WO2014041890A1 - Résine phénolique modifiée par de la colophane, composition de vernis pour encre et encre d'impression - Google Patents

Résine phénolique modifiée par de la colophane, composition de vernis pour encre et encre d'impression Download PDF

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Publication number
WO2014041890A1
WO2014041890A1 PCT/JP2013/069416 JP2013069416W WO2014041890A1 WO 2014041890 A1 WO2014041890 A1 WO 2014041890A1 JP 2013069416 W JP2013069416 W JP 2013069416W WO 2014041890 A1 WO2014041890 A1 WO 2014041890A1
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Prior art keywords
rosin
mass
phenolic resin
modified phenolic
ink
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PCT/JP2013/069416
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English (en)
Japanese (ja)
Inventor
伊藤　元陽
博 江波戸
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Ｄｉｃグラフィックス株式会社
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Priority to JP2013546476A priority Critical patent/JP5543676B1/ja
Publication of WO2014041890A1 publication Critical patent/WO2014041890A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/08—Printing inks based on natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention is a rosin-modified phenolic resin obtained by reacting polyhydric alcohol and phenol having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position as essential raw material components
  • the present invention relates to an ink varnish composition containing the rosin-modified phenolic resin and a printing ink.
  • offset printing dampening water is attached to a printing plate composed of an oleophilic part and a hydrophilic part, and water is attached to the hydrophilic part.
  • This is a printing method in which an oleophilic part to which oil-based ink adheres is used as an image line part, the ink is transferred to a blanket, and this is transferred again to paper, etc.
  • Offset sheet-fed printing, offset rotary printing, offset newspaper printing, etc. Can be mentioned. While offset printing is a general-purpose printing technique, the performance required of printing ink is very large and complex, and in order to optimize the balance of various performances, the design of ink resins is important.
  • offset printing uses water at the time of printing, so the printing ink needs to have moderate hydrophilicity, but if the hydrophilicity is too high, the ink adheres to the part that should originally be a non-image area.
  • problems such as blurring and the printing surface being difficult to dry and the setting being delayed.
  • the hydrophilicity of the ink is too low, there is a problem that the ink is not placed on the boundary between the hydrophilic portion and the oleophilic portion, and the portion that should originally become the image line portion is not printed.
  • the viscosity and elasticity of the printing ink must be high to some extent. However, when the viscosity is too high, the fluidity is lowered and the printed surface is inferior in gloss.
  • an object of the present invention is to provide a printing ink that is excellent in setability and misting resistance and that can provide a high gloss printing surface, a varnish composition for the printing ink, and a rosin-modified phenolic resin.
  • the present inventors have obtained a rosin-modified phenolic resin obtained by using a phenol having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position. Has optimal emulsification ability and fluidity for printing inks, so that printing inks obtained using this have excellent setability and misting resistance, and a highly glossy printing surface can be obtained. As a result, the present invention has been completed.
  • the present invention relates to a phenol compound (A), rosin or rosin derivative (B), aldehyde (C) and polyhydric alcohol (unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position).
  • the present invention relates to a rosin-modified phenolic resin obtained by reacting D) as an essential raw material component.
  • the present invention further relates to an ink varnish composition containing the rosin-modified phenolic resin and the organic solvent (E) as essential components.
  • the present invention further relates to a printing ink containing the varnish composition for ink and the pigment (F) as essential components.
  • the varnish composition for printing ink, and rosin modification A phenolic resin can be provided.
  • the rosin-modified phenolic resin of the present invention comprises a phenol compound (A), rosin or rosin derivative (B), aldehyde (C) and polyhydric acid having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position. It is obtained by reacting a monohydric alcohol (D) as an essential raw material component.
  • a phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position is used as a raw material for the rosin-modified phenol resin.
  • the phenol compound (A) is represented by the following general formula (1).
  • R represents an unsaturated hydrocarbon group having 10 to 20 carbon atoms
  • R ′ represents a hydrocarbon group having 1 to 4 carbon atoms, a carboxyl group, a hydroxyl group, This represents any substituent selected from the group consisting of methoxy groups, and n represents an integer of 0-2.
  • n represents an integer of 0-2.
  • the said phenol compound (A) may be used individually by 1 type, and may use 2 or more types together.
  • a rosin-modified phenol resin having emulsifiability suitable for ink use can be obtained.
  • the number of carbon atoms is less than 10
  • the resulting rosin-modified phenolic resin has too high hydrophilicity, so that ink adheres or bleeds to the part that should be the non-image area, or the printed surface is Problems such as difficulty in drying and slow setting.
  • the hydrophilicity of the obtained rosin-modified phenolic resin is lowered when it exceeds 20, the ink does not appear on the boundary between the hydrophilic part and the lipophilic part, and the part that should originally become the image line part is not printed. Will occur.
