JPH01123873A - Actinic radiation-curable coating composition - Google Patents

Abstract

PURPOSE:To obtain the above composition which can be cured by irradiation with, e.g., ultraviolet rays and is excellent in printability, by mixing a resin obtained by thermally polymerizing an ester compound of an epoxy compound with a specified monocarboxylic acid with a monomer having a radical- polymerizable double bond and, optionally, a radical polymerization initiator. CONSTITUTION:A resin (A) is obtained by thermally polymerizing a product obtained by esterifying an epoxy compound (a) such as a glycidyl ether epoxy resin having at least one epoxy group in the molecule with a radical- polymerizable double bond-containing monocarboxylic acid or its mixture with a monocarboxylic acid having no radical-polymerizable double bond at a ratio of 0.1-1mol. of component B to one epoxy group in the presence of, optionally, a thermal polymerization initiator. 5-60pts.wt. resin A is mixed with 95-40pts. wt. monomer having a radical-polymerizable double bond (B) such as trimethylolpropane alkylene oxide tri(meth)acrylate and 1-30wt.%, based on the composition, radical polymerization initiator.

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 furthermore, The present invention relates to an active energy ray-curable coating composition that has excellent printability and the like.

(Prior Art) In recent years, research on coating compositions curable with active energy rays has been actively conducted, and among them, printing inks,
Practical applications are progressing in fields such as clear faces, paints, adhesives, and photoresists. These are composed of radically polymerizable monomers and prepolymers that have radical polymerizability, and if necessary, radical polymerization initiators and pigments.The prepolymers include alkyd acrylate, alkyd acrylate,
Polyester acrylates, epoxy acrylates, urethane-modified acrylates, etc., and when fast curing is required, bisphenol A alkylene oxide adduct diacrylates are used as the 7-mer.

Neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, dipentaerythritol hexaacrylate alkylphenol alkylene oxide adduct monoacrylate, etc. were used.

However, when a curable coating composition using these compounds is used as a printing ink, for example, poor transfer often occurs due to staining during printing and emulsification of the ink.

This is thought to be due to the low molecular weight of the resin in the active energy ray-curable coating composition. Therefore, the actual situation is that the scope of application of these curable coating materials has been narrowed.

"Structure of the Invention" (Means for Solving Problems) The present invention has been developed as a result of intensive research to improve these drawbacks.
Excellent curability and printability. This led to the invention of an active energy ray-curable coating.

Namely.

(A) A resin obtained by thermally polymerizing a product obtained by esterifying an epoxy compound and a monocarboxylic acid containing a monocarboxylic acid having a radically polymerizable double bond, using a thermal polymerization initiator as necessary. .

(B) Monomer having a radically polymerizable double bond.

(C) A radical polymerization initiator if necessary.

The present invention relates to an active energy ray-curable coating composition comprising:

In the resin of the present invention (A), the epoxy compound is a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, or a glycidyl amine type epoxy resin having one or more epoxy groups in one molecule.

These include linear aliphatic epoxy resins and alicyclic epoxy resins.

Examples of glycidyl ether type epoxy resins include bisphenol A diglycidyl ether, bisphenol A di-
β-methyl glycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ε-caprolactone adduct of the above glycidyl ether compound, glycidyl ether of alkylene oxide adduct of bisphenol A, S or F, (alkyl)phenol novolac glycidyl Examples include ether, polyalkylene glycol polyglycidyl ether, and epoxy urethane resin. Further, as glycidyl ester type epoxy resins, there are dibasic acid diglycidyl esters such as phthalic acid, adipic acid, and dimer acid, and tribasic acid triglycidyl esters such as trimellitic acid. In addition, triglycidyl isocyanate and the like are examples of glycidylamine type epoxy resins.

In addition, linear aliphatic epoxy resins include epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, etc., and alicyclic epoxies include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis( 3,4 epoxy, cyclohexyl)
etc. can be mentioned.

Furthermore, the -valent carboxylic acid essentially includes one carboxylic acid having a radically polymerizable double bond.

