JPH0813953B2 - Active energy ray curable coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Object of the Invention" (Field of Industrial Application) The present invention relates to an active energy ray-curable coating composition, and more specifically, it is cured by irradiation with ultraviolet rays or electron beams, and The present invention relates to an active energy ray-curable coating composition excellent in printability and the like.

(Prior Art) In recent years, active energy ray curable coating compositions have been extensively researched, and among them, practical application is progressing in the fields of printing inks, clear varnishes, paints, adhesives and photoresists. ing. These are composed of radically polymerizable monomers and prepolymers having radical polymerizability, and optionally radical polymerization initiators and pigments. As prepolymers, alkyd acrylate, polyester acrylate, epoxy acrylate, urethane modified acrylate, etc. As the monomer, bisphenol A alkylene oxide adduct diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol hexaacrylate, alkylphenol alkylene oxide adduct monoacrylate, etc. are used. It was being done.

However, when a curable coating composition using these compounds is used for a printing ink, for example, a transfer failure often occurs due to stains during printing and emulsification of the ink. Therefore, it is the actual situation that the application range of these curable coating compositions is narrowed.

"Structure of the Invention" (Means for Solving Problems) The present invention has been conducted as a result of intensive research to improve these drawbacks.
The inventors have invented an active energy ray-curable coating composition having excellent printability and the like. That is, the present invention relates to (A) an alkyd resin obtained by subjecting a polyhydric alcohol, a polyvalent carboxylic acid containing at least pentadecenylsuccinic acid or an anhydride thereof and a monovalent carboxylic acid to an esterification reaction, and (B) The present invention relates to an active energy ray-curable coating composition containing a monomer having a radical-polymerizable double bond.

The present invention is described in detail. Generally, an alkyd resin is a polyhydric alcohol in which a polyvalent carboxylic acid as a cross-linking agent and a monovalent carboxylic acid as a modifier are subjected to an esterification reaction. In addition, pentadecenyl succinic anhydride is used.

As the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexanediol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane , Terramethylolmethane, dipentaerythritol, polycyclopentadiene diallyl alcohol copolymer, spiroglycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F
Examples thereof include ethylene oxide adduct, bisphenol F propylene oxide adduct (the number of moles of alkylene oxide added is usually 1 to 2 mol per 1 hydroxyl group of bisphenol), water-added bisphenol A, water-added bisphenol F and the like.

It should be noted that addition of alkylene oxide to bisphenols is carried out by adding bisphenols in the autoclave,
About 0.5% by weight of sodium hydroxide as a catalyst (based on the total amount of alkylene oxide included) was charged.
It was gradually poured an alkylene oxide, 160 ° C., and reacted at 5 kg / cm ² or less, and ending at a gauge pressure of 0.1 kg / cm ² or less.

When pentadecenyl succinic acid or its anhydride is further used as a polycarboxylic acid, the polycarboxylic acid to be used in combination, that is, the organic compound having two or more carboxyl groups is oxalic acid, malonic acid, or succinic acid. Acid, dodecenyl succinic acid, glital acid, maleic acid or their acid anhydrides, fumaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, OSK-DASL-12, OSK-DA
SL-20, OSK-DASB-12, OSK-DASB-20, OSK-DAUL-20, O
SK-DAUB-20 (OSK series is Okamura Oil (manufactured) long chain dibasic acid), aliphatic dicarboxylic acids such as linseed oil fatty acid and tung oil fatty acid dimer acid, o-phthalic acid, water-added o-phthalic acid, Hymic acid, methylhymic acid, diphenic acid, trimellitic acid, pyromellitic acid, naphthalic acid,
Benzophenone tetracarboxylic acid and their acid anhydrides, isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid, prenitic acid, melophanoic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, homophthalic acid, ompphenylenediacetic acid, o-phenylene Examples thereof include aromatic polycarboxylic acids such as acetic acid-β-propionic acid and dimer acid of rosin.

Examples of monovalent carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, n-heptanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, coconut oil fatty acid, palmitic acid, stearic acid,
Aromatic carboxylic acids such as aliphatic carboxylic acids such as oleic acid, linoleic acid and linolenic acid, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid, benzoylbenzoic acid and naphthoic acid , Rosin, and water-added rosin. Further, there is an esterified product of the above-mentioned divalent carboxylic acid and an esterified product in which a monohydric alcohol or one alcoholic hydroxyl group remains.

In addition, as monohydric alcohol, methyl alcohol,
Ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, capryl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and other aliphatic alcohols, benzyl alcohol, phenol, alkylphenol Examples thereof include aromatic alcohols such as adducts of alkylene oxides, cyclohexanol, rosin alcohol, and water-added rosin alcohol. The esterified product having one alcoholic hydroxyl group left is an esterified product with the monovalent carboxylic acid described above.