  • a rosin-modified phenol which is more excellent in emulsification ability is obtained, and therefore a phenol having an unsaturated hydrocarbon group having 12 to 18 carbon atoms in the meta position is more preferable, and having 14 to 16 carbon atoms.
  • Particularly preferred is a phenol having an unsaturated hydrocarbon group in the meta position at the meta position.
  • the unsaturated hydrocarbon group having 10 to 20 carbon atoms in the phenol compound (A) used in the present invention has an unsaturated bond
  • the unsaturated bond will be described later.
  • the carboxyl group of rosin or rosin derivative (B) and various hydroxyl groups By reacting with the carboxyl group of rosin or rosin derivative (B) and various hydroxyl groups, a crosslinked structure is formed, and appropriate viscoelasticity and emulsification performance are imparted.
  • the resin having a high molecular weight by the reaction has a characteristic of having a low viscosity while being highly elastic.
  • hydrocarbon groups having unsaturated bonds in the range of 1 to 5 are preferred, and unsaturated bonds in the range of 2 to 3 because a resin for printing ink having excellent fluidity and emulsification suitability can be obtained.
  • the hydrocarbon group is particularly preferable.
  • the most preferable phenol compound (A) is an unsaturated hydrocarbon group having a carbon atom number in the range of 14 to 16 and an unsaturated bond number in the range of 2 to 3.
  • This is a phenol compound (a) having a meta position.
  • Such a compound may be a pure product of the compound represented by the general formula (1) or a compound derived from a natural product such as cardanol.
  • a rosin-modified phenolic resin having high elasticity and low viscosity is obtained, and a printing ink excellent in fluidity and gloss is obtained, and since it is easily available, a compound derived from a natural product such as cardanol is used. It is preferable to use it.
  • cardanol is a mixture of four phenolic compounds having a hydrocarbon group having 15 carbon atoms in the meta position shown in Table 1 below, and the average number of double bonds possessed by the hydrocarbon group is 2. is there.
  • the phenolic compound (A) has a good balance between elasticity and viscosity, and becomes a rosin-modified phenolic resin having excellent fluidity and gloss when inked. Therefore, the total amount of the phenolic compound (A) is 100 parts by mass. In contrast, the phenol compound (a) is preferably contained in an amount of 50 parts by mass or more, and more preferably 75 parts by mass or more.
  • Naturally derived compounds such as cardanol mentioned as the phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position include, for example, urushiaceae such as urushi, mango and cashew. It can be obtained as a component contained in the extract and purified from the plant.
  • urushiaceae such as urushi, mango and cashew. It can be obtained as a component contained in the extract and purified from the plant.
  • cashew shell oil obtained by heating and purifying an oily liquid contained in cashew husks contains the above-mentioned cardanol in higher purity and can be obtained industrially at a low price. To preferred.
  • an extraction product such as cashew shell oil
  • the rosin-modified phenol resin is excellent in emulsification suitability, has a good balance between elasticity and viscosity, and has excellent fluidity and gloss when inked.
  • the phenol compound (A) is preferably used in the range of 0.5 to 40 parts by mass, more preferably in the range of 5 to 35 parts by mass with respect to parts by mass.
  • the phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position is used as the phenol component. If necessary, the phenol compound (A) Other phenol compounds (A ′) other than those may be used in combination.
  • Examples of the other phenol compound (A ′) include phenol, cresol, amylphenol, bisphenol A, p-tert-butylphenol, dibutylphenol, and dimethylphenol.
  • p-tert-butylphenol is preferred because a rosin-modified phenolic resin can be stably produced, a printing ink can be obtained that has excellent setability and anti-misting properties and can provide a high gloss printing surface.
  • a ′ is preferably used in the range of 5 to 70 parts by mass.
  • rosin or rosin derivative (B) used in the present invention will be described.
  • examples of the rosin used in the present invention include gum rosin, tall oil rosin, wood rosin and the like, and these are natural resins.
  • the hydrogenated rosin is obtained by saturating a part or all of the unsaturated bonds by hydrogenating rosin.
  • the polymerized rosin is obtained by polymerizing rosin in the presence of a catalyst such as sulfuric acid, and is a mixture containing not only a dimer but also a monomer and a multimer of trimers or more.
  • the disproportionated rosin is obtained by transferring hydrogen between molecules by heating the rosin or the like to saturate the unsaturated bond of one molecule and simultaneously unsaturate the other saturated bond. .
  • the reinforced rosin is a modified rosin obtained by modifying a rosin with an ⁇ , ⁇ -unsaturated carboxylic acid such as maleic anhydride, fumaric acid or acrylic acid.
  • the rosin ester is a rosin obtained by modifying rosin with a polyhydric alcohol such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol. These may be used alone or in combination.
  • a polyhydric alcohol such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol.
