JPH02238013A - Active energy ray-curable resin composition and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent adhesive property by removing monobasic carboxylic acid from a reaction product of a hydroxyl- containing alkyd resin, etc., and a monobasic carboxylic acid anhydride and compounding the product with a monomer containing radically polymerizable double bond. CONSTITUTION:The objective composition is produced by compounding (A) preferably 15-50 pts.wt. of a reaction product (preferably having a weight- average molecular weight of 8,000-30,000) produced by reacting a hydroxyl- containing alkyd resin or epoxy ester resin with a monobasic carboxylic acid anhydride (e.g. acetic anhydride) and removing by-produced monobasic carboxylic acid, (B) preferably 20-70 pts.wt. of a monomer containing radically polymerizable double bond (e.g. neopentyl glycol diacrylate) and, as necessary, (C) preferably 0-15 pts.wt. of a radical polymerization initiator (e.g. benzoin). A printing ink having excellent print effect can be produced by compounding the composition as a vehicle.

Description

Detailed Description of the Invention [Object of the Invention] (Industrial Application Field) 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.

(Conventional technology) Recent years. Research on coating compositions that can be cured by active energy rays has been actively conducted, including printing inks and clear coats. Paint, adhesive. Practical use is progressing in fields such as photoresists. These are a radically polymerizable resin and heptamer, and if necessary, a radical polymerization initiator. It is made of pigment. Examples of radically polymerizable resins include alkyd (meth)acrylate polyester (meth)acrylate, epoxy (meth)acrylate, and urethane-modified (meth)acrylate, and examples of monomers include bisphenol A alkylene oxide adduct di(meth)acrylate. Neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, diventaerythritol hexa(meth)acrylate. Alkylphenol alkylene oxide adduct mono (meth)acrylate, etc. were used.

but. Curable coating compositions using these compounds can be used, for example, in printing inks. Dirt during printing. Poor transfer often occurs due to emulsification of the ink. Also, the adhesion is not good. Therefore, the reality is that the scope of application of these curable coatings has been narrowed.

Also. Recently, attempts have been made to improve printability by using a vehicle in which an alkyl resin or an epoxy ester resin is dissolved in a radically polymerizable monomer. however. These resins had residual hydroxyl groups from the reaction, and were not necessarily satisfactory.

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

[Structure of the invention]

(Means for solving the problems) The present invention is as follows. Resin (A) containing a product obtained by reacting a hydroxyl group-containing alkoxy resin or epoxy ester resin with a monovalent carboxylic acid anhydride and removing the by-produced monovalent carboxylic acid. A monomer having a radically polymerizable double bond (B
), and, if necessary, an active energy ray-curable resin composition and a printing ink composition containing a radical polymerization initiator (C).

In the present invention. Alkyd resin is generally made by subjecting a polyhydric alcohol to an esterification reaction with a polyhydric carboxylic acid as a crosslinking agent and a monohydric carboxylic acid as a modified resin. During this reaction, excess hydroxyl groups are used to ensure sufficient reaction of the acid component. Usually OH/CoOH base ratio 1.01-1.
20, so the hydroxyl group remains.

Also. The epoxy ester resin in the present invention is a reaction product of an epoxy compound and a monovalent carboxylic acid, and refers to a reaction product produced by an esterification reaction of an epoxy group or a secondary hydroxyl group produced by the reaction.

Also. Epoxy compounds are glycidyl ether type epoxy resins and glycidyl ester type epoxy resins that have one or more epoxy groups in one molecule. These include glycidylamine type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, etc.

+ CI as a monohydric carboxylic acid? I C+a aliphatic carboxylic acid, aromatic alicyclic carboxylic acid, carboxylic acid such as rosin. The esterification reaction is carried out by a conventional method.

If the secondary hydroxyl groups remain in this epoxy ester resin, it will cause problems when used as a vehicle for offset printing ink. The ink emulsifies. It causes stains and deterioration of adhesion.

Usually, the hydroxyl group before esterification is 5 to 5 after esterification.
30% of hydroxyl groups remain.

The reaction between the hydroxyl group-containing alkyd or epoxy ester resin produced in this way and the monovalent carboxylic acid anhydride is as follows.
Usually at 100 to 200°C, preferably 115 to 150°C, for 1 to 4 hours while blowing air. It is carried out under the following conditions. The ratio during the reaction is 0.1 to 1 mol of monovalent carboxylic acid anhydride per hydroxyl group, and when used as an offset printing ink, it is 0.8 mol or more, and in some cases 1 mol.
It is also effective to use a molar or more excess of monocarboxylic acid anhydride. In this case, the excess acid anhydride is removed together with the monovalent carboxylic acid by-produced after hydrolysis by distillation under reduced pressure or by washing with water.

