JP2003268283A - Ink varnish and ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink varnish and an ink which permit sharp reduction in misting in high-speed printing, suppression of increase in ink tack and reduction of the amount of the resin component in the ink, dispense with the use of formaldehyde and phenols as starting materials for the ink varnish, and exhibit printing aptitudes and printing performances equal or superior to inks obtained by using a conventional rosin-modified phenolic resin. <P>SOLUTION: The ink varnish comprises a resin, which is a reaction product of rosins containing at least 20-80 wt.% of a dimerized rosin, hydrocarbon resins, an α,β-unsaturated carboxylic acid and/or an anhydride thereof, and a polyhydric alcohol. The ink is obtained using the varnish. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink varnish and an ink varnish which are excellent in ink misting resistance and ink tack rise suppression during high-speed printing and which do not use a resin raw material such as formaldehyde or phenols which has an environmental load. Concerning ink.

[0002]

2. Description of the Related Art Conventionally, rosin-modified phenolic resins have been generally used for offset ink varnishes and inks because of their excellent printability. For these rosin-modified phenol resins, formaldehyde, p-alkylphenols such as p-nonylphenol and p-tertiarybutylphenol, and phenols such as bisphenol are used as raw materials for production.

Of the above-mentioned raw materials for production, formaldehyde is a causative substance causing hypersensitivity of chemical substances, and p-alkylphenols include chemical substances suspected of having endocrine disrupting action. , At the time of manufacturing the rosin-modified phenolic resin, there is a risk of unreacted raw materials diffusing into the atmosphere or drainage, and from the viewpoint of environmental problems and work safety, use resins that do not use these raw materials. Varnishes and inks are desired.

For this reason, rosin ester resins which do not use the above-mentioned raw materials have been proposed. However, since these resins are obtained by esterification of rosins and alcohols, they have a relatively low molecular weight and a high speed. At the time of printing, the ink scattering phenomenon (misting) around the printing machine tends to increase. Further, since a large amount of resin component is required when designing the ink, the tack value of the ink becomes high. Furthermore, the number of selectable resins is smaller than that of conventional rosin-modified phenolic resins. Therefore, there is a problem that it is difficult to design a wide variety of varnishes and inks.

As described above, from the viewpoint of environmental problems and work safety, formaldehyde and phenols are not included as raw materials for resin production, and misting during high-speed printing using a recent high-speed rotary printing machine is greatly reduced. Moreover, an ink in which the amount of resin component in the ink is reduced can be designed, and an ink having print performance comparable to or higher than that of an ink using a conventional rosin-modified phenolic resin and printability is not provided.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to significantly reduce misting in high-speed printing using a recent high-speed rotary printing machine, and increase the ink tack value by reducing the amount of resin component in the ink. To provide an ink varnish and an ink which have a printability and printing performance comparable to or better than an ink using a conventional rosin-modified phenolic resin, which does not use formaldehyde or phenols as an ink varnish material as a manufacturing raw material. Is.

[0007]

The above object can be achieved by the present invention described below. That is, in the present invention, rosins (a component) containing at least 20 to 80% by weight of dimerized rosin, hydrocarbon resins (b component), α, β-
Unsaturated carboxylic acid and / or its anhydride (component c)
And an ink varnish (hereinafter, simply referred to as a varnish) containing a resin (e) which is a reaction product of a polyhydric alcohol (component d) and an ink using the varnish.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The resin (e) that characterizes the present invention is a reaction product obtained by the reaction of the a component, the b component, the c component, and the d component.

As the dimerized rosin contained in the component a, natural rosins such as wood rosin, gum rosin and tall oil rosin are treated in the presence of an acidic catalyst such as sulfuric acid to dimerize unreacted monomers. And a dimerized rosin derivative such as a dimerized rosin ester and a polymerized rosin containing a dimerized rosin obtained by polymerizing the above natural rosin (dimeric rosin).

The component a preferably comprises at least one selected from the group consisting of the above dimerized rosin, partially dimerized rosin and dimerized rosin derivative, and rosin other than the dimerized rosin group. Examples of the rosin other than the dimerized rosin group include pine resin, gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, hardened rosin, polymerized rosin, and other rosin derivatives, and mixtures thereof. Can be mentioned. Specific examples of the component a include a mixture of partially dimerized rosin and gum rosin or wood rosin.

