JP3392126B2 - Offset printing ink composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an offset printing ink composition, and more specifically, backing when a printed matter is stacked on a stick immediately after printing (hereinafter referred to as primary blocking) and blocking when a printed matter is processed ( Hereinafter, the present invention relates to an offset printing ink composition that enables production of an offset printed material having excellent blocking resistance and settability without causing secondary blocking).

[0002]

2. Description of the Related Art Generally, offset printing inks are composed of colorants, binder resins, petroleum solvents such as mineral oils, etc., and various additives are used as necessary to improve various suitability for printing. Has been done.

In recent years, recognition of environmental problems has been increasing, and environmental measures are required in the printing ink industry. One of the countermeasures is to replace some or all of the mineral oils that have been used as raw materials with vegetable oils such as soybean oil, etc., and use non-VOC or low-VOC (VOC = VoC).
Inks made of latile organic compounds have been attracting attention (Japanese Patent Laid-Open No. 5-112745).

However, if a large amount of vegetable oil is used in the current offset printing ink, problems such as deterioration of setting property, primary blocking and secondary blocking occur.
This is because the release of the solvent from the ink printed on the paper is slow,
This is due to the large amount of vegetable oil component remaining, which is because the vegetable oil component has a higher viscosity than mineral oils and has a high property of dissolving a resin. At present, environmental measures and these performances are not compatible.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, an object of the present invention is to provide an offset such as settability and blocking resistance (primary blocking resistance, secondary blocking resistance) while taking environmental measures. An object of the present invention is to provide an offset printing ink composition capable of satisfying the required performance required for printing.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a polymer obtained by polymerizing at least one of an olefinic monomer and a diene monomer The sex parameter is 19 (M
It was found that the above problems can be overcome by incorporating a polymer having a Pa of less than ^1/2 and being compatible with the solvent component into the offset printing ink composition, and has completed the present invention.

Namely, the invention according to claim 1, colorant, rosin-modified phenolic resin and / or rosin-modified maleic acid resin, an offset printing ink containing a vegetable oil component and mineral oils as a solvent component as a binder resin A polymer obtained by polymerizing at least one of an olefinic monomer and a diene monomer in the composition, wherein the solubility parameter is 19 (MP
a) Polymer smaller than ^1/2 and compatible with solvent components (provided that polybutadiene and modified polybutadiene are used)
(Excluding a) is contained in the ink composition in an amount of 0.1 to 10% by weight.

In the invention according to claim 2, the polymer is
The offset printing ink composition according to claim 1, which is liquid at room temperature.

The invention according to claim 3 relates to the offset printing ink composition according to claim 1 or 2, wherein a part or all of the vegetable oil component is a vegetable oil-derived fatty acid ester compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The offset printing ink composition of the present invention will be described in more detail below.

As the colorant used for obtaining the offset printing ink composition of the present invention, a colorless or colored inorganic or organic pigment conventionally used in offset printing inks can be used. Specifically, titanium dioxide, barium sulfate, calcium carbonate, inorganic pigments such as magnetic iron oxide, azo pigments, lake pigments, phthalocyanine pigments, isoindoline pigments, anthraquinone pigments,
Organic pigments such as quinacridone pigments and carbon black can be used. The content of the colorant in the offset printing ink composition is preferably about 3 to 40% by weight.

As the binder resin used to obtain the offset printing ink composition of the present invention, a rosin-modified phenol resin or a rosin-modified maleic acid resin can be used without particular limitation. Moreover, if necessary, an alkyd resin, a petroleum resin, or the like can be used together. Although the content of the binder resin is not particularly limited, it is usually suitable in the range of 20 to 60% by weight in the offset printing ink composition.

To obtain the offset printing ink composition of the present invention having improved blocking resistance such as primary and secondary blocking resistance and settability, at least one of an olefinic monomer and a diene monomer is polymerized. The polymer obtained by
Parameter) is less than 19 (MPa) ^1/2 , and
Polymer compatible with solvent components (however, polybutadiene
And modified polybutadiene) . The polymer more preferably has a solubility parameter of 15 to
It is 18 (MPa) ^1/2 and is liquid at room temperature. Examples of the polymer include homopolymers and copolymers of olefin-based monomers, homopolymers and copolymers of diene-based monomers, and copolymers of olefin-based monomers and diene-based monomers. isobutylene, Po polyisoprene, isoprene - like isobutylene copolymers. A polymer that is not compatible with the solvent component is not sufficiently miscible with other components. If the solubility parameter of the polymer is higher than the above range, the compatibility with other components becomes too high, and the settability and blocking resistance cannot be improved.