  • rosins such as gum rosin, tall oil rosin, and wood rosin are preferable because they are excellent in reactivity with other components and are industrially inexpensive, and more, there are many abietane skeletons having unsaturated bond sites. Gum rosin is more preferable because of its high reactivity.
  • aldehyde (C) used in the present invention examples include formaldehyde, acetaldehyde, propionaldehyde and the like.
  • examples of the formaldehyde include decomposition products such as formalin, paraformaldehyde, and trioxane. These may be used alone or in combination. Among these, formaldehyde is preferable and paraformaldehyde is more preferable because of its high reactivity with the phenol compound (A).
  • the aldehyde (C) contains an aldehyde (C) with respect to a total of 1 mol of hydroxyl groups contained in the phenol compound (A) because a rosin-modified phenol resin having excellent misting resistance and emulsification suitability is obtained.
  • the carbonyl group to be used is preferably used in a ratio of 1.5 to 3.0 mol.
  • the phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position and the other phenol compound (A ′) are used in combination, the phenol In such a ratio that the carbonyl group contained in the aldehyde (C) is in the range of 1.5 to 3.0 moles per 1 mole of the total hydroxyl group contained in the compound (A) and the phenol compound (A ′). It is preferable to use it.
  • Examples of the polyhydric alcohol (D) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, and nonane.
  • Examples include dihydric alcohols such as diol and neopentyl glycol; trihydric or higher alcohols such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.
  • the trivalent or higher alcohol is preferable, and glycerin or pentaerythritol is preferable.
  • the polyhydric alcohol (D) can easily adjust the molecular weight of the obtained rosin-modified phenol resin to a preferable value, and has excellent misting resistance and emulsification suitability. Therefore, the rosin or rosin derivative (B ) Is preferably used in such a ratio that the hydroxyl group contained in the polyhydric alcohol (D) is in the range of 0.5 to 1.5 moles with respect to 1 mole of the carboxyl group.
  • the rosin-modified phenolic resin of the present invention may contain vegetable oil or the like as a raw material component in addition to the phenol compound (A), rosin or rosin derivative (B), aldehyde (C) and polyhydric alcohol (D).
  • the vegetable oils used here include, for example, vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, and other vegetable oils that have been regenerated after using these vegetable oils for food processing, etc.
  • Examples include vegetable oil fatty acid monoesters such as fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, and the like. These may be used alone or in combination of two or more. When other raw material components such as vegetable oil are used, the effect of the present invention is remarkably exhibited as a resin having excellent emulsification suitability and fluidity, excellent setability and misting resistance, and high gloss printing ink can be obtained.
  • Examples of the rosin-modified phenolic resin of the present invention include those obtained by any of the following methods (1) to (3).
  • Method (2) A phenol compound (A) having an unsaturated hydrocarbon group having a carbon atom number in the range of 10 to 20 in the meta position, rosin or rosin derivative (B), and aldehyde (C) are reacted, and then a polyhydric alcohol ( A method of adding D) and causing an esterification reaction.
  • Method (3) A condensate obtained by reacting a phenol compound (A) having an unsaturated group having 10 to 20 carbon atoms at the meta position with an aldehyde (C), rosin or a rosin derivative (B) and a polyhydric alcohol (D) A method in which a rosin ester obtained by reacting is separately produced, and then the condensate is reacted with a rosin ester.
  • the condensate obtained by reacting an aldehyde (C) with a phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 atoms in the meta position is, for example, ( ⁇ ) a resole obtained by reacting a phenolic compound (A) having an unsaturated hydrocarbon group having 10 to 20 atoms in the meta position with an aldehyde (C) in the presence of a basic catalyst, ( ⁇ ) A phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 atoms in the meta position and an aldehyde (C) are reacted in the presence of an acidic catalyst in advance, and then an aldehyde (C ) And a novolak resole obtained by reacting in the presence of a basic catalyst.
  • a resol is preferable because a printing ink with little resin coloring and excellent color development can be obtained.
  • the other phenol compound (A ′) when the other phenol compound (A ′) is used, a method of charging and reacting with the phenol compound (A) may be used, or the other phenol compound (A ′).
  • a natural product-derived raw material such as cashew shell oil
  • the other phenol compound (A ′) and aldehyde (C) are reacted.
  • a method of adding a raw material derived from natural products such as cashew shell oil together with polyhydric alcohol (D) may be used.
  • the basic catalyst used is, for example, a metal catalyst such as sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, zinc acetate, etc.
  • alkylamines such as ammonia, methylamine, dimethylamine, diethylamine, trimethylamine, ethylamine, diethylamine and triethylamine, and alkanolamines such as ethanolamine, diethanolamine and triethanolamine.
  • the acidic catalyst used is, for example, sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, or the like.
  • sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, or the like.
  • mineral acids such as sulfuric acid and hydrochloric acid.
