JP2000080326A - Rosin ester resin and activation energy ray curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve compatibility with a general-purpose reactive diluent, curability, adherence and emulsification resistance of an activation energy ray curable resin composition by addition reacting rosins with a compound containing polyfounctional (meth)acryloyl group, and thereafter esterifying a carboxylic acid of the rosins with a polyol. SOLUTION: One equivalent of conjugated double bonds in rosins containing 0.6-0.8 mole of a resin acid having the conjugated double bonds in 1 mole of a raw material, rosin and 0.3-0.8 equivalent of (meth)acryloyl group of a compound containing a polyfunctional (meth)acryloyl group of 2-6 functions undergo an addition reaction at a temperature of 180-250 deg.C for 3-8 hr to produce a mixture of a (meth)acrylate adduct of the rosins having a plurality of carboxylic acids and the rosins having one carboxylic acid and no addition of (meth) acrylate. One equivalent of the carboxylic acid group in this mixture and 0.5-1.5 equivalents of a hydroxyl group in polyol of 2-4 functions undergo an esterification reaction at a temperature of 180-270 deg.C for 8-20 hr, thus obtaining the objective activation energy ray curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel rosin ester resin and an active energy ray-curable resin composition containing the rosin ester resin. The active energy ray-curable resin composition of the present invention is cured at a high speed by irradiation with ultraviolet rays or electron beams, and is particularly useful as a vehicle for offset inks.

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable resin compositions comprising a resin and a reactive diluent as main components have been used in various fields such as printing inks, paints, adhesives and overprint varnishes. I have. Particularly, offset inks have excellent curability and coating film hardness as reactive diluents.
Diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate,
Pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are widely used.

[0003] On the other hand, various resins have been proposed for the offset ink, but few resins having good compatibility with the reactive diluent and excellent suitability for offset printing are known. Examples of the resin having good compatibility with the reactive diluent include diallyl phthalate resin, which is exclusively used as an active energy ray-curable ink binder. However, the diallyl phthalate resin has poor emulsification resistance and poor adhesion to various substrates. Also,
Since diallyl phthalate resin does not have a functional group (such as a carboxylic acid) suitable for aluminum chelation, aluminum chelation cannot be performed, and it is difficult to impart the viscoelasticity required for offset ink, and the printability is insufficient. Absent. Therefore, such offset inks using diallyl phthalate resin cause problems such as insufficient image reproducibility and misting. Therefore, the offset inks can be used in applications such as cartons, business forms, etc., which require very little image reproducibility. Are not limited to those areas.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin which can be a new vehicle in place of the diallyl phthalate resin. That is, the present invention shows good compatibility with reactive diluents commonly used in active energy ray-curable offset inks such as ditrimethylolpropane tetraacrylate, curability, adhesion,
It is an object of the present invention to provide a novel resin having excellent emulsification resistance, which can be aluminum-chelated, and can impart the viscoelasticity required for offset inks, and an active energy ray-curable resin composition containing the resin. Aim.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have carried out an addition reaction of a rosin with a polyfunctional (meth) acryloyl group-containing compound,
Further, the present inventors have found that a novel rosin ester-based resin obtained by subjecting a carboxylic acid of a rosin and a polyol to an esterification reaction is suitable for a vehicle of an active energy ray-curable offset ink and can solve the above-mentioned problems, and the present invention It was completed.

That is, the present invention relates to a rosin ester system obtained by subjecting a rosin to an addition reaction of a polyfunctional (meth) acryloyl group-containing compound and further subjecting the carboxylic acid of the rosin to an esterification reaction with a polyol. resin;
A method for producing a rosin ester-based resin in which a rosin is subjected to an addition reaction of a polyfunctional (meth) acryloyl group-containing compound and a carboxylic acid of the rosin is further esterified with a polyol; The present invention relates to an active energy ray-curable resin composition containing a hydrophilic diluent.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The rosin ester-based resin of the present invention undergoes an addition reaction of a rosin with a compound having a polyfunctional (meth) acryloyl group, and further performs an esterification reaction of a carboxylic acid of the rosin with a polyol. It can be obtained by:

The rosins include so-called raw rosins such as gum rosin, wood rosin, tall oil rosin and the like. The raw material rosin is a mixture containing several kinds of resin acids having a conjugated double bond in a rosin skeleton such as abietic acid, neoabietic acid, levobimaric acid, and parastolinic acid, which can undergo an addition reaction of the acryloyl group-containing compound. The raw material rosin varies depending on the type of rosin, the place of production, and the like.
About 0.6 to 0.8 mol is contained in the mol. In addition, disproportionated rosin, hydrogenated rosin, and stabilized rosin such as colorless rosin have almost no conjugated double bond in the rosin skeleton, and therefore are not suitable as the rosins of the present invention. A partially stabilized rosin with controlled disproportionation and hydrogenation so that conjugated double bonds remain may be used. It is also possible to use the raw material rosin as a main component and to use a stabilized rosin together for the purpose of adjusting the network structure. Of course, for example, abietic acid alone can be used without using rosin, but it is not economically effective.

