JP3344240B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition having excellent rub resistance, blocking resistance, printability, water repellency and wiping properties.

[0002]

2. Description of the Related Art Hitherto, with the increase in printing speed, friction resistance, blocking resistance, and printability at the lower limit of water width on a triangular plate during off-wheel printing at high speed are not always satisfactory. Was. Further, an overprint varnish (hereinafter, referred to as an OP varnish) is used for improving the gloss of the printed matter and protecting the film of the printed matter. That is, after printing each color of printing ink (yellow, red, indigo, and black), a colorless and transparent OP varnish is printed. However, if coffee, juice, etc. spills on the printed matter, the surface will be stained, and the printed matter will be sticky, or if exposed to the weather, such as a poster, the water repellency will be insufficient. The film is attacked.
Furthermore, it is not always sufficient against heat and scratches. As a countermeasure for these, conventionally, a polyethylene wax or a silicon-based additive has been used for the OP varnish, but it has not always been sufficient.

[0003]

SUMMARY OF THE INVENTION The present invention particularly provides a coating composition having excellent rub resistance, blocking resistance, printability, water repellency and wiping properties.

[0004]

That is, the present invention provides a rosin-modified phenolic resin (A), a drying oil (B) and / or a drying oil fatty acid ester (C), a diluent (D), and a fluororesin powder. (E), wherein at least one of the rosin-modified phenolic resin (A), the drying oil (B) and / or the drying oil fatty acid ester (C), and the diluent (D) contains a fluorinated component. A coating composition characterized by the following:

[0005] The present invention further relates to the above coating composition, wherein the fluororesin powder is a polyfluoroalkylene.

Further, the present invention relates to the above coating composition, wherein the drying oil (B) is a mixture of the fluorinated compounds represented by the general formulas (1) and (2). R ¹ COOCH ₂ (CHOOCR ¹ ) CH ₂ OOCR ¹ (1) (R ¹ COO) r R ² (2) (wherein, R ¹ is an alkyl group or a perfluoroalkyl group [CF ₃ (CF ₂ ) n of a drying oil] , N represents an integer of 0 to 15.], and all R ¹ are not simultaneously an alkyl group, R ² is an aliphatic chain residue having 2 to 10 carbon atoms, and r is 2 to 6 Represents an integer.)

Further, the present invention relates to the above coating composition, wherein the drying oil fatty acid ester (C) is a fluorinated compound represented by the general formula (3). R ¹ COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ (3) (wherein, R ¹ is an alkyl group of a fatty acid in the drying oil, and n is 0 to 0)
Indicates an integer of 15. )

Further, the present invention relates to the above coating composition, wherein the phenol component of the rosin-modified phenol resin (A) is a fluorinated compound represented by the general formula (4). _{CF 3 (CF 2) n (} CH 2) m-φ-OH (4) ( wherein, phi is a phenylene group, n represents an integer of 0 to 15, m is an integer of 0 to 2.)

Further, the present invention relates to the above coating composition, wherein the diluent (D) is a mixture of the fluorine compounds represented by the general formulas (5) and (6). R ³ COOCH ₂ (CHOOCR ³ ) CH ₂ OOCR ³ (5) (R ³ COO) rR ² (6) (wherein R ³ is an alkyl group or a perfluoroalkyl group of a fatty oil, and all R ³ are simultaneously R ² is an aliphatic hydrocarbon residue having 2 to 10 carbon atoms, and r is an integer of 2 to 6.)

The present invention further relates to the above coating composition, wherein the diluent (D) is a fluorinated compound represented by the general formula (7). R ⁴ [COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ ] x (7) (wherein, R ⁴ is an optionally fluorinated aliphatic hydrocarbon residue or aromatic ring residue, and n is 0 to 15) And x represents an integer of 1 to 4.)

Further, the present invention relates to the above coating composition, wherein the diluent (D) is a fluorinated compound represented by the general formula (8). R ⁵ [OOC (CF ₂₎ yCF _3] z (8) (wherein, R ⁵ is an aliphatic hydrocarbon residue, y is an integer of 0 to 15, z is an integer of 2-4.)