 Next, the reaction method will be described.

Stirrer 4-neck flask with polyhydric alcohol, polyhydric carboxylic acid, monovalent carboxylic acid functional group ratio (OH / COOH group ratio) 0.5 ~
Charge between 2.0 and, if necessary, add an inert reaction solvent, and while blowing an inert gas such as nitrogen or carbon dioxide, at a reaction temperature of 80 to 300 ° C, preferably 150 to 260 ° C, 90% of the theoretical amount. Let them react. It is better to follow the reaction by acid value.

In addition, when a monovalent carboxylic acid is a monovalent carboxylic acid having a radical double bond, such as (meth) acrylic acid, sorbic acid, cinnamic acid, vinyl acetic acid, and crotonic acid, polyhydric alcohol and polyvalent carboxylic acid are reacted. The reaction is carried out at 80-120 ℃ with the residual OH compound obtained by the esterification reaction of acid and monovalent carboxylic acid. At that time, hydrochloric acid, sulfuric acid, P
-Use a reaction catalyst such as toluene sulfonic acid or a polymerization inhibitor such as hydroquinone.

The coating composition of the present invention contains, in addition to the resin (A), one or more other prepolymers or monomers (B) having a radically polymerizable double bond, if necessary.
The monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth). Acrylate, capryl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, alkylene oxide addition of alkylphenol Examples thereof include monofunctional monomers such as (meth) acrylate and cyclohexyl (meth) acrylate. Further, as a bifunctional or higher functional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol (meth) Acrylate, neopentyl glycol di (meth) acrylate, hydroxypiparyl hydroxypivalate di (meth) acrylate, hexanediol di (meth) acrylate, (di) glycerin tri (meth) acrylate, diglycerin alkylene oxide tetra (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolpropane alkylene oxide tri (meth) acrylate, ditrimethylolpropane Pantetra (meth) acrylate, ditrimethylolpropane alkylene oxide tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolethane tri (meth) acrylate, trimethylolethane alkylene oxide tri (meth) acrylate, ditrimethylolethane alkylene Oxide tetro (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, dihydroxybenzene alkylene oxide di (Meth) acrylate, trihydroxybenzene alkylene oxide di ( Data) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate,
Examples thereof include water-added bisphenol A alkylene oxide adduct di (meth) acrylate and water-added bisphenol F alkylene oxide adduct di (meth) acrylate. Other examples include lactone adduct monomers. That is, polyethylene glycol polylactonate di (meth) acrylate, polypropylene glycol polylactonate di (meth) acrylate, alkylene glycol polylactonate di (meth) acrylate, glycerin polylactonate tri (meth) acrylate, diglycerin polylactonate Tetra (meta)
Acrylate, trimethylolpropane polylactonate tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol polylactonate tetra (meth) acrylate, dipentaerythritol polylactonate hexaacrylate, and other polyol lactonate polyacrylates Is. The lactone of the above-mentioned monomer is a compound containing in the ring a functional group —CO—O— of an ester such as γ-butyrolactone 8-valerolactone, ε-caprolactone.

In the use of the coating agent of the present invention, when the active energy ray is ultraviolet light, it is necessary to add a photosensitizer having a radical polymerization initiation function, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. , Α-Acrylicbenzoin and other benzoin sensitizers, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, o-benzoylmethyl benzoate, acetophenone and other alurketone sensitizers, 4,4- Dialkylamino aryl ketone sensitizers such as bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate and p-dimethylaminoacetophenone, and polycyclic carbonyl sensitizers such as thioxanthone, xanthone and halogen-substituted compounds thereof. These can be used alone or in an appropriate combination. These photosensitizers can be used in the composition in an amount of 1 to 30% by weight, preferably 1 to 15% by weight.

Further, the resin of the present invention (A) is combined with a drying oil, paraffin, olefin, aromatic solvent or the like to perform thermal polymerization,
It can also be used in an oxidative polymerization type.

To prepare an active energy ray-curable ink composition, a pigment is usually dispersed in the above-mentioned diluted varnish, but this method is not particularly limited, and it can be carried out by a conventional dispersion method such as three rolls or ball mill. it can. Also organic
In addition to the inorganic and extender pigments, if necessary, a plasticizer, a surfactant, a thermal polymerization inhibitor, etc. can be added. Of course, there may be an ink composition containing no pigment. Further, other resins can be used in combination within the range that does not impair the effects of the present invention.