  • the molecular weight and solvent solubility of the obtained rosin-modified phenol resin can be easily adjusted, and the rosin-modified phenol is excellent in misting resistance and drying properties.
  • the condensate obtained by reacting the compound (A ′) is preferably in the range of 15 to 70 parts by mass.
  • esterification reaction temperature is preferably 200 ° C. or higher and lower than 300 ° C. Below 200 ° C., the reaction proceeds very slowly and is not suitable for practical use. On the other hand, at 300 ° C. or higher, the decomposition reaction tends to occur, and the desired resin physical properties are difficult to obtain.
  • a catalyst As the catalyst, an acid catalyst or a metal catalyst is used.
  • Known acid catalysts can be used for the esterification reaction.
  • examples thereof include sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and sulfuric acid.
  • sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and sulfuric acid.
  • p-toluenesulfonic acid is preferable from the viewpoints of price and compatibility with the resin.
  • Examples of the metal catalyst used in the esterification reaction include zinc oxide, zinc acetate, magnesium oxide, calcium oxide, calcium hydroxide, and lithium hydroxide.
  • a phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position, rosin or rosin derivative (B), and aldehyde (C) are reacted.
  • a process can be performed more efficiently and in a short time, for example by heating in a sealed state using a pressure-resistant reaction kettle.
  • the phenol compound (A) having an unsaturated hydrocarbon group having 10 to 20 carbon atoms in the meta position can be easily introduced into the resin, and the misting resistance,
  • the method (1) is preferable because a resin having excellent gloss and fluidity can be easily obtained.
  • the acid value is preferably 50 mgKOH / g or less, and more preferably in the range of 1 to 30 mgKOH / g.
  • the weight average molecular weight (Mw) of the rosin-modified phenolic resin of the present invention is preferably in the range of 10,000 to 200,000, and is preferably in the range of 30,000 to 130,000, since it has a viscosity suitable for printing ink applications. More preferably, it is the range.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device “HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HZ-H” manufactured by Tosoh Corporation + Tosoh Co., Ltd.
  • TSK-GEL SuperHZM-H x 4 detectors: RI (differential refractometer)
  • Data processing “GPC-8320 EcoSEC application” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 0.6 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320 EcoSEC application”.
  • the cloudiness temperature of the rosin-modified phenolic resin of the present invention is in the range of 30 to 220 ° C. because it is easy to obtain a printing ink having a sufficiently high viscosity and excellent misting resistance and excellent pigment dispersibility. It is preferable.
  • the cloudiness temperature means that 2 g of rosin-modified phenolic resin and 18 g of an organic solvent (“AF Solvent 6” manufactured by Nippon Oil Corporation) are placed in a glass tube, a magnetic stirrer is added, and the temperature is increased. It is the temperature at which the temperature becomes normal turbidity after being heated and dissolved at 230 ° C., and measured with a fully automatic turbidity measuring device [NOVOCONTROL manufactured by Chemotronic II] under the following conditions. Is the value to be It shows that the solubility to a solvent is so favorable that temperature is low. Holding time: 2 minutes Rotation speed N1: 1100 rpm Rotation speed N2 ... 800rpm Rotation speed N13 ... 1000rpm Holding temperature T1 ... 230 ° C Temperature T3 ... 80 ° C Turbidity detection level 4 Turbidity calibration mode: Ac
  • the ink varnish composition of the present invention contains the rosin-modified phenolic resin and the organic solvent (E) as essential components.
  • Examples of the organic solvent (E) include vegetable oils and petroleum solvents.
  • the vegetable oil includes, for example, vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, and regenerated vegetable oils that have been regenerated after these vegetable oils have been used for food processing or the like, as well as linseed oil fatty acid methyl
  • the vegetable oil fatty acid monoesters such as soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, and the like.
  • vegetable oils having unsaturated bonds in the molecules such as linseed oil, tung oil, soybean oil and the like are preferable because an ink having excellent drying properties is obtained, and soybean oil and its regenerated oil are more preferable because of low environmental load. .
  • Examples of the petroleum solvent include, for example, No. 0 solvent, No. 4 solvent, No. 5 solvent, No. 6 solvent, No. 7 solvent, AF solvent No. 4 and AF solvent 5 which are petroleum solvents manufactured by Nippon Oil Corporation. No., AF Solvent No. 6, AF Solvent No. 7 and the like. These may be used alone or in combination of two or more. Among them, since the load on the environment is small, the boiling point of AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7, etc. is 200 ° C. or higher and the aromatic hydrocarbon content is 1% by mass or less. Some petroleum solvents are preferred.
  • the rosin-modified phenolic resin of the present invention can be used for various printing ink applications, but when used for offset ink applications, the viscosity of the organic solvent (E) in the ink varnish composition can be adjusted. Since it is easy, it is preferably 40 to 75% by mass. At this time, it is preferable to use only vegetable oil as the organic solvent (E) in order to reduce VOC and make ink with a small environmental load. On the other hand, when used for ink applications, such as for web offset printing, where the solvent component is evaporated by hot air to promote setting, there are many cases where a petroleum-based solvent is used more than vegetable oil. In the present invention, vegetable oil and petroleum solvent may be used in an appropriate ratio depending on the purpose.
