JPH02189371A - Active energy ray-curable resin composition and printing ink composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Object of the Invention] (Industrial Field of Application) The present invention relates to active energy ray-curable resin compositions, and particularly coating compositions and printing ink compositions that are cured by irradiation with ultraviolet rays or electron beams. The present invention relates to a resin composition useful for products.

(Prior art) In recent years, research has been actively conducted on coating compositions that can be cured by active energy rays, and practical applications are progressing in the fields of printing inks, clear coats, paints, adhesives, photoresists, etc. ing. These are composed of radically polymerizable resins and monomers, as well as radical polymerization initiators and pigments as necessary. Examples of radically polymerizable resins include alkyd (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate. ) acrylate, urethane-modified (meth)acrylate, etc. Monomers include bisphenol A alkylene oxide adduct di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetra Methylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkylphenol alkylene oxide adduct mono(meth)acrylate, etc. were used.

In this specification, (meth)acrylate refers to acrylate and/or methacrylate, and (meth)acrylic acid refers to acrylic acid and/or methacrylic acid.

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. Therefore, the actual situation is that the scope of application of these curable coatings has been narrowed.

To solve this problem, some attempts have been made to improve printability by using a vehicle in which Epon ester or diallyl phthalate polymer, which is solid at room temperature, is dissolved in a monomer or prepolymer having a radical double bond. There are still problems that need to be solved regarding dirt.

(Problems to be Solved by the Invention) The present invention provides an active energy ray-curable resin composition and a printing ink composition using the same, which particularly solves the problems of staining and poor transfer during printing as described above. be.

"Structure of the Invention" (Means for Solving the Problems) The present invention provides an alkylated tetrahydrophthalic anhydride or hexahydrophthalic anhydride whose alkyl groups have a total number of carbon atoms of 2 to 18, or an acid anhydride thereof (a ) and an active energy ray-curable resin composition in which acrylic acid or methacrylic acid is reacted with an esterified product (A) obtained by reacting an acid component containing polyhydric alcohol with an excess of OH groups, and the resin composition. An active energy radiation curable printing ink composition is provided, comprising the active energy radiation curable printing ink composition as a vehicle component.

The acid component (a) above is a compound represented by (1) or (11) below or an acid anhydride thereof.

Alternatively, it is an alkyl group, and the total number of carbon atoms in the alkyl group is 2 to 18. ) In the present invention, the ester compound (A) contains a polyhydric alcohol, and is further esterified with a polyhydric carboxylic acid as a crosslinking agent and a partially carboxylic acid as a modifier with an excess of OH groups. The compound (a) is used as part or all of this polyhydric carboxylic acid. This ester compound (A) is further imparted with crosslinkability by irradiation with active energy rays by subjecting acrylic acid or methacrylic acid to an esterification reaction.

The polyhydric carboxylic acid of the ester compound (A) in the present invention contains the above-mentioned compound (a) or its anhydride as an essential component. The total number of alkyl groups is preferably 2 to 18. If the total number of alkyl groups is less than 2, there will be a problem in printability, and if it is 19 or more, there will be problems in curability. The weight average molecular weight is 3,000 to 30,000, preferably 800, as determined by gel vermiaceidin chromatography.
It ranges from 0 to 30,000.

Other polyhydric carboxylic acids or anhydrides thereof that can be used in combination with the above compound (a) include, for example, oxalic acid, malonic acid, succinic acid, dodecenyl succinic acid, pentadecenyl succinic anhydride, glutaric acid, and maleic acid. or their acid anhydrides, fumaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, 03K
-DASL-12,0SK-DASL-20,03K-
DASB-12,05K-DASB-20,03K-D
AUL-20,0SK-DAUB-20 (O3K series is a long-chain dibasic acid manufactured by Kenzai Oil Co., Ltd.), aliphatic dicarboxylic acids such as dimer acids such as linseed oil fatty acids and tung oil fatty acids,
0-phthalic acid, water-added 0-phthalic acid, methylated hydrogenated hymic acid, methylhimic acid, diphenic acid, trimellitic acid, pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides , isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid, brenidic acid, merofanic acid, benzenepentacarboxylic acid,
Benzene hexacarboxylic acid, homophthalic acid, 0% mz
Examples include aromatic polycarboxylic acids such as p-phenyleneacetic acid M and o-phenyleneacetic acid-β-propionic acid, rosin dimer acid, and the like.

