JP2958895B2 - Thermal decomposition / oxide of α-olefin copolymer and thermal transfer ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermal decomposition / oxide of an α-olefin copolymer and a thermal decomposition / oxide containing the α-olefin copolymer. With regard to the thermal transfer ink composition, in particular, it is possible to obtain a print excellent in print quality and print accuracy such as bleeding and background contamination of a printing medium, and to form a heat-sensitive transfer layer having good adhesion to a base film. The present invention relates to a method for obtaining a thermal decomposition / oxide of an α-olefin copolymer suitable as a binder for a thermal transfer ink, and a thermal transfer ink composition containing the thermal decomposition / oxide.

<Related Art> In recent years, as a printing device in a device such as a facsimile, a personal computer, and a word processor, a printing device using a thermal transfer method has been widely used.

Such a thermal transfer type printing apparatus uses an ink ribbon having a thermal transfer ink layer mainly composed of a coloring component and a binder on one side, and prints the ink ribbon by using a heating point provided on a thermal head. Heating is performed in response to a signal to melt or soften the heat-sensitive transfer ink and transfer the ink to the surface of a printing medium on paper or the like to perform printing.

This thermal transfer ink transfers sufficiently to the surface of the printing medium, does not cause blurring or bleeding of printing, and does not stain the background of the printing medium, so that good printing quality can be obtained. Accordingly, there is a demand for a printing medium which can always obtain printing with good printing accuracy even on a printing medium having a poor surface smoothness.

Therefore, as this thermal transfer ink, those using various waxes as a binder have been used.
JP-A-62-21594 proposes a resin using a resin having a number average molecular weight of 30,000 or less as a binder.

<Problems to be Solved by the Invention> However, even with the above-mentioned conventional wax or a binder made of a resin having a number average molecular weight of 30,000 or less, it is possible to obtain a print having excellent print quality such as bleeding and background stains on a printing medium. It is difficult to form a heat-sensitive transfer layer having good adhesion to the base film.

Therefore, an object of the present invention is to solve the above-mentioned problems, and when used as a binder for a thermal transfer ink, it is possible to obtain a print excellent in printing quality and printing accuracy such as bleeding, background contamination of a printing medium, and the like. The present invention provides a thermal decomposition / oxide of an α-olefin copolymer capable of forming a thermal transfer layer having good adhesion to a base film, and further comprises a thermal transfer ink composition containing the thermal decomposition / oxide. Is to provide.

<Means for Solving the Problems> In order to solve the above problems, the present invention provides a thermal decomposition product of a copolymer of propylene and at least one selected from α-olefins having 4 to 10 carbon atoms. There, 135 ℃
Thermal decomposition / oxide of an α-olefin copolymer including a step of reacting an intrinsic viscosity measured in decalin of 0.02 to 0.7 dl / g in the presence of an oxygen-containing gas at 110 to 220 ° C. Is provided.

Further, the present invention also provides a thermal transfer ink composition containing 1 to 95% by weight of the thermal decomposition / oxide of the above-mentioned α-olefin copolymer.

 Hereinafter, the present invention will be described in detail.

The α-olefin-based copolymer which is a raw material of the thermal decomposition / oxide of the present invention is composed of propylene and at least one selected from α-olefins having 4 to 10 carbon atoms, preferably 4 to 6 carbon atoms. Copolymer. The α-olefin may be linear or branched, for example, butene-1, pentene-1, hexene-1, heptene-
1, octene-1, nonene-1, decene-1, 3-methylpentene-1, 4-methylpentene-1, 5-methylhexene-1, 6-methylheptene-1, and the like. One of these α-olefins or two or more thereof may be contained in the α-olefin-based copolymer.
Among these, an α-olefin-based copolymer containing butene-1, pentene-1, and hexene-1 is particularly preferable as the α-olefin.

The content of the α-olefin having 4 to 10 carbon atoms in the α-olefin-based copolymer is usually about 2 to 45 mol%, preferably about 4 to 30 mol%.

The thermal decomposition / oxide of the α-olefin copolymer of the present invention (hereinafter, abbreviated as “thermal decomposition / oxide”) is obtained by oxidizing the thermal decomposition product of the above-mentioned α-olefin copolymer. Things.

The thermal decomposition product of the α-olefin copolymer has an intrinsic viscosity of 0.02 to 0.7 dl / g, preferably 0.06 to 0.5 dl / g. Here, the intrinsic viscosity is a value measured in decalin at 135 ° C.

The thermal decomposition product having the above characteristics can be obtained by thermally decomposing the α-olefin copolymer in the presence or absence of a peroxide.

When thermally decomposing in the presence of a peroxide, the heating temperature is usually 150 to 380 ° C, preferably 170 to 300 ° C.
It is.