  • the ink varnish composition of the present invention may contain additives such as a gelling agent and an antioxidant in addition to the organic solvent (E).
  • the gelling agent is used for the purpose of adjusting the viscoelasticity of the ink varnish composition.
  • the gelling agent is used for the purpose of adjusting the viscoelasticity of the ink varnish composition.
  • Various known materials such as isocyanate and isophorone diisocyanate can be used without particular limitation. These may be used alone or in combination of two or more.
  • the amount of the gelling agent used is adjusted according to the target viscoelasticity, but is usually in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the ink varnish composition.
  • the antioxidant is used for the purpose of preventing skinning of the ink varnish composition, and various known ones such as 2,6-di-tert-butyl-4-methylphenol are used without any particular limitation. it can.
  • the amount of the antioxidant used is determined in consideration of the storage period and the like, but is usually in the range of 0.1 to 1.0 part by mass with respect to 100 parts by mass of the ink varnish composition.
  • the ink varnish composition can be produced by mixing and stirring the above-mentioned components, but when mixing and stirring, these are usually heated to a temperature in the range of 100 ° C to 240 ° C. Thus, each component is dissolved and mixed.
  • the printing ink of the present invention contains the ink varnish composition, that is, the rosin-modified phenol of the present invention, the organic solvent (E), and the pigment (F) as essential components.
  • Examples of the pigment (F) include colored pigments such as yellow, red, indigo or black, and colorless extender pigments.
  • the content of the pigment (F) is preferably in the range of 5 to 55 parts by mass in 100 parts by mass of the printing ink because it has excellent colorability and high fluidity.
  • the printing ink of the present invention may contain various additives such as a wax, a drying accelerator (dryer), a drying inhibitor, in addition to the ink varnish composition and the pigment (F).
  • a drying accelerator dryer
  • a drying inhibitor in addition to the ink varnish composition and the pigment (F).
  • the wax is added for the purpose of improving the friction resistance, anti-blocking property, slipperiness, anti-scratch property, etc. of the ink coating film, such as carnauba wax, wax, lanolin, montan wax, paraffin wax. And natural waxes such as microcrystalline wax; synthetic waxes such as Fischer-Trops wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound.
  • the content of the wax is excellent in abrasion resistance and blocking resistance, and is excellent in color tone and gloss. Therefore, the content of the wax is in the range of 0.1 to 7.0 parts by mass with respect to 100 parts by mass of the printing ink. Preferably there is.
  • the drying accelerator (dryer) is added for the purpose of improving the drying property of the ink coating film.
  • metals such as cobalt, manganese, lead, iron, and zinc and octylic acid, naphthenic acid, neodecanoic acid are used.
  • metal soaps which are salts with carboxylic acids such as
  • the content of the drying accelerator is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the printing ink because an ink having excellent drying properties can be obtained.
  • the drying inhibitor is added for the purpose of improving storage stability and suppressing skinning, and examples thereof include hydroquinone, methoquinone, tert-butylhydroquinone, and the like.
  • the content of the drying inhibitor is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the printing ink since the ability to suppress skinning is sufficiently exhibited.
  • These various additives added to the printing ink may be added at any stage of the printing ink production as long as they can be uniformly mixed in the printing ink. Specifically, it may be added at the final stage of printing ink production, or may be added in advance at the production stage of the ink varnish composition.
  • the pigment can be stably dispersed and it is easy to adjust the viscosity to be suitable for printing. Therefore, the organic solvent (E) is added in an amount of 10 to 65 to 100 parts by mass of the printing ink. It is preferable to contain in the range of mass parts.
  • the printing ink of the present invention uses, for example, a raw material containing rosin-modified phenol resin, organic solvent (E) and pigment (F) as essential components, using a known ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, or a sand mill. It can be obtained by cooking and preparing meat.
  • a known ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, or a sand mill. It can be obtained by cooking and preparing meat.
  • a part and% are a mass part and the mass%, respectively.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured under the following conditions using a gel permeation chromatograph (GPC).
  • Measuring device “HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HZ-H” manufactured by Tosoh Corporation + Tosoh Co., Ltd. “TSK-GEL SuperHZM-H” x 4 detectors: RI (differential refractometer)
  • Data processing “GPC-8320 EcoSEC application” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 0.6 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320 EcoSEC application”.
  • the cloudiness temperature is a value measured under the following conditions.
  • a glass tube is charged with 2 g of rosin-modified phenolic resin and 18 g of an organic solvent (“AF Solvent No. 6” manufactured by Shin Nippon Oil Co., Ltd.), a magnetic stirrer is added, the temperature is increased by stirring, the solution is dissolved at 230 ° C., and then cooled.
