partially peeled but recognizable ×: Many peels, unrecognizable

<Cellophane tape peeling test>: After forming a print film on a polypropylene film with a jet printer, a cellophane tape was stuck on the printed portion, the cellophane tape was peeled off, and the presence or absence of the dot film peeling was confirmed. evaluated. ：: No abnormality ○: Partially peeled but recognizable ×: Many peels, unrecognizable

<Transfer resistance test>: A print film was formed on a polypropylene film using a jet printer, and then the polypropylene film was overlaid on the polypropylene film to obtain 50 kgf / c.
After pressurization with a force of m ² and left at 40 ° C. for 24 hours, the presence or absence of transfer to the stacked substrates was examined and evaluated according to the following criteria. ：: no transfer ×: transfer was partially observed The results were as shown in Table 2.

[0026]

[Table 1]

[0027]

As is clear from the results shown in Table 2,
The print film formed using the composition for inkjet printing of the present invention showed excellent results in an adhesion test, a cellophane peel test and a transfer resistance test. On the other hand, printing formed using the inkjet printing composition of Comparative Example 1, which contains a chlorinated polyolefin-based resin and a resin which is liquid at room temperature and has at least one epoxy group, but does not contain a silicone acrylic resin. The coating failed the transfer resistance test, and the chlorinated polyolefin resin
A printed film formed using the inkjet printing composition of Comparative Example 2 containing a silicone acrylic resin but not containing a liquid resin at room temperature having at least one epoxy group has an adhesion test and a cellophane peel test. Was rejected. Comparative Example 3 using other resin as binder
In Nos. And 4, the adhesion test, the cellophane peel test and the transfer resistance test failed.

[0029]

The composition for inkjet printing of the present invention can form a printed film having excellent adhesion to the surface of a polyolefin-based resin substrate, and the same polyolefin-based resin base is formed on the printed film. Even when materials are stacked, a printed film that is not transferred to the stacked base material can be formed.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuneo Shirota 1-18-3 Nakazato, Minami-ku, Yokohama-shi, Kanagawa Prefecture

Claims (3)

[Claims] 1. An ink jet printing composition comprising a chlorinated polyolefin resin, a resin having at least one epoxy group and being liquid at room temperature, and a silicone acrylic resin. 2. A chlorinated polyolefin resin having a chlorine content of 10 to 60% by weight and a weight average molecular weight of 1,000 to 100,000, and 1 to 500 parts by weight based on 100 parts by weight of the chlorinated polyolefin resin. The resin according to claim 1, wherein the resin contains a liquid resin at room temperature having at least one epoxy group and 1 to 100 parts by weight of a silicone acrylic resin with respect to 100 parts by weight of the chlorinated polyolefin resin. Composition for inkjet printing. 3. An additional component other than the composition component according to claim 1 or 2, wherein a resin having at least one epoxy group and being compatible with a liquid resin at ordinary temperature is added to 100 parts by weight of a chlorinated polyolefin resin. 3. The composition for inkjet printing according to claim 1, wherein the composition is contained in an amount of 50 to 1000 parts by weight.