Therefore, there are only -valent carboxylic acids having a radically polymerizable double bond, one carboxylic acid having a radically polymerizable double bond, and one carboxylic acid having no radically polymerizable double bond.

Single carboxylic acids having radically polymerizable double bonds include (meth)acrylic acid, sorbic acid, vinyl acetic acid,
These include crotonic acid, cinnamic acid, oleic acid, linoleic acid, linuric acid, linseed oil fatty acid, and dehydrated castor oil fatty acid.

Single carboxylic acids without radically polymerizable double bonds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, n-mebutanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, and coconut oil fatty acid. ,
Palmitic acid, stearic acid.

Aliphatic carboxylic acids such as oleic acid, linoleic acid, luronic acid, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid,
Examples include aromatic carboxylic acids such as benzoylbenzoic acid and naphthoic acid, rosin, and water-added rosin. Furthermore, there is an esterified product of the above-mentioned dihydric carboxylic acid, a -hydric alcohol or one alcoholic hydroxyl group, and an esterified product in which the -hydric alcohol or one alcoholic hydroxyl group remains.

- As the alcohol, methyl alcohol is used.

Ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol.

Hexyl alcohol, octyl alcohol, caprylic alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol.

Aliphatic alcohols such as stearyl alcohol, aromatic alcohols such as benzyl alcohol, phenol, alkylene oxide adduct 1 of alkylphenol, cyclohexanol, rosin alcohol.

Examples include water-added rosin alcohol. Moreover, the esterified product with one alcoholic hydroxyl group remaining is the esterified product with the monohydric carboxylic acid described above.

For example, the reaction between an epoxy compound and a monocarboxylic acid is as follows:
-(meth)acrylic acid as the carboxylic acid.

In reactions using sorbic acid, vinyl acetic acid, and cinnamic acid,
The reaction is carried out in a four-roof flask equipped with a stirrer at a temperature of 70 to 130°C, preferably 80 to 120°C while blowing air.

Further, a catalyst such as an amine compound and a polymerization inhibitor such as hydroquinone are used. The reaction ratio is 0.1 to 1 mole per epoxy group of the epoxy compound. The reaction with oleic acid, linoleic acid, linuric acid, linseed oil fatty acid, dehydrated castor oil fatty acid, and saturated carboxylic acid is carried out at 80 to 260° C. in a four-hole flask equipped with a stirrer. Further, an amine compound catalyst can also be used. The reaction ratio is 0.1 to 1 mole per epoxy group of the epoxy compound. Furthermore, in order to react with the secondary hydroxyl group generated at that time, 170 to
The reaction is carried out at 260°C, and a reaction solvent such as toluene or xylene is used as necessary. Further, when (meth)acrylic acid, sorbic acid, vinyl acetic acid, and cinnamic acid are contained, the reaction is carried out at a temperature of 80 to 120°C while blowing air.

The obtained esterification reaction product is thermally polymerized at 80 to 200°C. A thermal polymerization initiator can also be used if necessary.

As a thermal polymerization initiator, benzoyl peroxide peroxide and tetramethylthiuram disulfide are used.

Examples include azobisisobutyronitrile. Note that the drying oil fatty acid may be oxidatively polymerized at 180 to 280°C while blowing air.

Monomers of the present invention (B) 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 Caprylic (meth)acrylate, Decyl (meth)acrylate, Lauryl (meth)acrylate Myristyl (meth)acrylate, Cetyl (meth)acrylate, Stearyl (meth)acrylate, Benzyl (meth)acrylate, Alkylene oils of alkylphenols Examples include monofunctional monomers such as side adducts (meth)acrylate and cyclohexyl (meth)acrylate. Furthermore, as monomers with more than two functionalities, 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, dipropylene glycol di(meth)acrylate,
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, hydroxybiparyl Hydroxypiparate 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 tetra(
meth)acrylate, ditrimethylolpropane alkylene oxide tetra(meth)acrylate Trimethylolethanetri(meth)acrylate, ditrimethylolethanetri(meth)acrylate, trimethylolethanealkyleneoxidetri(meth)acrylate, ditrimethylolethanealkyleneoxidetetra(meth)acrylate meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxybi di(meth)acrylate.