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the coating composition of the present invention are described below. From non-fluorinated (non-fluorinated) rosin-modified phenolic resin, fluorinated drying oil and / or fluorinated drying oil fatty acid ester, non-fluorinated (non-fluorinated) diluent, and fluorinated resin powder Coating composition comprising:

2. Coating composition comprising fluorinated rosin-modified phenolic resin, non-fluorinated (non-fluorinated) drying oil and / or drying oil fatty acid ester, non-fluorinated (non-fluorinated) diluent, and fluorinated resin powder object.

3. A coating composition comprising a fluorinated rosin-modified phenolic resin, a fluorinated drying oil and / or a fluorinated drying oil fatty acid ester, a non-fluorinated diluent, and a fluorinated resin powder.

4. A coating composition comprising a non-fluorinated rosin-modified phenolic resin, a fluorinated drying oil and / or a fluorinated drying oil fatty acid ester, a fluorinated diluent, and a fluorinated resin powder.

5. A coating composition comprising a fluorinated rosin-modified phenolic resin, a non-fluorinated drying oil and / or a drying oil fatty acid ester, a fluorinated diluent, and a fluorinated resin powder.

6. A coating composition comprising a fluorinated rosin-modified phenolic resin, a fluorinated drying oil and / or a fluorinated drying oil fatty acid ester, a fluorinated diluent, and a fluorinated resin powder. The fluorinated component can be used as a mixture of non-fluorinated components. For example, a mixture of fluorinated and non-fluorinated drying oils can be used.

The fluorinated drying oil and fluorinated drying oil fatty acid ester which can be used in the present invention include compounds represented by formulas (1) and (2). These compounds can be obtained, for example, by transesterifying a drying oil (having an iodine value of 130 or more) with a polyol [R ¹ (OH) r] and then reacting with a perfluoroalkylcarboxylic acid. Here, the drying oil refers to a drying oil having an iodine value of 130 or more, such as linseed oil, tung oil, and soybean oil.

R ¹ COOCH ₂ (CHOOCR ¹ ) CH ₂ OOCR ¹ (1) (R ¹ COO) r R ² (2) (where R ¹ is an alkyl group or perfluoroalkyl group of a drying oil [CF ₃ (CF ₂ ) n and n each represent an integer of 0 to 15.], and not all of R ¹ are alkyl groups at the same time, R ² is an aliphatic chain residue having 2 to 10 carbon atoms, and r is It represents an integer of 2 to 6.)

In the transesterification reaction, a drying oil and a polyol species, for example, a polyhydric alcohol having at least two or more hydroxyl groups in a molecule such as ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol are converted into sodium alkoxide, Using sodium, pyridine, aluminum alkoxide, titanate or the like as a catalyst, the reaction is carried out at a temperature in the range of 70 to 240 ° C. Further, thereafter, an esterification reaction with a perfluoroalkylcarboxylic acid is performed in the same temperature range to obtain a fluorinated dry oil and a fluorinated dry oil fatty acid ester. If necessary, an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid can be used.

Perfluoroalkylcarboxylic acid [CF ₃
(CF ₂₎ nCOOH, n is an integer of 0 to 15. ]
As perfluoromethylcarboxylic acid, perfluoroethylcarboxylic acid, perfluoropropylcarboxylic acid, perfluorobutylcarboxylic acid, perfluoropentylcarboxylic acid, perfluorohexylcarboxylic acid, perfluorooctylcarboxylic acid, perfluorononylcarboxylic acid, perfluorodecylcarboxylic acid, perfluorododecyl Carboxylic acid, perfluorohexadecylcarboxylic acid and the like can be mentioned.

Examples of polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol,
Examples include aliphatic polyhydric alcohols such as 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol.

As the fluorinated drying oil fatty acid ester which can be used in the present invention, there is a compound represented by the general formula (3). R ¹ COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ (3) (wherein, R ¹ is an alkyl group of a fatty acid in the drying oil, and n is 0 to 0)
Indicates an integer of 15. This compound hydrolyzes a drying oil (iodine value of 130 or more) into fatty acid components such as linseed oil, tung oil, soybean oil, etc., and combines these fatty acid components with 2-perfluoroalkylethanol [HOCH ₂ CH ₂ (CF ₂ )]. nCF ₃ , n is 1 to 15
Indicates an integer. ] In the temperature range of 50 to 220 ° C. under a catalyst (or without a catalyst) such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or the like.