A polymer obtained by polymerizing at least one of an olefinic monomer and a diene monomer of the present invention, which has a solubility parameter of 19 (MPa) ^1/2.
Smaller and, to improve the setting property and blocking resistance by the use of a polymer which is compatible with the solvent component (a vegetable oil component and mineral oils), the solubility parameter is apart from the binder resin component It is believed that the compatibility of the polymer with the solvent component improves the releasability from the resin component of the solvent system as a whole. In addition,
The solubility parameter of a polymer obtained by polymerizing at least one of an olefin-based monomer and a diene-based monomer can be determined by a dissolution method or a swelling method,
The main ones are Polymer Handbook (J. Brandrup and E.
H. Immergut, Polymer Handbook 3rd ed., John Wiley
& Sons, Inc., New York, 1989, Section VII) and the like.

The amount of the polymer used is suitably 0.1 to 10% by weight in the offset printing ink composition. When the amount used is less than the above range, the settability, primary resistance, and sufficient effect for improving secondary blocking resistance cannot be obtained. On the other hand, when the amount exceeds the range, separation from the ink composition becomes severe,
Problems such as reduced gloss tend to occur. However,
Since an appropriate amount used depends on the binder resin used and the type of the polymer, it is preferable to select an appropriate amount within the above range.

The vegetable oil component that can be used to obtain the offset printing ink composition of the present invention includes vegetable oils and fatty acid ester compounds derived from vegetable oils.

Examples of the vegetable oil include soybean oil, cottonseed oil, linseed oil, safflower oil, tung oil, tall oil, dehydrated castor oil, canola oil and other drying oils or semi-drying oils. These may be used alone or in combination of two or more.

Examples of the fatty acid ester compound derived from the vegetable oil include monoalkyl ester compounds of fatty acids derived from the drying oil or the semi-drying oil. The fatty acid constituting the fatty acid monoester has 16 to 16 carbon atoms.
20 saturated or unsaturated fatty acids are preferable, and stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid and the like can be illustrated. The alcohol-derived alkyl group constituting the fatty acid monoester preferably has 1 to 10 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and 2-ethylhexyl. These fatty acid monoesters can be used alone or in combination of two or more kinds.

In the offset printing ink composition of the present invention, vegetable oil and fatty acid ester may be used alone or in combination as the vegetable oil component.
The amount of the fatty acid ester used is preferably 3% by weight or more in the offset printing ink composition.

In the offset printing ink composition of the present invention, examples of mineral oils that can be used as a solvent include those having a boiling point of 160 ° C or higher, preferably 200 ° C or higher, which are incompatible with water. Specifically, n-, which is generally used as an offset printing ink solvent,
Examples include paraffinic solvents, isoparaffinic solvents, naphthene-based solvents, aromatic solvents, petroleum-based solvents such as α-olefins, light oils, spindle oils, machine oils, cylinder oils, turpentine oils, and mineral spirits. These can be used alone or in combination of two or more.

The solvent in the offset printing ink composition of the present invention, a combination of plant oil component and mineral oils. Environmental terms of (by removal and non VOC or low VOC reduction of harmful ingredients, improvement and provide a harmless print printing working environment), mineral oils are Shi preferred that not recommended
Yes .

Further, in the offset printing ink composition of the present invention, if necessary, a gelling agent, a pigment dispersant, a drier, a drying retarder, an antioxidant, a surface leveling aid, a friction resistance improver, Additives such as a set-off preventing agent and a nonionic surfactant can be appropriately used. As a gelling agent,
Aziridine compounds such as trimethylolpropane-tris-β-N-aziridinylpropionate, pentaerythritolpropane-tris-β-N-aziridinylpropionate, glycerol polyglycidyl ether,
Epoxy compounds such as trimethylolpropane polyglycidyl ether, aluminum acetoacetate aluminum diisopropoxide, aluminum chelate compounds such as aluminum trisethylacetoacetate, aluminum triisopropoxide, mono-sec-butoxyaluminum diisopropoxide, aluminum Tri-
Examples thereof include aluminum alcoholates such as sec-butoxide.