The above compound in polycarboxylic acid or its anhydride (a
) and other polyhydric carboxylic acid or its anhydride in a weight ratio of 10010 to 10/90, preferably 100/1.
0 to 50150 is preferable. When the usage ratio of the compound or its anhydride (a) in the polyhydric carboxylic acid increases, the solubility in the heptamer (B) having the radically polymerizable double bond is insufficient depending on the number of its alkyl groups. There is a tendency. In addition, if the amount is too small, the lipophilicity will be insufficient and the improvement in the printing effect, which is an effect of the present invention, cannot be expected.

Single carboxylic acids include formic acid, acetic acid, propionic acid,
butyric acid, valeric acid, trimethylacetic acid, caproic acid, n
- aliphatic carboxylic acids such as hebutanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, coconut oil fatty acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lilunic acid, etc.
Examples include aromatic carboxylic acids such as benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid, benzoylbenzoic acid, and naphthoic acid, rosin, and water-added rosin.

Furthermore, there are esterified products of the above-mentioned dihydric carboxylic acids and -valent alcohols or esterified products in which one alcoholic hydroxyl group remains. When selecting this -valent carboxylic acid, short chain fatty acids such as formic acid, acetic acid, and propionic acid, benzoic acid, and hydrogenated rosin are used in order to obtain the alkyd resin composition (A) that is solid at room temperature. These -valent carboxylic acids are preferably used for the purpose of raising the gel point.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and propylene glycol.

Dipropylene glycol, tripropylene glycol.

Polypropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexanediol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, tetramethylolmethane, dipentaerythritol, polycyclopentadiene diallyl Alcohol copolymer, spiroglycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, bisphenol F propylene oxide adduct (the number of moles of alkylene oxide added is usually 1 per hydroxyl group of bisphenol) ), water-added bisphenol A1, water-added bisphenol F, etc.

Next, a method for reacting the ester compound (A) will be described.

Add the acid component (a) and alcohol component (b) to a flask with four stirrers at a functional group ratio (OH/C0OH group ratio) of 1.05 to
1.80°C, add an inert reaction solvent as necessary, and while blowing inert gas such as nitrogen or carbon dioxide, the reaction temperature is 80 to 300°C, preferably 15°C.
90% or more of the theoretical amount is reacted at 0 to 260°C. The reaction is preferably followed by checking the acid value, which is 10 or less, preferably 3 or less.

The composition according to the present invention includes the above ester compound (A),
Esterification reaction of acrylic acid or methacrylic acid. The reaction is carried out at a temperature of 80-120° C. in the presence of air or inert gas, using a polymerization inhibitor such as hydroquinone, a mass-produced acidic catalyst such as p-toluenesulfonic acid, etc. The acid value shall be 20 or less.