Examples of 2-perfluoroalkylethanol include 2-perfluoromethylethanol, 2-perfluoroethylethanol, 2-perfluoropropylethanol, 2-perfluorobutylethanol, 2-perfluoropentylethanol, 2-perfluorooctylethanol, Perfluorodecyl ethanol, 2
-Perfluorododecylethanol, 2-perfluorohexadecylethanol and the like.

Next, a non-fluorinated general rosin-modified phenolic resin is obtained by reaction with a rosin or a derivative thereof, a phenol formaldehyde addition condensate (so-called resol), and, if necessary, a polyhydric alcohol. It was done. Here, the rosins or derivatives thereof represent rosins or carboxyl group-containing derivatives thereof. Rosins include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, water-added rosin and polymers thereof, and carboxyl group-containing derivatives thereof include unsaturated carboxylic acids such as maleic acid, itaconic acid and crotonic acid. Rosin derivatives to which an acid has been added are exemplified.

The phenols used in the phenol-formaldehyde addition condensate include phenolic acid and carbon atoms having 1 carbon atom.
Alkyl-substituted phenols substituted with up to 20 linear, branched or cyclic alkyl groups, such as p-cresol, m
-Cresol, p-propylphenol, p-tert
-Butylphenol, p-amylphenol, p-cyclohexylphenol, p-tert-octylphenol, p-nonylphenol, p-decylphenol,
Alkyl-substituted phenols such as p-dodecylphenol, aromatic-substituted phenols such as phenylphenol and cumylphenol, and polyhydric phenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol S, and bisphenol F may be mentioned. it can.

As a method for producing a corresponding phenol formaldehyde addition condensate using the above-mentioned phenols, a method in which the above-mentioned phenols and aldehydes are heated and reacted in an aqueous or organic solvent in the presence of an alkali catalyst, that is, resole A method for producing a phenolic resin, or a phenol and an aldehyde are heated and reacted in an aqueous or organic solvent in the presence of an acidic catalyst to first produce a novolak phenolic resin, and then in the presence of an aldehyde and an alkali catalyst. And a method for obtaining a resolated phenolic resin by heat reaction.

The aldehydes used include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, glyoxazole and furfural, and the like.
Examples of the acid catalyst include potassium hydroxide and calcium hydroxide, and examples of the acid catalyst include acetic acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, sulfuric acid, p-toluenesulfonic acid, trifluoromethylsulfuric acid, and trifluoromethylacetic acid. The preferred degree of polymerization of the phenol resin obtained here is such that the number of phenol nuclei is at least 2 units, more preferably 3 units.
Those having a unit or more are preferred from the viewpoint of solubility.

Examples of polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol,
Examples include aliphatic polyhydric alcohols such as 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol.

The non-fluorinated rosin-modified phenolic resin of the present invention comprises a rosin, a resole and, if necessary, a polyhydric alcohol in any order at an elevated temperature, preferably in a temperature range of 150 ° C. to 300 ° C. It is obtained by heating and reacting. If necessary, an acidic catalyst can be used in the reaction. Examples of such an acidic catalyst include sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, and sulfuric acid. And mineral acids such as hydrochloric acid. In order to prevent coloring, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate or the like can be used in combination. As a catalyst other than the acidic catalyst, magnesium salts such as magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, magnesium acetate, magnesium formate, and magnesium oxalate may be used. Further, the pressure can be reduced in order to promote the condensation reaction.

Further, the rust of the metal can be prevented by neutralizing the hydrogen ions derived from the remaining acid catalyst and the like. As the neutralizer, hydroxides, oxides, or salts of carboxylate salts of metals such as lithium, cesium, magnesium, calcium, strontium, barium, aluminum, zinc, titanium, zirconium, antimony, and selenium can be used. is there.

The non-fluorinated general diluents include solvents for printing inks of paraffinic, olefinic and naphthenic types, and are solvents No. 0-8, 4-8, manufactured by Nippon Petrochemical Co., Ltd. No. AF (aroma-free) solvent.

Next, the fluorinated rosins-modified phenol resin which can be used in the present invention will be described. The fluorinated rosin-modified phenolic resin is obtained by the same reaction operation as the above-mentioned non-fluorinated general rosin-modified phenolic resin, but is obtained from a fluorinated phenol represented by the general formula (4) as a resole. The resulting fluorinated phenol formaldehyde addition condensate (so-called fluorinated resol) can be used for the reaction. Rosins or derivatives thereof and polyhydric alcohols may be the same as those described above.