The component a contains at least 20 to 80% by weight, preferably 3%, of the above-mentioned dimerized rosin in the component a.
It contains 0 to 50% by weight. When the content of the above dimerized rosin exceeds the above upper limit, the viscosity of the resulting varnish is increased, the fluidity of the ink using the varnish is decreased, and the phenomenon of tightness in the ink of the printed matter or printing. On the other hand, when the content of the varnish is less than the above lower limit, the viscosity of the varnish obtained is too low, and the ink obtained by using the varnish sinks into the printing paper (the absorbability is low). If it becomes large), misting increases during high-speed printing.

The component b is preferably a hydrocarbon resin and / or an acid-modified hydrocarbon resin. Examples of the hydrocarbon resin include hydrocarbon resins obtained from raw materials such as petroleum cracked distillate, turpentine distillate oil, coal tar, monoolefins and diolefins. Examples of the preferable hydrocarbon resin include petroleum resins and copolymerized petroleum resins made from unsaturated hydrocarbon-based materials such as indene-based, cyclopentadiene-based, dicyclopentadiene-based, and pentadiene-based materials.

Examples of the above-mentioned petroleum resin and copolymerized petroleum resin include dicyclopentadiene-based petroleum resin (DCPD system) containing cyclopentadiene and dicyclopentadiene as main raw materials; pentene, pentadiene and isoprene as main raw materials. C5 petroleum resin; C9 petroleum resin made from indene, methylindene, vinyltoluene, styrene, etc .; Copolymerized petroleum resin made from DCPD raw material and C5 raw material; Copolymer made from DCPD raw material and C9 raw material Polymerized petroleum resin; Copolymerized petroleum resin composed of C5-based raw material and C9-based raw material; Petroleum resin such as co-polymerized petroleum resin composed of DCPD-based raw material, C5-based raw material and C9-based raw material, and a mixture thereof; Is a softening point of 90 to 120
° C, acid value 0 mgKOH / g, weight average molecular weight 1,500
.About.1,700 petroleum resins. These petroleum resins can be obtained from Maruzen Petrochemical Co., Ltd. under the trade name of T200A and used in the present invention.

Examples of the acid-modified hydrocarbon resin include reaction products (partial reaction products) of the above-mentioned hydrocarbon resins with unsaturated fatty acids and / or their anhydrides. Examples of the unsaturated fatty acid and / or its anhydride used in the reaction product include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, tetrahydrophthalic acid, and their anhydrides. Is mentioned.

As the c component to be reacted with the a component and the b component, α, which is used in the Diels-Alder reaction,
Examples include β-unsaturated monocarboxylic acids and / or α, β-unsaturated dicarboxylic acids and / or their anhydrides. As the α, β-unsaturated monocarboxylic acid, for example,
Acrylic acid such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, and α-ethylcrotonic acid is preferable. Also, α,
Examples of the β-unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like, preferably maleic acid and fumaric acid. Examples of the above α, β-unsaturated dicarboxylic acid anhydrides include maleic anhydride and itaconic anhydride, and preferably maleic anhydride.

Examples of the component d used in the above reaction include ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol and 1,7-. Dihydric alcohols such as heptanediol, diethylene glycol and triethylene glycol; trihydric alcohols such as glycerin, trimethylolpropane and trimethylolethane; 4 such as diglycerin, triglycerin, erythritol and pentaerythritol.
At least one polyhydric alcohol selected from alcohols having a valence of at least one is included, and preferably pentaerythritol is included.

The resin (e) which characterizes the present invention can be obtained by subjecting the above-mentioned a component, b component, c component and d component to known Diels-Alder reaction and esterification reaction. In the above reaction, the a component and the b component are hot-melt mixed in a nitrogen atmosphere, the c component is added to the mixture at 180 ° C., and the addition reaction product is added to the d product. The components are esterified at about 270 to 280 ° C.

Resin (e) obtained by the above reaction
Has a weight average molecular weight of 10,000 to 100,000,
An acid value of 5 to 30 mg KOH / g and a softening point of 150
˜180 ° C., preferably a weight average molecular weight of 12,
000-30,000, acid value 10-20mgKOH /
g, and the softening point is 160 to 180 ° C. When the weight average molecular weight exceeds the above upper limit, the solubility of the obtained ink in a non-aromatic solvent is lowered and sufficient ink fluidity cannot be obtained. On the other hand, the weight average molecular weight is
If it is less than the above lower limit, the viscosity of the obtained ink does not increase, misting is likely to occur in high-speed printing, and the ink is scattered around the printing machine or the printing surface, and good printability cannot be obtained. . On the other hand, when the acid value exceeds the above upper limit, the solubility in non-aromatic solvent or vegetable oil decreases, while when the acid value is less than the above lower limit, the affinity with water deteriorates. If the softening point exceeds the above upper limit, the solubility of the obtained ink in a solvent is lowered,
On the other hand, when the softening point is less than the above lower limit, ink bleeding appears on the printed matter due to thermal melting of the ink when the ink is heat set on the printing paper surface.