  • the temperature at which the specified turbidity was reached was measured with a fully automatic turbidity point measuring device ["Cemotronic II” manufactured by NOVOCONTROL Co., Ltd.] under the following conditions.
  • Holding time 2 minutes
  • Rotation speed N1 1100 rpm Rotation speed N2 ... 800rpm Rotation speed N13 ... 1000rpm
  • Turbidity detection level 4 Turbidity calibration mode: Ac
  • the maximum emulsification rate is a value measured under the following conditions. Using an emulsification tester (“High Speed Lithotronic Emulsification Tester” manufactured by Novo Control), under the following conditions, continuously measure the torque value when water is gradually added to the sample. When the standard deviation of the latest 10 measured values exceeded 100 after starting to fluctuate stably, the value calculated by the following formula was defined as the maximum emulsification rate.
  • Maximum emulsification rate (%) [Drip amount of water (g)] / [Sample amount (g) ⁇ 100] Conditioning time (preliminary stirring time without adding water) ... 300 sec Stirring speed ... 1200rpm Sample amount ... 25g Temperature ... 40 ° C Dripping amount of water ...
  • N-Heptane tolerance is the amount (mL) of n-heptane that was gradually dropped into 1 g of a sample and dropped to the cloud point where the letters on the newspaper laid under the bottom of the flask disappeared.
  • a four-necked separable flask equipped with a stirrer, a reflux condenser with a separator, and a thermometer was charged with 800 parts by weight of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. It was. While stirring the molten gum rosin, the whole amount of the condensate (F-1) solution obtained above and 5 parts by mass of zinc oxide were added, and the temperature was further raised to 220 ° C.
  • the acid value of the obtained rosin-modified phenol resin (1) was 24.0 mgKOH / g, the weight average molecular weight (Mw) was 60,000, and the cloudiness temperature was 180 ° C.
  • the rosin-modified phenol resin (1) is a resin using 1.0% by mass of cardanol with respect to 100 parts by mass of the resin raw material.
  • Example 2-1 Production of rosin-modified phenolic resin (2) In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 130 parts by mass of pt-butylphenol, 130 parts by mass of cardanol, 92% After charging 85 parts by mass of paraformaldehyde and 187 parts by mass of toluene and heating the contents to 50 ° C., 1.3 parts by mass of 48% aqueous sodium hydroxide solution was added. The contents were further heated to 80 ° C. and reacted for 6 hours, neutralized by adding 1.7 parts by mass of 35% hydrochloric acid, and washed with 51 parts by mass of water. After standing for 7 hours, the aqueous layer was removed to obtain a condensate (F-2) solution.
  • F-2 condensate
  • a four-necked separable flask equipped with a stirrer, a reflux condenser with a separator, and a thermometer was charged with 800 parts by weight of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. It was. While stirring the molten gum rosin, the whole amount of the condensate (F-2) solution obtained above and 5 parts by mass of zinc oxide were added, and the temperature was further raised to 220 ° C. Next, 72 parts by mass of glycerin was added, and the temperature was raised to 240 ° C. while taking toluene and water out of the reaction system with a reflux condenser with a separator.
  • F-2 condensate
  • the acid value reached 30 mgKOH / g When the acid value reached 30 mgKOH / g, the pressure in the four-necked flask was reduced to 20 mmHg with a vacuum pump, and maintained under reduced pressure for 60 minutes to obtain rosin-modified phenolic resin (2).
  • the acid value of the obtained rosin-modified phenol resin (2) was 25.6 mgKOH / g, the weight average molecular weight (Mw) was 120,000, and the cloudiness temperature was 209 ° C.
  • the rosin-modified phenol resin (2) is a resin using 12.0% by mass of cardanol with respect to 100 parts by mass of the resin raw material.
  • Example 3-1 Production of rosin-modified phenolic resin (3)
  • a stirrer 130 parts by mass of pt-butylphenol, 65 parts by mass of cardanol, 92%
  • a reflux condenser 130 parts by mass of pt-butylphenol, 65 parts by mass of cardanol, 92%
  • a reflux condenser 130 parts by mass of pt-butylphenol, 65 parts by mass of cardanol, 92%
  • 1.1 parts by mass of 48% aqueous sodium hydroxide solution was added.
  • the contents were further heated to 80 ° C. and reacted for 6 hours, neutralized by adding 1.4 parts by mass of 35% hydrochloric acid, and washed with 39 parts by mass of water.
  • the aqueous layer was removed to obtain a condensate (F-3) solution.