As the peroxide used, for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexyne-3, dibutyl peroxide, dicumyl peroxide,
t-butyl cumyl peroxide, α, α'-bis (t
Dibutyl peroxide such as -butylperoxy-metaisopropyl) benzene, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3- Hydroperoxides such as tetramethylbutyl hydroperoxide and the like can be mentioned. These may be used alone or in combination of two or more. Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-dimethyl-2,5-di (t-butylperoxy) hexane is suitable in that the half-life is appropriate at the heating temperature in the present invention.
Dimethyl-2,5-di (t-butylperoxy) hexane-3 is preferred. The amount of the peroxide used is usually α-
The ratio is about 0.01 to 5 parts by weight, preferably about 0.05 to 3 parts by weight, based on 100 parts by weight of the olefin copolymer.

When the thermal decomposition is carried out in the absence of peroxide, the heating temperature is from 300 to 460 ° C, preferably from 350 to 440 ° C from the viewpoints of productivity and quality of the separated product.

The apparatus for performing the above thermal decomposition reaction may be any apparatus, and is not particularly limited. For example, a tubular reactor, a tank reactor, a single-screw or twin-screw extruder, and the like can be used.

When performing a thermal decomposition reaction using a tubular reactor,
Since high-temperature heating is easy, it is suitable for a thermal decomposition reaction performed in the absence of peroxide.

In the case where an extruder is used, kneading is sufficiently performed, and thus the extruder is suitable for a thermal decomposition reaction in the presence of a peroxide.

In the present invention, the thermal decomposition product obtained as described above is reacted at 110 to 220 ° C. in the presence of an oxygen-containing gas to obtain a thermal decomposition oxide.

The oxygen-containing gas to be used may be composed of only oxygen, or a mixed gas of oxygen and an inert gas such as nitrogen, argon, and helium, for example, air. Further, a peroxide gas such as ozone may be contained as an oxidation promoter.

The reaction temperature is from 110 to 220 ° C, preferably from 130 to 200 ° C.

The reaction may be performed using any reactor such as a tank reactor, a tube reactor, and an extruder.

The reaction may be performed by blowing an oxygen-containing gas into the reactor.

Further, in order to carry out the reaction efficiently, a catalyst or an organic peroxide is used in an amount of 0.01 to 1 with respect to 100 parts by weight of the thermal decomposition product.
You may add about weight part.

The acid value of the thermal decomposition / oxide of the present invention is high (40 or more)
In this case, the product becomes sticky and is likely to be blocked, so that it is usually about 0.1 to 40 mgKOH / g, and preferably about 0.1 to 40 mgKOH / g.
It is about 1 to 25 mg · KOH / g.

Further, the present invention provides a thermal transfer ink composition containing the above-mentioned thermal decomposition / oxide, wherein the thermal decomposition / oxide is 1 to 95%.
An object of the present invention is to provide a thermal transfer ink composition containing 15% by weight, preferably 15 to 80% by weight. When the amount of the thermal decomposition / oxide in the thermal transfer ink composition is in the range of 1 to 15% by weight, it is effective in preventing the background of the printing medium from becoming dirty, and in the range of 15 to 95% by weight. If so, it is possible to obtain printing with less blurring in addition to prevention of background contamination.

This thermal transfer ink composition contains a coloring component, a wax, a resin component, and the like as components other than the thermal decomposition / oxide.

As the coloring component used in the thermal transfer ink composition of the present invention, any of those conventionally used in this type of thermal transfer ink can be used and is not particularly limited. For example, inorganic or organic pigments such as carbon black, titanium white, phthalocyanine blue, phthalocyanine green, ultramarine blue, cobalt blue, chromium oxide, lead chromate, porcelain, mioli blue, quinacridone red, and permanent red; oil black, maracaine green, rhodamine B and the like, and these are used singly or in combination of two or more so as to obtain printing of a desired color tone.

The amount of the coloring component in the thermal transfer ink composition is usually about 5 to 50% by weight, preferably about 10 to 40% by weight.

Examples of the wax used in the thermal transfer ink composition of the present invention include, for example, vegetable wax such as carnauba wax and candelilla wax; animal wax such as beeswax and shellac wax; and mineral wax such as montan wax. Petroleum waxes such as paraffin wax and microcrystal wax; polyhydric alcohol esters of higher fatty acids, higher amides, higher amines, condensates of fatty acids with aliphatic or aromatic amines, and synthetic waxes such as synthetic paraffin and chlorinated paraffin. No. These may be used alone or in combination of two or more.

The compounding amount of the wax in the thermal transfer ink composition of the present invention is usually about 0 to 94% by weight, preferably 10 to 75% by weight.
It is about.

As the resin component, it is preferable to use a thermoplastic resin having a softening point in the range of 60 to 150 ° C. As such a thermoplastic resin, specifically, a polyolefin,
Polyolefin copolymer, vinyl chloride copolymer, vinylidene chloride copolymer, polystyrene, styrene copolymer,
Coumarone-indene resin, terpene resin, picolite,
Acrylic resin, polyacrylonitrile, acrylonitrile copolymer, diacetone acrylamide polymer, vinyl acetate, vinyl acetate copolymer, polyvinyl ether,
Polyamide, polyester, polyvinyl acetal resin, polyurethane resin, cellulose derivative, polycarbonate, ionomer, condensate of cyclic ketone and formaldehyde, condensate of m-xylene or mesitylene and formalin, rosin modified product of this condensate and petroleum resin And the like.