The fluorinated alkylphenol is obtained by introducing a fluorine atom into the alkyl chain in the alkylphenol, and examples thereof include the following fluorinated alkylphenols. Specifically, perfluoroalkylphenol such as perfluoromethylphenol, perfluoroethylphenol, perfluoropropylphenol, perfluorobutylphenol, perfluoropentylphenol, perfluorohexylphenol, perfluorooctylphenol, perfluorononylphenol, perfluorodecylphenol, perfluorododecylphenol, perfluorohexadecylphenol, etc. No. Furthermore, perfluoromethylmethylphenol, perfluoroethylmethylphenol, perfluoropropylmethylphenol, perfluorobutylmethylphenol, perfluoropentylmethylphenol, perfluorohexylmethylphenol, perfluorooctylmethylphenol, perfluorononylmethylphenol, perfluorodecylmethylphenol, perfluorododecylmethylphenol And perfluoroalkylmethylphenol such as perfluorohexadecylmethylphenol.
Furthermore, 2-perfluoromethylethylphenol, 2-
Perfluoroethylethylphenol, 2-perfluoropropylethylphenol, 2-perfluorobutylethylphenol, 2-perfluoropentylethylphenol, 2-perfluorohexylethylphenol, 2-perfluoroheptylethylphenol, 2-
Perfluorooctylethylphenol, 2-perfluorononylethylphenol, 2-decylethylphenol, 2-perfluoroundecylethylphenol,
Examples thereof include 2-perfluorododecylethylphenol, 2-perfluorotridecylethylphenol, 2-perfluorotetradecylethylphenol, 2-perfluoropentadecylethylphenol, and 2-perfluorohexadecylethylphenol.

These perfluoroalkylphenols,
Perfluoroalkylmethylphenol and 2-perfluoroalkylethylphenols are prepared by converting phenolic acid and halogenated perfluoroalkanes (perfluoroalkane, halogenated perfluoroalkylmethane, 1-halogen-2-perfluoroalkylethane) into anhydrous aluminum chloride as a catalyst. It is synthesized by the Friedel Crafts reaction. Further, as a method for producing 2-perfluoroalkylethylphenol, 2-perfluoroalkylethanol is reacted with trifluoromethanesulfonic anhydride or trifluoromethanesulfonyl chloride to obtain a trifluoromethanesulfonic acid ester, and the ester is treated with an alkoxyhalobenzene and Mg using Grignard. Utilizing the reaction, 2-fluoroalkylethylalkoxybenzene can be synthesized by changing the alkoxy group to a hydroxy group by a known method.

In the present invention, as the phenol component used in the fluorinated alkylphenol formaldehyde addition condensate, in addition to 1% by weight or more of the above-mentioned fluorinated alkylphenol, 0 to 99% by weight of phenolic acid having 1 to 20 carbon atoms. Alkyl-substituted phenols substituted with linear, branched or cyclic alkyl groups, such as p-cresol,
m-cresol, p-propylphenol, p-ter
Alkyl-substituted phenols such as t-butylphenol, p-amylphenol, p-cyclohexylphenol, p-tert-octylphenol, p-nonylphenol, p-decylphenol, p-dodecylphenol, phenylphenol, cumylphenol and the like And phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol S, and bisphenol F. These fluorinated alkylphenol formaldehyde addition condensates can be obtained by the same operation as in the resol synthesis method described above.

A general method for synthesizing the fluorinated rosin-modified phenolic resin of the present invention is shown below. In addition,% shows weight%. (General synthesis method of fluorinated resol) The above-mentioned fluorinated alkylphenols and aldehydes were placed in a reaction vessel, and aldehydes were added in an amount of 0.2 mol per mole of fluorinated alkylphenols.
And a solvent such as toluene or xylene, and the solid content of the fluorinated alkylphenol formaldehyde resin (fluorinated resol) is 40 to 70%.
And dissolved at 50 ° C. Then, an insoluble basic salt such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium oxide as a catalyst is mixed with water and added as a slurry. Ammonia water and amines can also be used as catalysts, and both basic salts and amines can be synthesized in the range of 0.05 to 0.1 mol per mol of phenol. 0.05
If it is less than 0.1 mol, the reaction is slow and unreacted substances increase, and if it is 0.1 mol or more, the solubility of the obtained printing ink resin deteriorates. The amount of water is preferably 3 to 10% based on the total amount.
When the amount of water is 3% or less, the coloring of the resulting fluorinated resol becomes large, and when it is 10% or more, the progress of condensation is slowed, and a fluorinated resol having a required molecular weight cannot be obtained.
After the addition of the catalyst, the reaction is continued at a reaction temperature of 65 to 110 ° C. for 5 to 10 hours, cooled, and then washed with neutralized water with hydrochloric acid, formic acid, acetic acid, sulfuric acid or the like.