  • a four-neck separable flask equipped with a stirrer, a reflux condenser with a separator, and a thermometer was charged with 800 parts by mass of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. . While stirring the molten gum rosin, the whole amount of the condensate (F-3) solution obtained above was added, and the temperature was further raised to 215 ° C. Next, 65 parts by mass of glycerin and 8 parts by mass of pentaerythritol were added, and the temperature was raised to 250 ° C. while taking out toluene and water out of the reaction system with a reflux condenser with a separator.
  • the reaction was carried out for 4 hours while maintaining the temperature at 250 ° C., and 0.6 parts by mass of paratoluenesulfonic acid was added when the acid value reached 50 mgKOH / g, followed by further reaction for 5 hours.
  • the pressure in the four-necked flask was reduced to 20 mmHg with a vacuum pump, and kept under reduced pressure conditions for 60 minutes to obtain rosin-modified phenolic resin (3).
  • the acid value of the obtained rosin-modified phenol resin (3) was 21.6 mgKOH / g, the weight average molecular weight (Mw) was 34,000, and the cloudiness temperature was 130 ° C.
  • the rosin-modified phenolic resin (3) is a resin using 6.4% by mass of cardanol with respect to 100 parts by mass of the resin raw material.
  • Example 4-1 Production of rosin-modified phenolic resin (4)
  • a stirrer In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 54 parts by mass of pt-butylphenol, 433 parts by mass of cardanol, 92%
  • a reflux condenser After 117 parts by mass of paraformaldehyde and 329 parts by mass of toluene were charged and the contents were heated to 50 ° C., 1.8 parts by mass of 48% aqueous sodium hydroxide solution was added.
  • the contents were further heated to 70 ° C., reacted for 6 hours, neutralized by adding 2.4 parts by mass of 35% hydrochloric acid, and washed with 90 parts by mass of water. After standing for 7 hours, the aqueous layer was removed to obtain a condensate (F-4) solution.
  • F-4 condensate
  • a four-neck separable flask equipped with a stirrer, a reflux condenser with a separator, and a thermometer was charged with 800 parts by mass of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. .
  • the entire amount of the condensate (F-4) solution obtained above and 5 parts by mass of zinc oxide were added to the gum rosin, and the temperature was further raised to 220 ° C.
  • 58 parts by mass of glycerin was added, and the temperature was raised to 240 ° C. while taking toluene and water out of the reaction system with a reflux condenser with a separator.
  • the reaction was further carried out while maintaining the temperature at 240 ° C., and when the acid value reached 30 mgKOH / g, the inside of the four-necked flask was reduced to 20 mmHg with a vacuum pump, and kept under reduced pressure for 60 minutes, and rosin-modified phenol Resin (4) was obtained.
  • the acid value of the obtained rosin-modified phenol resin (4) was 27.2 mgKOH / g, the weight average molecular weight (Mw) was 100,000, and the cloudiness temperature was 161 ° C.
  • the rosin-modified phenol resin (4) is a resin using 33.2% by mass of cardanol with respect to 100 parts by mass of the resin raw material.
  • Example 5-1 Production of rosin-modified phenolic resin (5)
  • a stirrer a reflux condenser, and a thermometer
  • 78 parts by mass of pt-butylphenol 544 parts by mass of cardanol
  • 92% After charging 152 parts by mass of paraformaldehyde and 421 parts by mass of toluene and heating the contents to 50 ° C., 2.4 parts by mass of 48% aqueous sodium hydroxide solution was added.
  • the contents were further heated to 80 ° C., reacted for 6 hours, neutralized by adding 3 parts by mass of 35% hydrochloric acid, and washed with 115 parts by mass of water. After standing for 7 hours, the aqueous layer was removed to obtain a condensate (F-5) solution.
  • a four-neck separable flask equipped with a stirrer, a reflux condenser with a separator, and a thermometer was charged with 800 parts by mass of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. .
  • the whole amount of the condensate (F-5) solution obtained above and 5 parts by mass of zinc oxide were added, and the temperature was further raised to 220 ° C.
  • 69 parts by mass of glycerin was added, and the temperature was raised to 240 ° C. while taking toluene and water out of the reaction system with a reflux condenser with a separator.
  • the reaction was carried out while maintaining the temperature at 240 ° C., and when the acid value reached 30 mg KOH / g, the pressure in the four-necked flask was reduced to 20 mmHg with a vacuum pump, and the pressure was maintained for 60 minutes under the reduced pressure condition. (5) was obtained.
  • the acid value of the obtained rosin-modified phenol resin (5) was 28.0, the weight average molecular weight (Mw) was 80,000, and the cloudiness temperature was 158 ° C.
  • the rosin-modified phenol resin (5) is a resin using 36.6% by mass of cardanol with respect to 100 parts by mass of the resin raw material.
  • Table 1 summarizes the property values of rosin-modified phenolic resins (1) to (5) and (1 ').