The varnish of the present invention comprises the resin (e) 20 described above.
~ 50 parts by weight of at least one vegetable oil 20
˜50 parts by weight, 20 to 30 parts by weight of a solvent are added to the total amount of the resin (e) and vegetable oil, heated and dissolved at 220 ° C., and uniformly mixed and dissolved with a stirrer for about 1 hour to obtain be able to. As the above vegetable oil, soybean oil, rapeseed oil, semi-drying oil such as corn oil, linseed oil, tung oil, cinnamon oil,
Dry oils such as sesame oil, non-drying oils such as castor oil and olive oil, dehydrated castor oil, synthetic oils such as heat-polymerized oils, regenerated oils, and the like, and mixtures thereof. Soybean oil is preferred.

Examples of the above-mentioned solvent include at least one kind selected from petroleum-based solvents such as paraffin-based and naphthene-based solvents, and preferably non-aromatic petroleum-based solvents. Examples of the non-aromatic petroleum solvent include “AF Solvent No. 4”, “AF Solvent No. 5” from Mitsubishi Nisseki Co., Ltd.,
It can be obtained in trade names such as "AF Solvent No. 6" and "AF Solvent No. 7" and used in the present invention.

The above-mentioned varnish of the present invention comprises a colorant such as a dye or a pigment and the above non-aromatic petroleum solvent,
If necessary, other resin varnishes that do not use formaldehyde or phenols as a resin raw material, such as Gilsonite varnish, can be kneaded to the extent that the object of the present invention is not impaired to obtain the ink of the present invention. Further, if necessary, an anti-skinning agent such as methyl ethyl ketone oxime, cyclohexanone oxime, or an additive such as wax compound such as paraffin wax, carnauba wax, polyethylene wax, etc. may be used within a range not hindering the object of the present invention. it can.

Examples of the above-mentioned coloring agents include inorganic pigments such as titanium oxide, carbon black, calcium carbonate, barium sulfate, ultramarine blue, dark blue, red halo, zinc white, etc. , Insoluble azo pigments such as pyrazolone,
Copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine system, quinacridone system, pyrantrone system, diosazine system, anthrapyrimidine system, industron system, flavantron system, thioindigo system, anthraquinone system, perylene system, perinone system,
Examples include organic pigments and dyes such as isoindolinone-based metal complex salt-based and quinophthalone-based polycyclic and heterocyclic pigments.

The ink of the present invention is uniformly kneaded with the above-mentioned varnish, colorant, solvent, etc. of the present invention by a known method,
Obtained as illustrated in the examples. It is an essential condition that the resin (e) is contained in the ink in an amount of 10 to 40% by weight, preferably 20 to 30% by weight. If the compounding amount of the resin (e) exceeds the above upper limit, there is a problem that ink stability and printability are deteriorated. On the other hand, if the compounding ratio is less than the above lower limit, misting is significantly reduced. The desired effect of causing it cannot be obtained.

[0024]

EXAMPLES Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples. In the text, "part" or "%" is based on weight unless otherwise specified. <Production Example of Resin (e)> Production Example 1 (Resin e1) In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, under a nitrogen atmosphere, polymerized rosin (dimerized rosin content 50 to 60).
%) 1,000 parts, gum rosin 250 parts and petroleum resin T200A (manufactured by Maruzen Petroleum Co., Ltd.) 100 parts, and after heating and dissolving, 65 parts of maleic anhydride was added to obtain 18
The reaction was carried out at 0 ° C. To the obtained reaction product, 160 parts of pentaerythritol was added and uniformly mixed, 1 part of magnesium oxide was further added as a catalyst, and the reaction vessel was heated to 2 times.
The resin (e1) having a weight average molecular weight (polystyrene conversion) of 15,000 was prepared by heating to 75 ° C. and reacting for 8 hours.