(General Method for Synthesizing Rosin-Modified Phenolic Resin) A reaction vessel is charged with 40 to 70% by weight of rosin,
After heating and dissolving while blowing in an inert gas, for example, nitrogen gas or carbon dioxide gas, and raising the temperature to 150 to 260 ° C., 30 to 50% by weight of the fluorinated resol (solid content%)
) Was added dropwise at a time or over 2 to 5 hours, and then the polyol component was charged at 2 to 10% by weight,
Further, if necessary, an acid catalyst is charged at 0 to 1% by weight, and the acid catalyst is pumped out when the acid value becomes 25 or less. The charging order of the present invention is an example, and may be changed if necessary.

The compounds represented by the general formulas (5) and (6) among the fluorinated diluents (D) that can be used in the present invention will be described.

R ³ COOCH ₂ (CHOOCR ³ ) CH ₂ OOCR ³ (5) (R ³ COO) rR ² (6) wherein R ³ is an alkyl group or a perfluoroalkyl group of a fatty oil, and all R ³ is not an alkyl group at the same time, R ² is an aliphatic hydrocarbon residue having 2 to 10 carbon atoms, and r is an integer of 2 to 6.)

The compounds represented by the general formulas (5) and (6) can be obtained by transesterification of a fatty oil with a polyol [R ¹ (OH) r], followed by a reaction with a perfluoroalkylcarboxylic acid. Here, the fat oil is a natural fat oil having an iodine value of 130 or more and excluding a drying oil, for example, coconut oil,
Cottonseed oil, olive oil, safflower oil, sesame oil, rapeseed oil,
Soybean oil, fish oil, beef tallow and the like can be mentioned. These synthesis methods are based on the above-mentioned reaction method with a drying oil, a polyol and a perfluoroalkylcarboxylic acid.

Next, the compound represented by the general formula (7) among the diluents (D) of the present invention will be described. R ⁴ [COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ ] x (7) (wherein, R ⁴ is an optionally fluorinated aliphatic hydrocarbon residue or aromatic ring residue, and n is 0 to 15) And x represents an integer of 1 to 4.)

Compounds represented by the general formula (7) include aliphatic monocarboxylic acids (however, excluding unsaturated monocarboxylic acids having an iodine value of 130 or more), perfluoroalkylcarboxylic acids [CF ₃ (CF ₂ ) nCOOH], aliphatic polycarboxylic acid, aromatic monocarboxylic acid, aromatic polycarboxylic acid and 2
-With perfluoroalkyl ethanol in the presence of (or without) a catalyst such as sulfuric acid, para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.
It is obtained by an esterification reaction at a temperature of 0 to 220 ° C. Examples of the aliphatic monocarboxylic acid include carboxylic acids having 1 to 18 carbon atoms such as acetic acid, propionic acid, caproic acid, octylic acid, dodecylic acid, palmitic acid, and stearic acid. Examples of the aliphatic polycarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, and sebacic acid. Examples of the aromatic monovalent and polyvalent carboxylic acids include benzoic acid, tertiary butyl benzoic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid and the like.
Further, examples of the alicyclic carboxylic acid include tetrahydrophthalic anhydride, heptic acid, terpene maleic anhydride adduct and the like. Of the above, aliphatic carboxylic acids are preferred.

Next, the compound represented by formula (8) among the diluents (D) of the present invention will be described. R ⁵ [OOC (CF ₂₎ yCF _3] z (8) (wherein, R ⁵ is an aliphatic hydrocarbon residue, y is an integer of 0 to 15, z is an integer of 2-4.)

The compound of the general formula (8) can be produced by an ester reaction between a perfluoroalkylcarboxylic acid and a monohydric or polyhydric alcohol. These compounds are obtained by converting a perfluoroalkylcarboxylic acid and a monohydric or polyhydric alcohol with a catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or the like at a temperature of 50 to 220 ° C. It is esterified.