For producing the offset printing ink composition of the present invention, a conventionally known method can be used. For example, a binder resin, a vegetable oil component, and optionally a part of mineral oils are heated to obtain a varnish. At this time, a gelling agent may be added to form a gel varnish. Then, a colorant and, if necessary, a vegetable oil component, a mineral oil, a pigment dispersant or a pigment dispersant resin are added, and the mixture is kneaded and dispersed by a bead mill, a three roll mill or the like to obtain a base for offset printing ink. Further, a polymer obtained by polymerizing at least one of an olefin-based monomer and a diene-based monomer on the obtained base for offset printing ink, which has a solubility parameter of less than 19 (MPa) ^1/2 and a solvent. A polymer compatible with the components and, if necessary, other additives such as a drier are added, and the viscosity is adjusted to a predetermined viscosity with a vegetable oil component and, if necessary, mineral oil or the like to obtain an offset printing ink composition. The polymer may be blended when preparing the ink base.

[0024]

EXAMPLES The offset printing ink composition of the present invention and the method for producing the same will be described in more detail below with reference to Examples, but the present invention is not limited to these without departing from the spirit and the scope of application thereof. Absent. In the following description, “part” means part by weight.

[Production of Varnish for Offset Printing Ink] (Varnish A) A four-necked flask equipped with a condenser, a thermometer and a stirrer had a weight average molecular weight of 90,000 and an acid value of 15 mg.
KOH / g rosin-modified phenolic resin A (manufactured by Hitachi Chemical Polymer Co., Ltd.), soybean oil, and mineral oil (manufactured by Nippon Petrochemical Co., Ltd., AF Solvent No. 6, hereinafter the same) were each formulated in Table 1 (each). The amount of the components to be blended is indicated by the number of parts, the same shall apply hereinafter), the temperature is raised to 200 ° C., and the mixture is heated and dissolved at the same temperature for 1 hour. ) Kawaken Fine Chemical Co., ALCH) was prepared so as to have the composition shown in Table 1, and heated and maintained at 170 ° C. for 60 minutes to give varnish A.
Got

(Varnish B) In the production of varnish A, rosin-modified phenol resin A
With a weight average molecular weight of 140,000 and an acid value of 15 mg KOH
Varnish B was obtained in the same manner as the method for obtaining varnish A except that the amount of rosin-modified phenolic resin B (manufactured by Hitachi Chemical Co., Ltd.) was changed to / g.

(Varnish C) In a four-necked flask equipped with a condenser, a thermometer and a stirrer, fatty acid ester A (manufactured by Lawter Inc., soybean oil fatty acid methyl ester), rosin-modified phenol resin A,
Soybean oil and mineral oil were charged so as to each have the composition shown in Table 1, heated to 200 ° C., dissolved by heating at the same temperature for 1 hour, and then a gelling agent was prepared so as to have the composition shown in Table 1.
The varnish C was obtained by heating and holding at 70 ° C. for 60 minutes.

(Varnish D) Varnish D was prepared in the same manner as in Varnish C except that fatty acid ester A was replaced with fatty acid ester B (Lawter Inc., soybean oil fatty acid isobutyl ester) in the production of varnish C. Obtained.

(Varnish E) In a four-necked flask equipped with a condenser, a thermometer and a stirrer, rosin-modified phenolic resin A, soybean oil and fatty acid ester A were charged so as to have the formulations shown in Table 1 and heated to 200 ° C. After heating and melting at the same temperature for 1 hour, the gelling agent was charged to have the composition shown in Table 1, and 170
The varnish E was obtained by heating and holding at 60 ° C. for 60 minutes.

(Varnish F) Varnish F was obtained in the same manner as in the method of obtaining varnish E except that fatty acid ester A was changed to fatty acid ester B in the production of varnish E.

[Manufacture of Offset Printing Ink Composition] Examples 1 to 4 and Reference Examples 1 to 9 Varnishes A to F and carbon black (Mitsubishi Chemical Co., Ltd., MA-7) were blended as shown in Table 2 ( The respective compounding amounts are shown in parts, the same shall apply hereinafter), and the mixture is kneaded with a bead mill and three rolls in order to obtain each ink base. Then
With respect to each ink base, the composition of Table 2 has a solubility parameter of 17.2 (MPa) ^1/2 , a liquid polybutadiene at room temperature (hereinafter simply referred to as polybutadiene), and a solubility parameter of 16.6 (MPa) ^{1 /} Polyisoprene which is liquid at room temperature at ² (hereinafter simply referred to as polyisoprene), polyisobutylene which is liquid at room temperature at a solubility parameter of 15.2 (MPa) ^1/2 (hereinafter simply referred to as polyisobutylene),
Wax compound (manufactured by Shamrock, polyethylene wax compound, the same applies below), dryer, mineral oil, fatty acid ester A and fatty acid ester B were added and stirred, and the offset printing ink compositions of Examples 1 to 4 and Reference Examples 1 to 9 were added. I got a thing. In addition, Examples 1 to 4 and Reference Examples 1 to 5 are mineral oil-containing ink compositions and Reference Examples.
Nos. 6 to 9 are mineral oil-free ink compositions.