Production Example 2 (Resin e2) 600 parts of polymerized rosin (dimerized rosin content of 50 to 60%), 600 parts of gum rosin and petroleum resin T200A (Maruzen) were placed in a reaction kettle having the specifications of Production Example 1 under a nitrogen atmosphere. After adding 100 parts of Petroleum Co., Ltd. and heating and melt | dissolving, 80 parts of acrylic acid was added and it was made to react at 180 degreeC. To the obtained reaction product, 158 parts of pentaerythritol was added and uniformly mixed, 1.3 parts of magnesium oxide was further added as a catalyst, and the reaction kettle was heated to 275 ° C.
Weight average molecular weight (polystyrene conversion) 2
1,000 resins (e2) were prepared.

Production Example 3 (Resin z1) 200 parts of toluene, 520 parts of p-octylphenol and 165 parts of 92% paraformaldehyde were placed in a reaction kettle having the specifications of Production Example 1 and dissolved by heating to 60 ° C.
Further, 2 parts of slaked lime previously dispersed in 5 parts of water was added, heated to 90 ° C. and reacted for 5 hours to obtain a resol resin.

Separately, 680 parts of gum rosin was charged into a reaction kettle having the specifications of Production Example 1 under a nitrogen atmosphere and heated to dissolve, and then 60 parts of glycerin was added at 200 ° C. and mixed uniformly. Further, 0.5 part of zinc oxide was added as a catalyst, the reaction kettle was heated to 275 ° C. and reacted for 2 hours, and the obtained reaction product was reacted with the above resole resin for another 4 hours to give a weight average molecular weight of 40. , 000 (polystyrene equivalent) resin (z1) was prepared.

Production Example 4 (Resin z2) In a reaction kettle having the specifications of Production Example 1, under a nitrogen atmosphere, 1,300 parts of gum rosin were charged and dissolved by heating, and then 30 parts of maleic anhydride was added. The reaction was carried out at 180 ° C. To the obtained reaction product, 140 parts of pentaerythritol was added, 1 part of magnesium oxide was further added as a catalyst, the reaction kettle was heated to 275 ° C. and reacted for 6 hours to give a weight average molecular weight (polystyrene conversion) 2. 000 resins (z2) were prepared.

Production Example 5 (Resin z3) In a reaction kettle having the specifications of Production Example 1, under a nitrogen atmosphere, 1,300 parts of gum rosin was charged and dissolved, and then 60 parts of acrylic acid was added to obtain 180 The reaction was carried out at ° C. To the obtained reaction product, 160 parts of pentaerythritol was added, and further 1 part of magnesium oxide was added as a catalyst,
Resin (z3) having a weight average molecular weight (polystyrene conversion) of 2,000 by heating the reaction kettle to 275 ° C. and reacting for 6 hours.
Was prepared.

Table 1 shows the physical properties of each resin obtained by the above production examples. Osol cloud point: Represents the solubility of each resin dissolved in O-solvent of Mitsubishi Nisseki Co., Ltd. until the solution becomes cloudy.

Examples 1 and 2 and Comparative Examples 1 to 3 (Method for preparing varnish) Using the above resins e1 to e2 and resins z1 to z3,
Each resin, vegetable oil, and non-aromatic petroleum solvent were blended according to the following blending example, and the blended amount was 2 under nitrogen atmosphere.
Dissolve while stirring uniformly at 20 ° C. for 1 hour.
Varnishes U1 and U2 of No. 2 and Varnishes V1 of Comparative Examples 1 to 3
~ V3 was prepared. In addition, Table 2 shows the physical properties of the prepared varnishes. (Formulation Example) Resin 40 parts Soybean oil 40 parts Non-aromatic petroleum solvent (AF Solvent No. 6) 20 parts

[0032] The above-mentioned tack value, viscosity and hexane tolerance show the following measured values. -Tack value: A value of 30 seconds under the conditions of 400 rpm and a roll temperature of 32 ° C using a digital incometer manufactured by Toyo Seiki Co., Ltd.・ Viscosity: Room temperature 25 ° C with L-type viscometer manufactured by Toyo Seiki Co., Ltd.
Measured value under the condition of. -Hexane tolerance: The amount of hexane required until 5 g of a sample was added dropwise with n-hexane and the mixture of varnish and n-hexane became cloudy.