Dihydroxybenzene alkylene oxide di(meth)
Acrylate, trihydroxybenzene alkylene oxide di(meth)acrylate water added bisphenol A
Di(meth)acrylate, water-added bisphenol F di(
Examples include meth)acrylate water-added bisphenol A alkylene oxide adduct di(meth)acrylate, water-added bisphenol F alkylene oxide adduct di(meth)acrylate, and the like. In addition, monomers of lactone adducts may be mentioned. That is, polyethylene glycol polylactonate di(meth)acrylate,
Polypropylene glycol borylactonate di(meth)
Acrylate, alkylene glycol polylactonate di(meth)acrylate, glycerin polylactonate tri(meth)acrylate, diglycerin polylactonate tetra(meth)acrylate.

Each polyol lactonate polyacrylate such as trimethylolpropane polylactonate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol polylactonate tetra(meth)acrylate, dipentaerythritol polylactonate hexaacrylate, etc. . In addition, the lactone of the above monomer is a functional group -C of an ester such as T-butyrolactone 8-va, lerolactone, and ε-caprolactone.
It is a compound containing O-O- in the ring.

Also, what is the ratio of these monomers to the resin (A)?

95-4075-60 (weight ratio).

When using the coating material of the present invention, when the active energy ray is ultraviolet rays, it is necessary to add a photosensitizer, that is, a radical polymerization initiator (also a radical polymerization accelerator) (C), and benzoin, benzoin Benzoin sensitizers such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-acrylic benzoin,
Benzophenone, p-methylbenzophenone, p-chlorobenzophenone.

Ketone-based sensitizers such as tetrachlorobenzophenone, methyl 0-benzoylbenzoate, and acetophenone, 4
．． 4-bisdiethylaminobenzophenone.

Examples include dialkylaminoaryl ketone sensitizers such as isoamyl p-dimethylaminobenzoate and p-dimethylaminoacetophenone, and polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products, and these may be used alone or as appropriate. They can also be used in combination. These photosensitizers can be used in the composition in an amount of 1 to 30% by weight, preferably 0 to 15% by weight.
A range of % by weight is desirable.

In order to obtain an active energy ray-curable ink composition, pigments are usually dispersed in the above-mentioned dilution phase, but this method is not particularly limited, and it can be carried out by a conventional dispersion method such as a three-roll mill or a ball mill. can. In addition to the organic and inorganic extender pigments, plasticizers, surfactants, thermal polymerization inhibitors, and the like can be added as necessary. Of course, there may be ink compositions that do not use pigments. Furthermore, it is also possible to use other resins in combination within a range that does not impede the effects of the present invention.

Production examples and examples are shown below, and numbers indicate parts by weight.

Production Example 1 71.7 parts of Ebiko) 828 (epoxy resin manufactured by Yuka Shell Epoxy ■), 28.3 parts of acrylic acid, 0.1 part of triethylenediamine, and 0.1 part of hydroquinone were placed in four flasks equipped with a stirrer, and air 1 while blowing
The reaction was carried out at 00°C, and after about 15 hours, when the acid value became 1 or less, it was pumped out.

This will be referred to as resin a.

Production example 2 Epicor) 828 (epoxy resin manufactured by Yuka Shell Epoxy ■) 71.7
Part acrylic acid 14.2
Part propionic acid 14.1
Part triethylenediamine 0.1 part Hydroquinone 0.1 part were added to 4 flasks with a stirrer while blowing air into 10 parts.
The reaction was carried out at 0°C for 15 hours, and the acid value became 1.

Furthermore, add 0.3 parts of benzoyl peroxide and heat at 100°C.
It was allowed to react for an hour and then pumped out.

Let's call this a resin.

Production example 3 DEN43B (Dow Chemical Novolac epoxy #M
fat) 895 parts nonyl acid
144 parts triethylenediamine 1.5 parts hydroquinone
1.5 parts were reacted at 100° C. for 14 hours while blowing air into a four-roof flask equipped with a stirrer, and when the acid value reached 2, it was pumped out.