Monovalent carboxylic acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, trimethylacetic anhydride,
Caproic anhydride, hebutanoic anhydride. Caprylic anhydride, pelargonic anhydride, methoxyacetic anhydride, nonylic anhydride.
Anhydrous coconut oil fatty acids. 9 Palmitic anhydride. Stearic anhydride, oleic anhydride, linoleic anhydride, linolenic anhydride. Examples include benzoic anhydride, alkylbenzoic anhydride, cinnamic anhydride, and acrylic anhydride.

The reaction between these monovalent carboxylic acid anhydrides and hydroxyl groups produces monovalent carboxylic acids as by-products, and if these monovalent carboxylic acids remain in the system, they cause stains during printing. This is undesirable because it causes corrosion of the printing press and ink filling can. Therefore, the remaining monovalent carboxylic acid is ? Jli pressure distillation. Alternatively, remove it by an appropriate method such as washing with water. An effective distillation pressure is 20 mmHg or less. Therefore, when removed by pressure distillation, carboxylic acids that can be removed under such conditions, such as acetic anhydride, propionic anhydride, methacrylic anhydride, butyric anhydride, and isobutyric anhydride. It is necessary to select valeric anhydride, isovaleric anhydride, caproic anhydride, etc., and to make this vacuum distillation more effective, acetic anhydride, propionic anhydride, acrylic anhydride, etc. It is best to choose from methacrylic anhydride, butyric anhydride, and isobutyric anhydride. In yet another embodiment, it is also preferable to add water during vacuum distillation to perform azeotropic distillation.

If the monohydric carboxylic acid produced as a by-product has a high boiling point and is difficult to remove by distillation under reduced pressure, it can also be removed by washing with water. Wash with amine or ammonia as necessary. Alkali can also be added, and washing with water is carried out two or three times or more.

The resin (A) thus obtained has reduced or disappeared hydroxyl groups, is solid at room temperature, and has a molecular weight of 3,000 to 3 on average as determined by gel permeation chromatography.
0 0. Preferably it is in the range of 8,000 to 30,000. This resin (A) is... The monomer (B) having radical polymerizability, a pigment and, if necessary, a radical polymerization initiator (C) are mixed and used as an active energy ray-curable coating composition or printing ink.

Also, when using aluminum octylate. Gelling agents such as aluminum stearate, aluminum triisopropoxide, etc. may also be used. In this case, alkyd resins or epoxy resins with an excess of hydroxyl groups are reacted with a monocarboxylic anhydride after reaction with a gel value agent, or after dissolving these resins in a radically polymerized monomer and reacting with a gel value agent. may be done.

In the present invention, monofunctional or polyfunctional acrylic monomers are used as the monomer (B) having a radically polymerizable double bond. For example, as a monofunctional molmer (C+
``Cps) alcohol (meth)acrylate and alicyclic (meth)acrylate, neopentyl glycol di(meth)acrylate borealkylene glycol di(meth)acrylate, bisphenol A propylene oxide adduct diacrylate as a polyfunctional monomer,
(di)trimethylolpropane(tetra)tri(meth)acrylate Glycerin (alkylene oxide adduct) tri(meth)acrylate. These are examples. Any (meth)acrylate of monohydric or higher alcohol can be used.

The resin (A) according to the present invention is dissolved in the monomer (B). The weight ratio of resin (A) and heptamer (B) used is 2.
0/80 to 60/40 is preferred. When the active energy rays are ultraviolet rays. Radical polymerization initiator (
C), such as benzoin, benzoin methyl ether. Benzoin ethyl ether. Penzoin isopyl ether. Benzoin-based exacerbants such as α-acrylic benzoin, penzophenone, p-methylbenzophenone, p-chlorobenzophenone, and tetrapenzophenone. Methyl 0-benzoylbenzoate,
Aryl ketone sensitizers such as acetophenone. 4.
4-Hisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate. Dialkylaminoarylketone sensitizers such as p-dimethylaminoacetophenone, polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products, Irgacure 90
7 (sensitizer manufactured by Ciba Geigy, trade name), etc. These can be used alone or in appropriate combinations. The amount of the radical polymerization initiator (C) used is 0 to 30 parts, preferably 0 to 15 parts, based on 100 parts by weight of the alkyd resin composition (A) and monomer (B).

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 colorants such as inorganic and extender pigments. Plasticizers, surfactants, thermal polymerization inhibitors, etc. can be added as necessary. Of course.
There may also 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.

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

Production Example-1 Tetrahydrophthalic anhydride 322 parts Glycerin 202 parts Benzoic acid
200 parts toluene
35 parts were charged into a fourth flask using a stirrer and reacted at 200° C. for 12 hours under a nitrogen gas stream. When the acid value reached 3.5, the solvent was removed and pumped out. This will be referred to as resin a. The hydroxyl value of this resin a is 89. The softening point was 95°C and the weight average molecular weight was 12,000.

Production Example-2 (Example) Methyl, ethyl. Propyltetra 446 parts Trimethylolpropane hydrophthalic anhydride 294 parts Benzoic acid 273 parts Toluene
60 parts were placed in a four-necked flask with a stirrer and reacted at 200°C for 11 hours under a stream of nitrogen gas, and when the acid value reached 3.0, the solvent was removed. I pumped it out. This will be referred to as resin b.