Perfluoroalkylcarboxylic acid [CF ₃
(CF ₂₎ nCOOH, n is an integer of 0 to 15. ]
As perfluoromethylcarboxylic acid, perfluoroethylcarboxylic acid, perfluoropropylcarboxylic acid, perfluorobutylcarboxylic acid, perfluoropentylcarboxylic acid, perfluorohexylcarboxylic acid, perfluorooctylcarboxylic acid, perfluorononylcarboxylic acid, perfluorodecylcarboxylic acid, perfluorododecyl Carboxylic acid, perfluorohexadecylcarboxylic acid and the like can be mentioned.

The monohydric or polyhydric alcohol includes, for example, methanol, ethanol, propanol, butanol,
Hexanol, octanol, decanol, dodecanol, cetyl alcohol, ethylene glycol, propylene glycol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol.

The fluorinated resin powder (E) used in the present invention is a powder of polyfluoroalkylene wax particles having a volume average particle diameter of 2 to 4 micrometers, and is made of polytetrafluoroethylene (PTFE). , Polyteorafluoropropylene (PTFP), polyhexafluoropropylene, and the like. The fluorinated resin powder is preferably contained in the coating composition of the present invention in an amount of 0.1 to 40% by weight.

Examples of the form in which the coating composition of the present invention is used include pigments 10 to 25 (% by weight) rosin-modified phenolic resins 20 to 35 alkyd resins 0 to 5 drying oils 0 to 25 solvents for printing inks 10 40 Fluorinated resin powder 0.1 to 40 Drying accelerator 0 to 3 Examples of printing inks composed of a composition comprising 0 to 10 other additives.

As the pigment, known general pigments, for example, benzidine yellow, lake red C, carmine 6B, phthalocyanine blue, carbon black, and, if necessary, an inorganic pigment or an extender pigment as a fluidity modifier are used.

In substantially producing a printing ink, it is customary to use a varnish obtained by dissolving the rosin-modified phenolic resin according to the present invention in a solvent (and / or drying oil). To prepare a varnish for printing ink, 100 parts of the resin is dissolved in a solvent (and / or drying oil) 50 to 15 parts.
Dissolve in 0 parts. It is also possible to use a gelling agent such as aluminum octylate, aluminum stearate, zirconium octylate, aluminum triisopropoxide, aluminum dipropoxide monoacetylacetonate on the varnish to use as a gel varnish.

Various additives such as a compound such as a friction resistance improver, an ink drier and a drying inhibitor are added to the printing ink, if necessary, and the printing ink is adjusted to have an appropriate viscosity, so that sheet offset can be achieved. It is an offset ink such as an ink or an off-wheel ink. This offset ink can be used as a normal printing ink using a fountain solution or as a printing ink for waterless lithographic printing without using a fountain solution. . Further, it can be used as news ink, stencil ink or letterpress ink.

Next, as a form in which the coating composition of the present invention is used, rosin-modified phenol resin 20 to 50 (% by weight) drying oil 0 to 30 solvent 10 to 60 fluorinated resin powder 0.1 to 40 drying Accelerators 1 to 5 OP varnishes composed of a composition comprising drying inhibitors 1 to 5 can be mentioned.

[0054]

Now, the present invention will be described with reference to specific examples. In the examples, "parts" indicates parts by weight. A. Example of synthesis of fluorinated drying oil In a reaction kettle, 880 parts of oil, 62 parts of glycerin, and 0.5 part of sodium methoxide were charged, and 20 parts were added under a nitrogen gas stream.
React at 0 ° C. for 4 hours. Thereafter, 846 parts of perfluorodecylcarboxylic acid were charged and reacted at 220 ° C. for 5 hours.
The reaction was completed when the acid value became 5 or less. Thereafter, the same reaction was performed.

[0055]

[Table 1]

(Synthesis Example of Dry Fatty Acid Fatty Acid Ester) A reaction kettle was charged with 280 parts of oil fatty acid and 564 parts of perfluorohexylethanol, and reacted at 200 ° C. for 8 hours under a nitrogen stream to conduct a reaction at an acid value of 5 or less. finished. The same procedure was performed as follows.

