JPS6241272A - Actinic energetic ray-curable coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled coating compsn. having excellent printability and adhesion to substrates, by blending a monomer contg. a radical- polymerizable double bond with a prepolymer derived from an epoxy compd. and (meth)acrylic acid. CONSTITUTION:A coating compsn. contains a prepolymer (A) obtd. by reacting acrylic acid and/or methacrylic acid with an epoxy compd., subjecting the reaction product contg. hydroxyl groups and a carboxylic acid anhydride to a half- esterification reaction and further reacting a monohydric alcohol with the product, a monomer (B) contg. a radical-polymerizable double bond and optionally, a radical polymn. initiator (C). The reaction of the epoxy resin with (meth) acrylic acid is carried out in a four-necked flask equipped with a stirrer at 70-130 deg.C while introducing air. When a compsn. having quick-curability is required, acrylic acid is preferred.

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 adhesion to substrates.

(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 varnishes, paints, adhesives, and photoresists. These are composed of a radically polymerizable upper polymer and a prepolymer, and if necessary, a radical polymerization initiator and a pigment, and the prepolymer is alkyd acrylate.
Polyester acrylate, epoxy acrylate, urethane-modified acrylate, etc., and as monomers,
Bisphenol A alkylene oxide adduct diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, alkylphenol alkylene oxide adduct monoacrylate, etc. were used.

Recently, printing and painting speeds have been increased, and in order to cope with this, active energy ray-curable coating compositions often use epoxy acrylate as a prepolymer, which cures quickly. However, epoxy acrylate has secondary hydroxyl groups and has little oil content, so it is used as a curable coating composition.

For example, when used in printing ink, it stains during printing.

Emulsification of ink often causes poor transfer.

Furthermore, the adhesion to the base material is also poor. For this reason, the actual situation is that the scope of application of these curable coating compositions 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.
We have now invented an active energy ray-curable coating composition that has excellent printability and adhesion to substrates.

That is, the present invention.

(A) A hydroxyl group-containing product obtained by reacting an epoxy compound with acrylic acid and/or methacrylic acid (hereinafter referred to as (meth)acrylic acid) is subjected to a Hafester reaction mainly with a carboxylic acid anhydride, and then reacted with a Sarani alcohol. Prepolymer.

(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 prepolymer (A) of the present invention, the epoxy compound refers to a glycidyl ether type epoxy resin having one or more epoxy groups in one molecule, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a linear aliphatic epoxy resin. , alicyclic epoxy resin, etc.

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, and glycidyl ethers obtained by adding water to them, as well as ε-caprolactone adducts of the above-mentioned glycidyl ether compounds, and glycidyl adducts of alkylene oxide adducts of bisphenol A, S, or F. ether, (alkyl)
Examples include phenol novolak glycidyl ether, glycol polyglycidyl ether of polyalkylene, 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. Furthermore, examples of glycidylamine type epoxy resins include triglycidyl isocyanate and the like. Also.

Linear aliphatic epoxy resins include epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, etc., and alicyclic epoxies include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate bis(3,4 epoxy, cyclohexyl), etc.

The reaction between the epoxy compound and (meth)acrylic acid is carried out, for example, in a four-hole flask equipped with a stirrer at a temperature of 70 to 130°C, preferably 80 to 115°C while blowing air. Additionally, amine compounds are used as catalysts.

Although epoxy groups may remain, it is desirable that they all be reacted with (meth)acrylic acid.

Furthermore, when a fast curing agent is required, it is desirable to use acrylic acid.

Hereinafter, the obtained product will be referred to as epoxy acrylate.

The Hafester reaction between the secondary hydroxyl group of the epoxy acrylate and the carboxylic anhydride is carried out at a temperature of 70 to 130"C at which the epoxy acrylate does not gel.

Preferably, it is carried out at 90 to 115°C for 1 to 4 hours.

The reaction ratio of the hydroxyl group-containing epoxy acrylate and the carboxylic anhydride is 0.1 to 1 mole of the carboxylic anhydride per hydroxyl group of the epoxy acrylate.

In addition, as carboxylic acid anhydrides, oxalic acid, malonic acid,
Aliphatic dicarboxylic acid anhydrides such as succinic acid, alkyl or alkenyl succinic acid, glutaric acid, maleic acid, 0-
(Water added) Phthalic acid, Himic acid.

Alicyclic or aromatic dicarboxylic acid anhydrides such as methylhimic acid, diphenic acid, naphthalic acid, etc. are used.

The method of reacting a monohydric alcohol with a carboxyl-containing reaction product produced by the Hafestel reaction is described in 70-1.
It is carried out at 30°C, preferably between 80 and 115°C, under reflux of an inert solvent. As the catalyst, an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid is used.

It is desirable that the reaction ratio be such that the number of carboxyl groups in Hafestel and the number of moles of monohydric alcohol are 1:0.9 to 1.1.