What is the hydroxyl value of this resin b? 6.0, softening point is 70℃. The weight average molecular weight was 13,000.

Production example-3 Ebiko} 1004 (epoxy resin manufactured by Shell Chemical ■) 1
600 parts nonyl acid 379 parts water-added gin 1320 parts triethylenediamine 3 parts xylol
Pour 150 parts into a four-necked flask with a stirrer. 150℃ under nitrogen gas flow. Let react for 1 hour. The temperature was further gradually increased and the reaction was carried out at 240°C for 8 hours until the acid value reached 5.0, so the mixture was cooled. A desolvation mechanism was developed. This will be referred to as resin C. The hydroxyl value of this resin C is 34.0. The softening point was 75°C and the weight average molecular weight was 8,500.

Production Example 1 650 parts of the resin a of Production Example 1, 158 parts of butyric anhydride. Pour 35 parts of triene into a fourth flask equipped with a stirrer and blow in nitrogen. 150℃. Let react for 2 hours. then 20
The pressure was reduced at 0°C to remove the raw butyric acid. This resin a-1
The hydroxyl value of is 1.1. The softening point was 90°C and the weight average molecular weight was 12,000.

Production Example 2 530 parts of the resin a of Production Example 1. 400 parts of anhydrous coconut oil fatty acid and 50 parts of toluene were placed in a four-necked flask equipped with a stirrer.
React at 150°C for 2 hours while blowing nitrogen.

Thereafter, it was cooled and the formed oleic acid was removed by washing with water. The hydroxyl value of this resin a-2 was 1.0. Softening point is 85
℃, and the weight average molecular weight was 12,000.

Hereinafter, an active energy ray-curable coating material was obtained according to Production Example 1.2. They are shown in Tables 1 and 2, respectively.

Table 1 (According to Production Example 1) Table 2 (According to Production Example 2) Below margin [Printing test] A test was conducted using the coating composition (printing ink) shown in Table 3. That is, Comparative Samples 1, 2, and 3 and Example Samples 1 to 6 were printed using KORD Heidelberg printing base, and the number of sheets with stains on non-image areas during printing and the number of stains in water (Note-1) were measured. The results are shown in Table 4.

(Note-1) Water width: Measured by installing a device to control the amount of dampening water in the printing press. ．． The number order of the lower limit represents the amount of contaminated water when the amount of water is decreased. Also,
The upper limit number represents the amount of water at which the ink becomes milky and transfers poorly when the amount of water is increased. The numbers are scales that represent the amount of dampening water, and there is no specific unit.

The monomers, photosensitizers, and pigments in Table 3 are as follows.

ABPE-4: Bisphenol A 4 mole ethylene oxide adduct diacrylate TMPTMA: }rimethylolpropane trimethacrylate TMPHOA: Trimethylolpropane 3 mole ethylene oxide adduct triacrylate Photosensitizer A: 4,4-bis(diethylamino)benzophenone /benzophenone=2/ Pigment: Fines Red F 2 BW: Red pigment manufactured by Toyo Ink Manufacturing Co., Ltd. Below margins Next, the coating compositions shown in Table 3 were coated with alkyd resin. Epoxyphenol resin (E/P). 30mg/100a with Rl tester made of TFS plate coated with acrylic resin.
Printing was carried out to give a dry coating amount of J.

For Comparative Examples 1 and 2 and Examples 1 to 4 in Table 3, 80W
The film was cured by irradiating it on a conveyor belt 10 cm below two high-pressure mercury lamps having an intensity of /am.

Also, Comparative Example 3. For Examples 5 and 6, irradiation was performed at 10 Mrad using a curtain beam type electron beam irradiation device. hardened. Table 4 shows the results regarding the adhesion of each coating film.

The adhesion value indicates the residual rate of the coating film in the cellophane tape peeling test.

Margin Table 4 Below: [Effects of the Invention] The active energy ray-curable coating composition of the present invention is... Compared to conventional coatings. As shown in Tables 3 and 5, the printing effect is good, the adhesion is excellent, and the range of application of active energy ray effective coating compositions can be expanded.

Claims (1)

[Scope of Claims] 1. Resin (A) containing a product obtained by reacting a hydroxyl group-containing alkyd resin or epoxy ester resin with a monovalent carboxylic acid anhydride and removing the monovalent carboxylic acid by-produced.
, a monomer (B) having a radically polymerizable double bond, and, if necessary, a radical polymerization initiator (C). 2. Monomer (B) to 15 to 50 parts by weight of resin (A)
) 20 to 70 parts by weight and radical polymerization initiator (C) 0
-15 parts by weight of an active energy ray-curable resin composition. 3. An active energy ray-curable printing ink composition comprising the resin composition according to claim 1 or 2 as a vehicle component.