[0057]

[Table 2]

B. Synthesis Example of Fluorinated Rosin-Modified Phenolic Resin Production Example 1 (Synthesis of Resol-Type Phenolic Resin) 4-A flask with a stirrer, reflux condenser and thermometer
(2-Perfluorohexylethyl) phenol 310
Parts, 60 parts of p-formaldehyde and 100 parts of xylene, and heated and stirred while blowing in N2 gas.
Then, 4 parts of calcium hydroxide are dispersed in 10 parts of water, the resulting dispersion is added, the temperature is raised to 90 ° C., and the mixture is reacted at the same temperature for 6 hours. Thereafter, the mixture is cooled, neutralized with hydrochloric acid, and washed with water. This resol-type phenol resin solution is referred to as Comparative Example and Example Resole. Thereafter, the reaction is carried out in the same manner as in Table 3.

[0059]

[Table 3]

Production Example 2 (Synthesis of fluorinated rosin-modified phenolic resin) The rosin shown in Table 2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, heated and dissolved, and then heated to 200 ° C. Charge while adding the resole type phenol resin solution dropwise,
Incubate for 1-3 hours. Thereafter, the temperature is raised, and a polyol is charged at 250 ° C. and reacted at the same temperature until the acid value stops decreasing. Further, while dropping a liquid in which p-toluenesulfonic acid dissolved in a small amount of water is dispersed, the mixture is reacted until the decrease in the acid value stops. If necessary, polio
In some cases. Then, pump out.
The reaction is performed as shown in Table 4 below.

[0061]

[Table 4] The amount of resol in the table is the amount of solid content.

C. Synthesis example of fluorinated solvent (a) Synthesis example of transesterification reaction between fatty oil and perfluoroalkylcarboxylic acid 638 parts of coconut oil, 47 parts of glycerin and 0.5 part of sodium methoxide were charged into a reaction vessel and reacted at 200 ° C for 4 hours. I let it. Thereafter, 546 parts of perfluorohexacarboxylic acid were charged and the acid value was 5 at 200 ° C. for 5 hours.
The reaction was performed up to the following. The reaction was performed as shown in Table 5 below.

[0063]

[Table 5]

(B) Example of Synthesis of Carboxylic Acid and 2-Perfluoroalkylethanol A reaction vessel was charged with 116 parts of caproic acid and 912 parts of 2-perfluorohexadecylethanol, and then charged at 200 ° C. for 5 hours.
The reaction was performed until the acid value reached 5 or less. The reaction was performed as shown in Table 6 below.

[0065]

[Table 6]

(C) Example of synthesizing alcohols and perfluoroalkylcarboxylic acid 130 parts of octanol and 864 parts of perfluorohexadecylcarboxylic acid were charged into a reaction vessel, and reacted at 200 ° C. for 5 hours to an acid value of 5 or less. The reaction was carried out as shown in Table 7 below.

[0067]

[Table 7]

Since the rosin-modified phenol resin is solid, it is dissolved with a solvent and a drying oil to make it easy to use. 4 above resin
5% by weight, drying oil 14% by weight, solvent 40% by weight, ALC
1% by weight of H (a gelling agent manufactured by Kawaken Fine Chemicals Co., Ltd.) is charged into a reaction vessel and dissolved at 190 ° C. for 1 hour.
This is called varnish.

The following combinations were used to make varnishes and inks and evaluated. (1) Fluorinated drying oil / non-fluorinated resin / non-fluorinated diluent / fluorinated resin powder

[0070]

[Table 8]

[0071]

[Table 9]

(2) Non-fluorinated drying oil / fluorinated resin /
Non-fluorinated diluent / fluorinated resin powder

[0073]

[Table 10]

[0074]

[Table 11]

(3) Fluorinated drying oil / fluorinated resin / non-fluorinated diluent / fluorinated resin powder

[0076]

[Table 12]

[0077]

[Table 13]

(4) Fluorinated drying oil / non-fluorinated resin /
Fluorinated diluent / fluorinated resin powder

[0079]

[Table 14]

[0080]

[Table 15]

(5) Non-fluorinated drying oil / fluorinated resin /
Fluorinated diluent / fluorinated resin powder

(6) Fluorinated dry oil / fluorinated resin / fluorinated diluent / fluorinated resin powder

[0083]

[Table 16]

[0084]

[Table 17]