Single alcohols include aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, caprylic alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Alcohol, benzyl alcohol, alkylene oxide adduct of phenol which may be substituted with alkyl, aromatic alcohol such as alkylene oxide adduct of α or β naphthol or hydroxybenzophenone, cyclohexanol, tricyclodecane monomethylol or its alkylene oxide Examples include alicyclic alcohols such as adducts, rosin alcohols, and monocarboxylic acid esters with one hydroxyl group remaining of polyhydric alcohols (ethylene glycol, trimethylolpropane pentaerythritol, etc.). Monocarboxylic acids include formic acid,
Acetic acid, propionic acid, butyric acid.

Valeric acid, trimethylacetic acid, capron 1% t+n-
Heptanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, nonyl acid, coconut oil fatty acid, valmitic acid.

Aliphatic carboxylic acids such as stearic acid, oleic acid, linoleic acid, lylunic acid, etc., aromatic acids such as benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid, benzoylbenzoic acid, naphthoic acid, etc. Examples include group carboxylic acids, rosin, and water-added rosin. Further examples include esterification products of the aforementioned dihydric carboxylic acids and monohydric alcohols or esterification products with one alcoholic hydroxyl group remaining, (meth)acrylic acid, and the like.

Examples of the seven polymers having a radically polymerizable double bond (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, Capryl (meth)acrylate, Decyl (meth)acrylate, Lauryl (meth)acrylate, Myristyl (meth)acrylate,
Examples include monofunctional monomers such as cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylate of an alkylene oxide adduct of alkylphenol, and cyclohexyl (meth)acrylate. In addition, monomers with more than two functions include ethyl alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate. (
meth)acrylate, tripropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, petyl glycol di(meth)acrylate, pentyl glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypiparyl hydroxypylene parate di(meth)acrylate,
Hexanediol di(meth)acrylate (di)glycerin poly(meth)acrylate, (di)glycerin alkylene oxide poly(meth)acrylate,
trimethylolpropane tri(meth)acrylate,
Trimethylolpropane alkylene oxide tri(
meth)acrylate ditrimethylolpropane tetra(
meth)acrylate, ditrimethylolpropane alkylene oxide tetra(meth)acrylate, trimethylolethane tri(meth)acrylate ditrimethylolethane tetra(meth)acrylate, trimethylolethane alkylene oxide tri(meth)acrylate, ditrimethylolethane alkylene oxide tetra(meth)acrylate meth)acrylate, tetramethylolmethanetetra(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 ) acrylate, trihydroxybenzene alkylene oxide di(meth)acrylate, water-added bisphenol A
Di(meth)acrylate, water-added bisphenol F di(
meth)acrylate, water-added bisphenol A alkylene oxide adduct di(meth)acrylate, water-added bisphenol F alkylene oxide adduct di(meth)
Examples include acrylate. In addition, monomers of lactone adducts may be mentioned. Namely, 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(meth)acrylate Trimethylolpropane polylactonate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate.

Pentaerythritol polylactonate tetra (meth)
acrylate, each polyol lactonate polyacrylate such as dipentaerythritol polylactonate hexaacrylate. The above-mentioned lactone is a compound containing an ester functional group -CO-O- in the ring, such as T-butyrolactone, 8-valerolactone, and ε-caprolactone.

When using the coating composition 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 methyl ether,
Benzoin sensitizers such as benzoin ethyl ether, benzoin isopropyl ether, α-acrylic benzoin, and benzophenone.

Aryl ketone sensitizers such as p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl 0-benzoylbenzoate, acetophenone, 4,4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate.

dialkylaminoarylketone sensitizers such as p-dimethylaminoacetophenone, thioxanthone;

Examples include polycyclic carbonyl sensitizers such as xanthone and halogen-substituted products thereof, and these can be used alone or in appropriate combinations. These photosensitizers can be used in the composition in an amount of 1 to 30% by weight, preferably in a range of 0 to 15% by weight.

To prepare an active energy ray-curable ink composition, pigments are usually dispersed in the above-mentioned diluted varnish, but this method is not particularly limited and 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, an ink composition that does not use a pigment may also be used. Furthermore, it is also possible to use other resins in combination within a range that does not impede the effects of the present invention.

The present invention will be explained below using specific examples. All parts in the table indicate parts by weight.

Production example 1 Epicor! 71.7 parts of -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 while blowing air,
The reaction was carried out at 0°C, and after about 15 hours, when the acid value became 1 or less, it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer a.

Production Example 2 895 parts of DEN438 (Dow Chemical's Novola, Queboxy resin), 362 parts of acrylic acid, 1 part of triethylenediamine, and 1 part of hydroquinone were placed in four flasks equipped with a stirrer, and reacted at 100°C while blowing air to produce approximately After 18 hours, when the acid value became 1 or less, it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer b.

Production Example 3 380 parts of Epicor) 828, 130 parts of acrylic acid, 1 part of triethylenediamine, and 1 part of hydroquinone were placed in a fourth flask equipped with a stirrer, and while blowing air, 10 parts of
The reaction was carried out at 0°C, and after about 15 hours, when the acid value became 1 or less, 266 parts of dodecenyl succinic anhydride was added.1.
React for 5 hours and then add Avitol (Rika Percules)
363 parts of rosin alcohol), 5 parts of sulfuric acid, and 50 parts of cyclohexane were charged, and after about 16 hours, the acid value reached 15, so it was pumped out. The obtained radically polymerizable prepolymer is referred to as Prepolymer C.