Comparative Examples 1 to 4 Varnish A or Varnish E and carbon black were mixed in the respective formulations shown in Table 2 and kneaded in order with a bead mill and three rolls to obtain respective ink bases. Then, polybutadiene, a poly (methyl acrylate) having a solubility parameter of 20.7, a wax compound, a dryer, a mineral oil and a fatty acid ester A were added to each ink base in the composition shown in Table 2 and stirred, and Comparative Examples 1 to 4 were used. To obtain an offset printing ink composition. Comparative Examples 1 to 3 are mineral oil-containing ink compositions, and Comparative Example 4 is a mineral oil-free ink composition.

[Performance Evaluation Test] The offset printing ink compositions of Examples 1 to 4, Reference Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated for printing performance as follows.

(1) Gloss Each offset printing ink composition was spread on a coated paper with an RI tester (Myo Seisakusho Co., Ltd.), and allowed to stand at room temperature for 1 day. (Murakami Color Research Laboratory, digital gloss meter).

(2) Settability Each offset printing ink composition was spread on coated paper with an RI tester (Akira Seisakusho Co., Ltd.). Fine paper was overlaid and the degree of ink adhesion to the fine paper was observed using an automatic ink set tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the time (minutes) required until the ink did not adhere was measured. The shorter this time is, the better the setability is.

(3) Primary Blocking Resistance Suitability Each offset printing ink composition was coated on a sheet-fed offset printing machine (NK-High Coat 73K, Nippon Paper Co., Ltd.).
Co., Ltd.), stack 10000 sheets on a stick, and print at room temperature for 24 hours.
The degree of blocking when left for a time was visually evaluated based on the following criteria. The better this evaluation is, the better the primary blocking resistance is. 3: Little blocking 2: Medium blocking 1: Large blocking

(4) Suitability for secondary blocking resistance Each offset printing ink composition was coated with a sheet-fed offset printing machine (NK-High Coat 73K, Nippon Paper Co., Ltd.).
Co., Ltd.), and allowed to stand at room temperature for 24 hours. Then, the degree of blocking when 200 sheets of printed matter were stacked and cut by a cutter was visually judged based on the following criteria. The more excellent this evaluation is, the more excellent the secondary blocking resistance and the drying property are. 3: Little blocking 2: Medium blocking 1: Large blocking

[Evaluation Results] Table 3 shows the results of the above evaluations of the offset printing ink compositions (mineral oil-containing systems) of Examples 1 to 4, Reference Examples 1 to 5 and Comparative Examples 1 to 3. Table 4 shows the results of the above-described evaluations of the offset printing ink compositions of Reference Examples 6 to 9 and Comparative Example 4 (mineral oil-free system).

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

Industrial Applicability The present invention has the following features: settability of printed matter, primary resistance,
Provided is an offset printing ink composition which is excellent in secondary blocking resistance and does not impair the gloss and dryness of the printing surface.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichi Kataura 1-23-37 Edobori, Nishi-ku, Osaka City Sakata Inx Co., Ltd. (72) Inventor Takashi Iwase 1-23-37 Edobori, Nishi-ku, Osaka Sakatax Inc. In-house (56) Reference JP-A 2-194075 (JP, A) JP-A 64-24874 (JP, A) JP-A 10-140070 (JP, A) JP-A 11-80644 (JP, A) ) JP-A-6-93220 (JP, A) JP-A-5-112745 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11 / 00-11 / 20

Claims (3)

(57) [Claims] 1. A colorant, a rosin-modified phenolic resin and / or rosin-modified maleic acid resin as a binder resin, in an offset printing ink composition containing a vegetable oil component and mineral oils as a solvent component, further, the olefin At least one of monomer and diene monomer
A polymer obtained by polymerizing seeds, which has a solubility parameter of less than 19 (MPa) ^1/2 and is compatible with the solvent component (provided that polybutadiene and
(Excluding polybutadiene) in the ink composition.
An offset printing ink composition comprising 10% by weight. 2. The offset printing ink composition according to claim 1, wherein the polymer is liquid at room temperature. 3. The vegetable oil-derived fatty acid ester compound as a part or all of the vegetable oil component according to claim 1 or 2.
The offset printing ink composition described.