The test methods in the table were performed as follows. The inks in the table were used with Mitsubishi Heavy Industries Web Offset Press BT2-800NE
Printing was performed with O, and the rub resistance, blocking resistance, and printability were examined. (Friction Resistance) The printed matter of each varnish was rubbed 20 times with a 2 lb load using a Sutherland Lab tester, and the degree of scratching of the printed matter was indicated on a five-point scale. (Good) 5+ to -1 (Poor) (Blocking resistance) Twenty sheets of the above printed matter were piled up, 3 kg
After applying a load (per square centimeter) and standing at room temperature for 24 hours, the degree of blocking was indicated by a five-point scale. The notation is the same as the friction resistance. (Printability) The printing press has a dampening solution supply dial of -2.
A printing press capable of changing the amount of dampening water by changing the amount in a range of +2 (-2 is a state without water, 0 is an amount of water during normal printing, and +2 is an excessive amount). The test was expressed as a water width dial value. The water width is the value of the water supply dial when the amount of water is reduced and the amount of water is increased when the printed matter starts to become stained (ink is applied to the non-image area), and when the amount of water is increased Indicates the width of the water supply dial value when emulsification results in poor transfer, and the larger the range, the better. (Water repellency) Drop one drop of commercially available coffee on printed matter,
After the customs separation, the stickiness of the printed matter when wiped off with a cloth was indicated by a five-point scale. (Excellent) 5 + -1 (Poor)

[0086]

The fluorinated coating composition of the present invention has abrasion resistance, blocking resistance, printability, water repellency, rub resistance,
Wiping properties can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 161/04-161/16 C09D 11/00-11/20 C08G 8/00-8/38

Claims (8)

(57) [Claims] 1. A rosin comprising a rosin-modified phenolic resin (A), a drying oil (B) and / or a drying oil fatty acid ester (C), a diluent (D), and a fluororesin powder (E). A coating composition characterized in that at least one of the modified phenolic resin (A), the drying oil (B) and / or the drying oil fatty acid ester (C) and the diluent (D) contains a fluorinated component. 2. The coating composition according to claim 1, wherein the fluororesin powder is a polyfluoroalkylene. 3. The coating composition according to claim 1, wherein the drying oil (B) is a mixture of the fluorinated compounds represented by the general formulas (1) and (2). R ¹ COOCH ₂ (CHOOCR ¹ ) CH ₂ OOCR ¹ (1) (R ¹ COO) r R ² (2) (wherein, R ¹ is an alkyl group or a perfluoroalkyl group [CF ₃ (CF ₂ ) n of a drying oil] , N represents an integer of 0 to 15.], and all R ¹ are not simultaneously an alkyl group, R ² is an aliphatic chain residue having 2 to 10 carbon atoms, and r is 2 to 6 Represents an integer.) 4. The coating composition according to claim 1, wherein the drying oil fatty acid ester (C) is a fluorinated compound represented by the general formula (3). R ¹ COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ (3) (wherein, R ¹ is an alkyl group of a fatty acid in the drying oil, and n is 0 to 0)
Indicates an integer of 15. ) 5. The coating composition according to claim 1, wherein the phenol component of the rosin-modified phenol resin (A) is a fluorinated compound represented by the general formula (4). _{CF 3 (CF 2) n (} CH 2) m-φ-OH (4) ( wherein, phi is a phenylene group, n represents an integer of 0 to 15, m is an integer of 0 to 2.) 6. The diluent (D) is a mixture of fluorine compounds represented by the general formulas (5) and (6).
Or the coating composition of 2. R ³ COOCH ₂ (CHOOCR ³ ) CH ₂ OOCR ³ (5) (R ³ COO) rR ² (6) (wherein R ³ is an alkyl group or a perfluoroalkyl group of a fatty oil, and all R ³ are simultaneously R ² is an aliphatic hydrocarbon residue having 2 to 10 carbon atoms, and r is an integer of 2 to 6.) 7. The coating composition according to claim 1, wherein the diluent (D) is a fluorinated compound represented by the general formula (7). R ⁴ [COOCH ₂ CH ₂ (CF ₂ ) nCF ₃ ] x (7) (wherein, R ⁴ is an optionally fluorinated aliphatic hydrocarbon residue or aromatic ring residue, and n is 0 to 15) And x represents an integer of 1 to 4.) 8. The coating composition according to claim 1, wherein the diluent (D) is a fluorinated compound represented by the general formula (8). R ⁵ [OOC (CF ₂₎ yCF _3] z (8) (wherein, R ⁵ is an aliphatic hydrocarbon residue, y is an integer of 0 to 15, z is an integer of 2-4.)