Production Example 4 900 parts of Epicoat 1001 (epoxy resin manufactured by Yuka Shell Epoxy ■), 130 parts of acrylic acid, 1.5 parts of triethylenediamine, and 1.5 parts of hydroquinone were placed in four flasks equipped with a stirrer, and the mixture was heated for 10 minutes while blowing air.
The reaction was carried out at 0°C, and after about 15 hours, when the acid value became 1 or less, 304 parts of tetrahydrophthalic anhydride was charged, and 1
．． After reacting for 5 hours, hexyl 7)Ii mycol 1 fu, 7.5 parts of WE acid, and 75 parts of cyclohexane were added, and after about 14 hours, the acid value reached 12, so it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer d.

Manufacturing example 5 DEN438 895 parts, acrylic acid 362 parts.

Charge 2 parts of triethylenediamine and 2 parts of hydroquinone into 4 flasks with a stirrer, and add 1 part of triethylenediamine while blowing air.
After about 18 hours, when the acid value became 1' or less, 444 parts of phthalic anhydride was charged, and the mixture was reacted for 2 hours, followed by 354 parts of benzyl alcohol, p) 10 parts of luenesulfonic acid, 100 parts of cyclohexane was charged, and after about 16 hours, the acid value reached 12, so it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer e.

Production Example 6 696 parts of Adekasizer o-t3op (epoxidized soybean oil manufactured by Kadenka ■), 194 parts of acrylic acid, 1 part of triethylenediamine, and 1 part of hydroquinone were placed in four flasks equipped with a stirrer, and heated at 105°C while blowing air. After about 14 hours of reaction, when the acid value became 1 or less, 444 parts of phthalic anhydride was added.

After reacting for 2 hours, 534 parts of tricyclodecane monomethylol, 10 parts of sulfuric acid, and 100 parts of cyclohexane were added, and after about 14 hours, the acid value reached 16, so it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer f.

Production example 7 Bis(3,4 epoxycyclohexyl) adipate 42
0 parts, 130 parts of acrylic acid, 0 parts of triethylenediamine.
5 parts of hydroquinone and 0.5 part of hydroquinone were charged into four reflux stirrer-equipped flasks, and reacted at 105°C while blowing air. After about 10 hours, when the acid value became 1 or less, 100 parts of anhydrous succinic RL was charged. After 2 hours of reaction, 110 parts of cyclohexanol was added.

5 parts of sulfuric acid and 50 parts of cyclohexane were charged, and after about 14 hours, the acid value reached 13, so it was pumped out. The obtained radically polymerizable prepolymer is referred to as prepolymer g.

Next, an active energy ray-curable coating composition was prepared using the prepolymer prepared in the production example and monomers. It is described in Table 9-1 below.

Table-1 (Note-1) Monomer ABPE-4: Bisphenol A 4 mol ethylene oxide adduct diacrylate TMPTA: ) Limethylolpropane triacrylate TMPEOA: Trimethylolpropane 3 mol ethylene oxide adduct triacrylate photosensitizer = 4, 4-bis(diethylamino)benzophenone/benzophenone-215 Pigment: Fines Red F2 BW: Red pigment manufactured by Toyo Ink Manufacturing Co., Ltd. Example 1 Coating composition (printing ink) shown in Table 1, i.e. Comparative Example Sample 1 ,2. KORD example samples 4 to 8
Printed with Heidelberg, stains on non-printing areas during printing,
In water (Note 1) was measured (Table 2).

Table 2 (Note 1) 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 Next, the active energy ray curable coating shown in Table 1 was applied to T
Samples 1 to 2 and 4 to 8 were coated with various paints of alkyd resin, epoxy phenol resin, and acrylic resin on FSi, respectively, with an R tester of 30.
Printed with a coating weight of mg/100 cni.

For sample 3.9, apply 7 coats with a bar coater to each painted board.
0mg/100cn! It was painted with a coating amount of . Table-3
Samples 1-2.4-8 were placed on a conveyor 10 cm below two high-pressure mercury lamps having an intensity of 80 W/cm, and irradiated to cure them.

Sample 3.9 was cured by irradiation of 10 Mrad using a curtain beam type electron beam irradiation device. Table 3 below shows the results regarding the adhesion of each coating film obtained.

Table 3 Adhesion values indicate the remaining rate of the coating film in the cellophane tape peeling test.

"Effects of the Invention" The active energy ray-curable coating composition of the present invention was found in Example 1 compared to conventionally known coating materials. As shown in Example 2, the printing effect is good, the adhesion is excellent, and the range of application of the active energy ray-curable coating composition can be expanded.

Claims (1)

[Claims] 1. (A) A hydroxyl group-containing product obtained by reacting an epoxy compound with acrylic acid and/or methacrylic acid is mainly subjected to a half-ester reaction with a carboxylic acid anhydride, and further reacted with a monohydric alcohol. An active energy ray-curable coating composition comprising: (B) a monomer having a radically polymerizable double bond; and (C) a radical polymerization initiator if necessary.