This will be referred to as resin C.

Production Example 4 DEN43B (Dow Chemical Novola Soque Evoxy Resin) 895 parts Acrylic acid 144 parts Nonyl acid 474 parts Triethylenediamine 1.5 parts Hydroquinone 1.5 parts were heated to 100°C while blowing air into 4 flasks with a stirrer.
After a period of reaction, the acid value became 2.

Furthermore, add 4.5 parts of azobisisobutyronitrile and
The mixture was reacted at 00°C for 3 hours and then pumped out.

This will be referred to as resin d.

Production example 5 Bis(3,4 epoxycyclohexyl) adipate 42
0 parts Linseed oil fatty acid 420 parts Water-added rosin 495 parts Triethylenediamine 1.5 parts Hydroquinone 1.5 parts were placed in four flasks equipped with a stirrer, and heated at 150°C under a nitrogen stream.
Allow time to react. After that, the temperature was raised to 240℃ for 10 hours,
Since the acid value was 5, the solvent was removed.

I pumped it out.

This will be referred to as resin e.

Production example 6 Bis(3,4 epoxycyclohexyl) adipate 42
0 parts Linseed oil fatty acid 420 parts Water-added rosin 495 parts Triethylene diamine 1.3 parts were placed in a four-bottle flask with a stirrer, and while blowing air, the mixture was heated to 150 parts.
Incubate at ℃ for 1 hour. After that, the temperature was increased and air was continued to be blown to 240℃ for 10 hours.

The acid value reached 5, so I pumped it out.

This is referred to as resin f.

Next, the resin made in the production example was subjected to high performance liquid chromatography (
The weight average molecular weight was measured using C, PC determination). In addition, active energy ray-cured wave AM products were produced using the above resin and Molmer.

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

(Left below) (Note-1) Monomer AB used in Production Example 1 composition formulation
PE-4: Bisphenol A 4 mole ethylene oxide adduct diacrylate TMPTA: l-rimethylolpropane triacrylate TMPEO/I: ) Dimethylolpropane 3 mole ethylene oxide adduct triacrylate TMMTA: Tetramethylolmethane tetraacrylate photosensitizer: 4,4-bis(diethylamino)benzophenone/benzophenone-215 Pigment: Fines Resodo F2BW: Toyo Ink Manufacturing■
Red Pigment Example 1 The coating composition (printing ink) shown in Table 1, that is, Comparative Samples 1 to 4. KORD example samples 5 to 8
Printed with Heidelberg, stains on non-printing areas during printing,
Measured in water (Note-2).

On the other hand, in Examples 5 to 8, all correspond to Comparative Examples 1 to 8.
4 (Comparative Example 1 and Example 5 correspond).

No staining was observed even when the number of sheets was about 5 times or more.

(Note-2) Underwater: Measured by installing a device to control the amount of dampening water in the printing press. The numbers are scales that represent the amount of dampening water, and there is no specific unit.

The lower limit number in the table represents the amount of water in which stains were generated when the amount of water was decreased. Further, the upper limit number represents the amount of water at which the ink becomes emulsified and poor transfer occurs when the amount of water is increased.

Example 2 The coating composition printed in Example-1 was used as comparative sample 1 to
3. Examples Samples 5 to 7 were irradiated with two high-pressure mercury lamps having an intensity of 80 W/port at 100 m/min by placing them on a conveyor. Comparative Example Samples 4.
Example sample 8 was irradiated at 3 Mr ad using a curtain beam type electron beam irradiation device. Both were hardened.

"Effects of the Invention 1 The active energy ray-curable coating composition of the present invention has better printing effects than conventionally known coatings, as shown in Examples 1 and 2. The range of application of the cured coating composition can be expanded.

Claims (1)

[Claims] 1. (A) A product obtained by esterifying an epoxy compound and a monovalent carboxylic acid containing a monovalent carboxylic acid having a radically polymerizable double bond, if necessary, using a thermal polymerization initiator. An active energy ray-curable coating composition comprising: (B) a monomer having a radically polymerizable double bond; (C) a radical polymerization initiator if necessary; .