Examples 3 to 4 and Comparative Examples 4 to 6 (Ink preparation method) Each of the varnishes obtained above was colored, a Gilsonite varnish and a non-aromatic petroleum solvent (AF Solvent No. 6).
Are blended as shown in Table 3, and an E-type viscosity (120-second value under the conditions of 25 ° C. and 50 rpm) is 5.0 to 5.5 Pa · s by using a sand mill. Y2) and comparative inks (X1 to X3) were prepared. For each of the inks obtained above, misting, viscosity, tack value, glass plate flow rate and emulsification rate were measured by the following measuring methods.

[0034] The numerical values in the above table represent the number of compounding parts.

The properties of each ink were measured using each of the above inks. The evaluation results are shown in Table 4. -Misting property: 2.62 cc of each of the above inks was adhered to an incometer manufactured by Toyo Seiki Co., Ltd.
C., the roll temperature of the incometer was set to 32.degree. C., the roll rotation speed was 2,000 rpm, and the weight of the ink attached to the misting sampling paper after 60 seconds was measured.

Viscosity: Measured with an E-type viscometer manufactured by Toyo Seiki Co., Ltd. at room temperature of 25 ° C. -Tack value: 1.31 cc of ink was adhered to an incometer manufactured by Toyo Seiki Co., Ltd., and at a room temperature of 25 ° C, the roll temperature of the incometer was set to 32 ° C and the roll rotation speed was 1,200 rpm for 30 seconds. Was measured. -Glass plate flow rate: 0.5 cc of ink at room temperature 25 ° C 10
The glass plate flow rate value after a minute was measured by the printing ink industry association "Group Standard Newspaper Offset Rotary Ink Test Method" 4.1-4. -Emulsification rate: 100 using a dissolver emulsification tester
200g of water was added to g of ink, and at 25 ° C,
After stirring at 2,000 rpm, the emulsification rate after 15 minutes was measured.

[0037]

[0038]

INDUSTRIAL APPLICABILITY The varnish obtained by the present invention and the ink using the varnish have a significantly reduced misting and can suppress the rise of ink tack by reducing the amount of resin in the ink, and can be used in the ink. The environmental load can be reduced by not using formaldehyde or phenols as a raw material for the varnish material.

Continued front page    (72) Inventor Fumie Yamazaki             450 Aoto-cho, Midori-ku, Yokohama-shi, Kanagawa The             Inktech Co., Ltd. F-term (reference) 4J039 AB08 AB10 AD09 AD13 AD16                       AD18 BC07

Claims (9)

[Claims] 1. A rosin (component a) containing at least 20 to 80% by weight of a dimerized rosin, a hydrocarbon resin (component b), an α, β-unsaturated carboxylic acid and / or its anhydride ( c component) and polyhydric alcohol (d component)
An ink varnish containing a resin (e) which is a reaction product of 2. The a-component comprises at least one member selected from the group consisting of dimerized rosin, partially dimerized rosin and dimerized rosin derivative, and rosin other than the dimerized rosin group. Ink varnish. 3. The ink varnish according to claim 1, wherein the component b is a hydrocarbon resin and / or an acid-modified hydrocarbon resin. 4. The component b is a dicyclopentadiene-based raw material, a C5-based raw material, a C9-based raw material petroleum resin, a copolymerized petroleum resin composed of a dicyclopentadiene-based raw material and a C5-based raw material, and a di-component. Cyclopentadiene raw material and C
Copolymerized petroleum resin consisting of 9 raw materials, C5 raw materials and C9
At least one selected from the group consisting of a copolymerized petroleum resin containing a raw material, a dicyclopentadiene raw material, a copolymerized petroleum resin containing a C5 raw material and a C9 raw material, and another petroleum resin containing an unsaturated hydrocarbon as a raw material. The ink varnish according to claim 1, which is present. 5. The resin (e) has a weight average molecular weight of 10,0.
00-100,000, acid value 5-30mgKOH /
The ink varnish according to claim 1, wherein g and the softening point are 150 to 180 ° C. 6. A vegetable oil is further added to the resin (e) 20-50.
20 to 50 parts by weight is contained with respect to parts by weight.
Ink varnish according to any one of 1. 7. The ink varnish according to claim 6, wherein the vegetable oil is soybean oil. 8. The ink varnish according to claim 1, further comprising a Gilsonite resin. 9. An ink obtained by kneading a non-aromatic petroleum solvent and a colorant with the ink varnish of claims 1 to 8 and containing a resin (e) in an amount of 10 to 40% by weight. .