The present invention will be described below with reference to specific examples. All parts in the examples are parts by weight.

Production Example-1 Trimethylolpropane 268 parts Phthalic anhydride 148 parts Toluene 20 parts were charged into a four-necked stirrer flask and charged under a nitrogen gas stream to 200
The reaction was carried out at ℃ for 5 hours and the acid value became 4.8, so it was cooled and charged with 0.6 parts of hydroquinone and 6 parts of p-toluenesulfonic acid and charged with 260 parts of acrylic acid while blowing air.
After 0 hours, the acid value reached 9.9, so the solvent was removed and drained.

 This is designated as resin a.

Production Example-2 Trimethylolpropane 268 parts Pentadecenyl succinic anhydride 310 parts Toluene 25 parts were charged into a four-necked stirrer flask and charged under a nitrogen gas stream to 200
After reacting at ℃ for 5 hours, the acid value became 4.9, it was cooled and charged with 0.7 parts of hydridoquinone and 7 parts of p-toluenesulfonic acid and 260 parts of acrylic acid while blowing air,
The acid value became 9.8 after 10 hours at ℃, so the solvent was removed and drained.

 This is designated as resin b.

Production Example-3 Glycerin 148 parts Succinic acid 118 parts o-Benzoylbenzoic acid 813 parts Toluene 75 parts Charged to a four-necked stirrer flask with a nitrogen gas stream for 200
After reacting for 11 hours at ℃, the acid value reached 4.7, so the solvent was removed and drained.

 This is designated as resin c.

Production Example-4 Glycerin 184 parts Pentadecenyl succinic acid 328 parts o-Benzoylbenzoic acid 813 parts Toluene 75 parts Charged to a four-necked stirrer flask under a nitrogen gas stream to 200
After reacting for 11 hours at ℃, the acid value became 4.8.

 This is designated as resin d.

Production Example-5 Pentaerythritol 272 parts Isophthalic acid 166 parts Water-added rosin 990 parts Toluene 70 parts Charged to a four-necked stirrer flask with a nitrogen gas stream for 200
The reaction was carried out at ℃ for 10 hours and the acid value became 4.0. After cooling, 1.3 parts of hydroquininone and 13 parts of p-toluenesulfonic acid were charged, and 194 parts of acrylic acid was charged while blowing air,
After 9 hours at 0 ° C., the acid value became 9.8, so the solvent was removed and drained.

 This is designated as resin e.

Production Example-6 Pentaerythritol 272 parts Pentadecenyl succinic anhydride 310 parts Water-added rosin 990 parts Toluene 75 parts Charged to a 4-necked stirrer flask under a nitrogen gas stream to 200
After reacting at ℃ for 10 hours, the acid value became 4.5 or less, so cool down,
Hydroquinone 1.6 parts, P-toluene sulfonic acid 16 parts were charged, and acrylic acid 194 parts were charged while blowing air 100
After 9 hours at ℃, the acid value became 9.7, so the solvent was removed and drained.

 This is designated as resin f.

Next, an active energy ray-curable coating composition was prepared using the above resin and monomer.

 The weight average molecular weight and the formulation of the composition are shown in the table below.

Example 1 The coating composition (printing ink) shown in Table 1, that is,
Comparative Samples 1 to 4 and Example Samples 5 to 8 were printed by KORD Heidelberg, and stains on the non-image area at the time of printing and water width (Note-2) were measured (Table-2).

The lower limit number in the table represents the amount of water that was contaminated when the amount of water was reduced. Also, the upper limit number represents the amount of water that became poorly transferred due to emulsification of the ink when the amount of water was increased.

Example-2 The coating composition printed in Example-1 was used as Comparative Example Sample 1
.About.3, Example Samples 5 to 7 were placed on a conveyor 10 cm below two high pressure mercury lamps having an intensity of 80 W / cm.
Irradiated at 100 m / min. For the comparative sample 4 and the example sample 8, a curtain beam type electron beam irradiation apparatus was used to
Irradiated with rad. Both were hardened.

〔The invention's effect〕

The active energy ray-curable coating composition of the present invention has a better printing effect as shown in Examples 1 and 2 as compared with the conventionally known coating agents, and the active energy ray-curable coating composition The range of application can be expanded.

Claims (1)

[Claims] 1. An alkyd resin obtained by subjecting (A) a polyhydric alcohol, a polyvalent carboxylic acid containing at least pentadecenylsuccinic acid or an anhydride thereof and a monovalent carboxylic acid to an esterification reaction, and (B) a radical. An active energy ray-curable coating composition containing a monomer having a polymerizable double bond.