  • Example 1-2 Production of Varnish Composition for ink (1) 40 parts by mass of crushed rosin-modified phenolic resin (1) obtained in Example 1-1, 30 parts by mass of soybean oil, and an organic solvent (new 30 parts by weight of Nippon Oil Co., Ltd. “AF Solvent No. 7”) is put into a four-necked separable flask, the contents are heated to 210 ° C. while blowing nitrogen gas, stirred for 1 hour, and then cooled to 130 ° C. did. 1.1 parts by mass of a gelling agent solution [a solution obtained by dissolving a gelling agent (“ALCH” manufactured by Kawaken Fine Chemical Co., Ltd.) with an equal amount of organic solvent (“AF Solvent No.
  • the temperature was raised to 160 ° C. and kept for 1 hour to obtain an ink varnish composition (1).
  • the resulting ink varnish composition had a cell viscosity of 6,000 dPa ⁇ s, a maximum emulsification rate (EC%) of 40%, and a heptane tolerance of 16 mL.
  • Example 2-2 to 5-2 and Comparative Example 1-2 The rosin-modified phenolic resin (1) is changed to the rosin-modified phenolic resin (2) to (5) or (1 ′) so that the bubble viscosity of the contents is in the range of 6,000 to 8,000 dPa ⁇ s.
  • Table 1 shows the cell viscosity, maximum emulsification rate (EC%), and heptane tolerance of the resulting ink varnish compositions (2) to (5) and (1 ′).
  • Example 1-3 Production of Printing Ink (1) 40 parts by mass of the ink varnish composition (1) obtained in Example 1-2 and 40 parts by mass of a yellow flash base were kneaded with a three roll, An organic solvent (“AF Solvent No. 4” manufactured by Shin Nippon Oil Co., Ltd.) was gradually added and adjusted so that the Raleigh viscosity was 13 to 18 Pa ⁇ s to obtain a printing ink (1).
  • An organic solvent (“AF Solvent No. 4” manufactured by Shin Nippon Oil Co., Ltd.) was gradually added and adjusted so that the Raleigh viscosity was 13 to 18 Pa ⁇ s to obtain a printing ink (1).
  • ⁇ “20% or more and 90% or less” is a level at which appropriate ink emulsification can be performed, and ink smear is hardly generated in the portion where the ink should be placed on the image area and become the non-image area.
  • ⁇ “Over 90% and 130% or less, or 10% or more and less than 20%”, so that a certain level of ink can be emulsified, and the ink should be placed on the image area to become a non-image area. Ink smear is at a level where there is no practical problem.
  • Gloss of printed surface 0.4 ml of the obtained printing ink (1) was developed on art paper using an RI tester, and this art paper was dried in an oven at 130 ° C. for 15 seconds to obtain an ink coating film. .
  • the 60 ° -60 ° reflectivity of the ink coating surface was measured by a gloss meter (“micro TRI gloss 4520” manufactured by BYK) and evaluated according to the following criteria.
  • ⁇ Gloss is slightly superior (60% or more and less than 70%)
  • ⁇ Gloss is at a practical level (55% or more and less than 60%)
  • X The gloss does not reach a practical level (less than 55%)
  • -Setting property 0.4 mL of the obtained printing ink (1) was developed on art paper using an RI tester, and this art paper was dried in an oven at 130 ° C for 15 seconds to obtain an ink coating film.
  • the dry touch state of the ink coating film was determined according to the following criteria. ⁇ : The printing surface layer and the inside of the printing surface layer are dry well and have no stickiness. X: The printing surface layer part and the inside of the printing surface layer are poorly dry and sticky.
  • Example 2-3 to 5-3 and Comparative Example 1-3 Printing inks (2) to (5) were prepared in the same manner as in Example 1-3 except that the ink varnish composition (1) was changed to the ink varnish compositions (2) to (5) or (1 ′). ) And (1 ′) were obtained, and various evaluation tests were conducted in the same manner as in Example 1-3. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

La présente invention a pour objet de proposer une encre d'impression caractérisée par de remarquables performances en matière de séchage, qui est non nébulisante et qui donne, en outre, une surface imprimée très brillante, ainsi qu'une composition de vernis pour ladite encre d'impression et une résine phénolique modifiée par de la colophane. Pour ce faire, l'invention fait appel à une résine phénolique modifiée par de la colophane obtenue en faisant réagir, en tant que composants de base, un composé phénolique (A) comportant un groupe hydrocarboné insaturé en C10 à C20 en position méta, une colophane (B), un aldéhyde (C) et un alcool polyhydrique (D).
PCT/JP2013/069416 2012-09-13 2013-07-17 Résine phénolique modifiée par de la colophane, composition de vernis pour encre et encre d'impression WO2014041890A1 (fr)

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WO2017099146A1 (fr) * 2015-12-09 2017-06-15 ハリマ化成株式会社 Résine pour encre d'impression, vernis pour encre d'impression, encre d'impression et procédé de production de résine pour encre d'impression

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