In the composition according to the present invention, not only the above-mentioned active energy ray-curable resin composition but also 7-mer-1 having a radically polymerizable double bond, such as 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,
Examples include monofunctional monomers such as myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate of an alkylene oxide adduct of alkylphenol, and cyclohexyl (meth)acrylate. Furthermore, as monomers having more than two functionalities, ethylene glycol di(meth)acrylate, diprolene glycol di(meth)acrylate, triprolene glycol di(meth)acrylate, polyprolene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, Diethylene 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, hydroxybivalyl hydroxybiparate di(meth)acrylate, hexanediol di(meth)acrylate, (di)glycerin tri( meth)acrylate, diglycerin alkylene oxide tetra(meth)acrylehet, trimethylolpropane tri(meth)acrylate, trimethylolpropane alkylene oxide tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane alkylene oxide tetra(meth)acrylate ) acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolethanetri(meth)acrylate, trimethylolethane alkylene oxide tri(meth)acrylate, ditrimethylolethane alkylene oxide tetro(meth)
Acrylate, Tetramethylolmethanetetra(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, Bisphenol A alkylene oxybi 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(meth)acrylate, water-added bisphenol A alkylene oxide adjunct di(meth)acrylate, water-added bisphenol F alkylene Examples include oxide adduct di(meth)acrylate. In addition, monomers of lactone adducts may be mentioned. Namely, polyethylene glycol borylactonate di(meth)acrylate, polypropylene glycol borylactonate di(meth)acrylate, alkylene glycol borylactonate di(meth)acrylate, glycerin polylactonate tri(meth)acrylate, diglycerin borylactonate tetra Polyols such as (meth)acrylate, trimethylolpropane polylactonate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol polylactonate tetra(meth)acrylate, dipentaerythritol polylactonate hexaacrylate, etc. Lactonate polyacrylate. In addition, the above-mentioned lactone can be used in combination with a compound containing an ester functional group -CO-O- in the ring, such as T-butyrolactone, 8-valerolactone, and ε-caprolactone, and the proportion of the combined use depends on the combination. Although it can be selected depending on the purpose, in general, if the proportion of the active energy ray-curable resin composition according to the present invention is less than 20% by weight, the effects of the present invention will decrease.

In addition, when the active energy ray is ultraviolet rays, it is necessary to add a radical polymerization initiator, such as benzoin-based sensitizers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and α-acrylic benzoin. , benzophenone,
Aryl ketone sensitizers such as p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl 0-benzoylbenzoate, acetophenone,
4. Dialkylaminoarylketone sensitizers such as 4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, and p-dimethylaminoacetophenone; polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products; Irgacure 90
7 (manufactured by Ciba-Geigy, trade name), etc., and these can be used alone or in appropriate combinations.

In the present invention, the pigment is dispersed in the resin composition to obtain the printing ink composition, 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. Also organic.

In addition to inorganic and extender pigments, plasticizers, surfactants, thermal polymerization inhibitors, etc. may 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 impair the effects of the present invention.

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

Production example-1 (comparative example) Tetrahydrophthalic acid 322 parts Glycerin 202 parts Toluene
35 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 12 hours under a stream of nitrogen gas. When the acid value reached 3.5, the solvent was removed, and then 8
Cool to 0°C, and at this temperature, 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-1-luenesulfonic acid, and 134 parts of methacrylic acid were charged under a uniform flow of nitrogen gas/air, and the temperature was gradually raised to 90~ The reaction was carried out at a temperature of 115°C, and when the acid value became 20 or less, the solvent was removed. This will be referred to as resin a. The weight average molecular weight of this resin a is 12
It was 000.

Production Example-2 (Example) Dimethyltetrahydrophthalic anhydride 376 parts Glycerin 202 parts Toluene
35 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 11 hours under a stream of nitrogen gas. When the acid value reached 3.0, the solvent was removed, and then 8
Cool to 0°C, and at this temperature, charge 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-toluenesulfonic acid, and 134 parts of methacrylic acid under a constant flow of nitrogen gas/air, and gradually raise the temperature to 90-115°C. When the acid value reached 20 or less, the solvent was removed. Let's call this a resin. The weight average molecular weight of this resin is 115
It was 00.

Production Example 3 (Comparative Example) Tetrahydrophthalic anhydride 288 parts Trimethylolpropane 294 parts O-benzoylbenzoic acid 147 parts Toluene
50 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 13 hours under a stream of nitrogen gas. When the acid value reached 3.1, the solvent was removed, and then at 80°C.
At this temperature, 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-)luenesulfonic acid and 72 parts of acrylic acid were charged under a uniform flow of nitrogen gas/air, and the temperature was gradually raised to 90-115°C. When the acid value reached 20 or less, the solvent was removed. This is resin C
shall be. The weight average molecular weight of this resin C was 11,500.