In addition, the thermal transfer ink composition of the present invention may, if necessary, suppress heat conduction and charging of metal powder and the like; so that the components of the transferred composition can be well penetrated into the printing medium. Various oils or high boiling solvents; plasticizers; stabilizers;
Ceramic particles and the like can also be blended.

The thermal transfer ink composition of the present invention can form a thermal transfer recording medium by forming a thermal transfer ink layer composed of this composition on a substrate composed of a conventional resin film.

As the resin film used as the substrate, for example, polyethylene terephthalate, polyethylene, polycarbonate, polyimide, polyamide, polyphenylene sulfide, polysulfine, aromatic polyester,
Made of resin such as polyetheretherketone, polyethersulfin, polyetherimide, thickness 0.8-2
A resin film of about 0 μm is exemplified.

The thermal transfer ink layer formed on the substrate by the thermal transfer ink composition of the present invention can be formed by melting or dissolving or dispersing the thermal transfer ink composition of the present invention on the surface of the substrate by a conventional method. Can be formed by applying and drying according to the following formula.

The thickness of the formed thermal transfer ink layer is the dry thickness,
Usually, it is about 0.5 to 20 μm.

As described above, the thermal decomposition / oxide of the present invention is suitably used in a thermal transfer ink composition, and further includes, for example, a pigment dispersant for a resin, an inorganic dispersant for a resin, a hot melt adhesive or a seal. It can also be suitably used for applications such as a viscosity adjusting agent for a toner, a binder for a toner for a heat fixing type copying machine, a release agent for the same, and a binder for a pressure fixing type toner.

<Example> Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

(Example 1) Propylene / 1-butene copolymer (intrinsic viscosity: 2.0 dl /
g, propylene content: 80 mol%) 10 g was charged into a test tube, and the inside of the test tube was sufficiently purged with nitrogen.
It was heated at 410 ° C. for 15 minutes using an aluminum block heater to cause a thermal decomposition reaction.

The intrinsic viscosity of the obtained thermal decomposition product was measured in decalin at 135 ° C. and found to be 0.24 dl / g.

50 g of this pyrolyzate was charged into a 200 ml separable flask, the internal temperature was maintained at 160 ° C., and oxygen was bubbled in from the bottom of the flask at a rate of 500 ml / min, followed by stirring for 3 hours.

The acid value of the generated thermal decomposition / oxide was measured according to the method of JIS K5902, and was found to be 4.6 mg · KOH / g.

(Example 2) The thermal decomposition / oxide obtained in Example 1, carbon black and carnauba wax were formulated as follows: Thermal decomposition / oxide (Example 1) 10% by weight Carbon black 20% by weight Carna The resulting mixture was heated and melted to obtain a composition in which carbon black was uniformly dispersed. Next, this composition was applied on a 9 μm-thick polyethylene terephthalate film to a thickness of 4 μm, and the film was cut to obtain a 6 mm-wide thermal transfer film.

The obtained thermal transfer film was set on a thermal printer and printed on plain paper (general-purpose PPC paper).

For the characters printed on plain paper, the degree of bleeding was evaluated on a scale of 1 (large bleeding) to 4 (small bleeding). As a result, the degree of bleeding of the printed characters was 3 and almost all bleeding was observed. Did not. In addition, the printed paper did not have background stains, and a clear transferred print image was obtained.

<Effects of the Invention> The thermal decomposition / oxide of the α-olefin copolymer of the present invention can provide printing excellent in printing quality and printing accuracy, such as bleeding and soiling of a printing medium, and a substrate. A thermal transfer layer having good adhesion to a film can be formed, and is suitable as a binder for thermal transfer ink.

Further, the thermal transfer ink composition of the present invention contains the above-mentioned thermal decomposition and oxide, and bleeding, while being able to obtain printing excellent in printing quality and printing accuracy such as background contamination of a printing medium, A heat-sensitive transfer layer having good adhesion to the base film can be formed and is suitable as a heat-sensitive transfer ink.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 8/00-8/50

Claims (2)

(57) [Claims] 1. A thermally decomposed product of a copolymer of propylene and at least one kind selected from α-olefins having 4 to 10 carbon atoms, having an intrinsic viscosity measured at 135 ° C. in decalin of 0.02 to 0.02. Thermal decomposition and oxide of an α-olefin copolymer obtained by reacting 0.7 dl / g at 110 to 220 ° C. in the presence of an oxygen-containing gas. 2. A thermal transfer ink composition containing from 1 to 95% by weight of a thermally decomposed oxide of the α-olefin copolymer according to claim 1.