Production Example 4 (Example) Methyl, ethyl, propyltetrahydro 446 parts Trimethylolpropane phthalic anhydride 294 parts Benzoic acid 147 parts Toluene 60 parts were placed in a flask equipped with four stirrers and heated at 200°C for 11 hours under a nitrogen gas stream. The reaction was carried out, and when the acid value reached 3.0, the solvent was removed, and then it was cooled to 80°C, and at this temperature, 50 parts of benzene, 1 part of hydroquinone, and 10 parts of p-toluenesulfonic acid were added under a uniform flow of nitrogen gas/air. 1 part and 72 parts of acrylic acid were charged, the temperature was gradually raised, the reaction was carried out in the range of 90 to 115°C, and when the acid value became 20 or less, the solvent was removed. This will be referred to as resin d. This resin d had a softening point of 81° C. and a weight average molecular weight of 11,000.

Production Example-5 (Comparative Example) Tetrahydrophthalic acid 327 parts Pentaerythritol 300 parts Propionic acid 74 parts Toluene
50 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 12 hours under a stream of nitrogen gas. When the acid value reached 3.3, the solvent was removed, and then 80%
At this temperature, 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-toluenesulfonic acid, and 245 parts of acrylic acid were charged under a uniform flow of nitrogen gas/air, and the temperature was gradually raised to 90-115°C. The acid value is 2.
When the temperature became 0 or less, the solvent was removed. This will be referred to as resin e. The weight average molecular weight of this resin e is 10,500
Met.

Production Example 6 (Example) Hexahydrophthalic acid 163 parts Dipropylmonohexatetrahydro 320 parts Pentaerythritol phthalic anhydride 300 parts Propionic acid 74 parts Toluene 60 parts were placed in a flask equipped with four stirrers and heated at 200°C under a stream of nitrogen gas.
The reaction was carried out for 1 hour, and when the acid value reached 2.8, the solvent was removed, and then the solvent was cooled to 80°C. At this temperature, 50 parts of benzene, 1 part of hydroquinone, and p
- 10 parts of toluenesulfonic acid and 245 parts of acrylic acid were charged and the temperature was gradually raised to react in a range of 90 to 115°C, and when the acid value became 20 or less, the solvent was removed. This is referred to as resin f. The weight average molecular weight of this resin f was 11,000.

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

Table 1 below shows the weight average molecular weight and the formulation of the composition.

Margin below (Note-1) Abbreviations in Table-1 are as follows.

ABPE-4: Bisphenol A mole ethylene oxide adduct diacrylate TMPTA: Trimethylolpropane triacrylate TMPEOA: +-limethylolpropane 3 mole ethylene oxide adduct triacrylate Photosensitizer = 4.4-bis(diethylamino)benzophenone/ Benzophenone-2F5 Pigment: Fines Red F2BW: Toyo Ink Manufacturing Red Pigment Examples 1 to 4 and Comparative Examples 1 to 4 Coating compositions (printing inks) shown in Table 1, i.e. Comparative Examples Samples 1 to 4 4. KORD example samples 1 to 4
Printed with Heidelberg, stains on non-printing areas during printing,
In water (Note-2) was measured and shown in Table-2.

Margin Table 2 (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 compositions printed in the above Examples and Comparative Examples were applied to Comparative Example Samples 1 to 3 and Example Samples 1 to 3.
10cm below two high-pressure mercury lamps with an intensity of W/cra.
The area was placed on a conveyor and irradiated at 100 m/min. Further, Comparative Example Sample 4 and Example Sample 4 were irradiated at 3 Mrad using a curtain beam type electron beam irradiation device. Both were hardened.

〔Effect of the invention〕

The active energy ray-curable coating composition of the present invention has a better printing effect than conventionally known coating materials, as shown in Examples and Comparative Examples, and the range of application of the active energy ray-curable coating composition is can be spread.

Claims (1)

[Scope of Claims] 1. An acid component containing alkylated tetrahydrophthalic anhydride or hexahydrophthalic anhydride whose alkyl groups have a total number of carbon atoms of 2 to 18, or an acid anhydride thereof (a), and a polyhydric alcohol An active energy ray-curable resin composition prepared by reacting an esterified product (A) with an excess of OH groups with acrylic acid or methacrylic acid. 2. An active energy ray-curable printing ink composition comprising the resin composition according to claim 1 as a vehicle component.