The polyfunctional (meth) acryloyl group-containing compound to be subjected to the addition reaction with rosin includes (meth)
Various compounds having a plurality of acryloyl groups can be used. As the number of functional groups of the (meth) acryloyl group increases,
In the later esterification, the network structure is easily formed, and the viscoelasticity of the active energy ray-curable resin composition is easily increased. However, the compatibility with the reactive diluent tends to deteriorate, so that (meth) acryloyl is used. The number of functional groups is appropriately determined according to the purpose of use. As the polyfunctional (meth) acryloyl group-containing compound, a compound having 2 to 6 functions is usually used. The number of functional groups of the (meth) acryloyl group in the polyfunctional (meth) acryloyl group-containing compound is preferably from 3 to 6. When only a monofunctional (meth) acryloyl group-containing compound is used, the addition product has only one carboxylic acid and does not take a network structure in the subsequent esterification. The monofunctional (meth) acryloyl group-containing compound can be used in combination with the polyfunctional (meth) acryloyl group-containing compound as long as the object of the above is not impaired.

Specific examples of polyfunctional (meth) acryloyl group-containing compounds include ethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, ethylene oxide added bisphenol A di (meth) acrylate, ethylene oxide added bisphenol F di (meth) acrylate, propylene oxide added bisphenol A di (meth) acrylate, propylene oxide added bisphenol F di (meth) ) Bifunctional (meth) acryloyl group-containing compounds such as acrylate and dicyclopentanyldi (meth) acrylate; Tyrolpropane tri (meth) acrylate, pentaerythritol triacrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added glycerin triacrylate, propylene oxide-added glycerin triacrylate Etc., trifunctional (meth) acryloyl group-containing compounds, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. tetrafunctional (meth) acryloyl group-containing compounds, dipentaerythritol hexa (meth) acrylate And hexafunctional (meth) acryloyl group-containing compounds. In addition,
Polyfunctional (meth) acryloyl group-containing compounds can be used alone or in combination as appropriate.

Polyfunctional (meth) for the rosins
The amount of the acryloyl group-containing compound used is such that the (meth) acryloyl group of the polyfunctional (meth) acryloyl group-containing compound does not exceed 1 equivalent relative to 1 equivalent of the conjugated double bond in the rosin. . Usually, the amount of the (meth) acryloyl group of the polyfunctional (meth) acryloyl group-containing compound is about 0.3 to 0.8 equivalent to 1 equivalent of rosin (1 equivalent of 1 mol of rosin). The equivalent of the (meth) acryloyl group is preferably 0.5 equivalent or more,
Further, the content is preferably 0.75 equivalent or less. When the equivalent of the (meth) acryloyl group is less than 0.3 equivalent, the ratio of the acrylate adduct of rosins having two or more carboxylic acid groups contained in the reaction product is reduced, and the ratio is reduced during the subsequent esterification. It is difficult to form a network structure, and it is difficult to obtain a target rosin ester-based resin. If it is more than 0.8 equivalent, the equivalent of the (meth) acryloyl group will exceed the equivalent of the resin acid having the conjugated double bond contained in the rosin, and the (meth) acryloyl group will be lost during the production. It is not preferable because a polymerization reaction easily occurs.

The method of the above addition reaction is not particularly limited, but after heating and melting the rosin, the polyfunctional (meth)
A method of charging an acryloyl group-containing compound dropwise,
It is easy to avoid polymerization reaction between (meth) acryloyl groups,
Appropriate. The reaction temperature after completion of the dropwise addition is usually 180 to 25.
The reaction time is usually about 0 to about 8 hours. Since the reaction is a high-temperature reaction, the reaction is desirably performed in an atmosphere of an inert gas such as nitrogen. The use of a catalyst, a polymerization inhibitor, a coloring inhibitor and the like are all optional.

By such an addition reaction, a mixture of a (meth) acrylate adduct of a rosin having a plurality of carboxylic acids and a rosin having one carboxylic acid to which no (meth) acrylate is added is usually obtained.

Next, in the present invention, an esterification reaction of the mixture with the polyol is performed. By reacting the polyol, a rosin ester-based resin having an arbitrary network structure can be synthesized.

Although various polyols can be used, it is usually preferable to use a polyol having about 2 to 4 functions. When a polyol having five or more functional groups is used, the network structure may be excessively advanced. As these polyols have a larger number of functional groups and a smaller molecular weight, they tend to have a network structure, and the viscoelasticity of the active energy ray-curable resin composition increases, but on the other hand, the compatibility with the reactive diluent tends to deteriorate. Therefore, the number of functional groups of the polyol is appropriately determined according to the purpose of use. In addition, usable reactive diluents are limited, and it is preferable to use a bifunctional polyol especially for applications requiring compatibility. In this case, in order to have an appropriate network structure, it is preferable to use a polyfunctional (meth) acryloyl group-containing compound having 3 to 6 functions.

Specific examples of the polyol include bifunctional polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, and 1,6-hexanediol; and trifunctional polyols such as glycerin and trimethylolpropane. Tetrafunctional polyols such as pentaerythritol; polyether polyols such as polyethylene glycol and polypropylene glycol, polyester polyols, bisphenol A with ethylene oxide and bisphenol A with propylene oxide. These polyols can be used alone or in combination as appropriate. When a monofunctional alcohol is used, the esterified product does not have a network structure, which is not suitable for the present invention. However, it is possible to use a monofunctional alcohol in combination with a polyol as a main component for the purpose of adjusting the network structure.

The amount of the polyol to be used in the mixture containing the (meth) acrylate adduct of the rosin is about 0.5 to 1.5 equivalent of the hydroxyl group of the polyol to 1 equivalent of the carboxylic acid group in the mixture. The hydroxyl equivalent of the polyol is preferably 0.7 equivalent or more, and more preferably 0.9 equivalent or less. The polyol has a hydroxyl equivalent of 0.
When the amount is less than 5 equivalents, the mixture containing the (meth) acrylate adduct of the rosin or the like becomes excessive, so that the network structure does not occur so much and it is difficult to obtain a desired resin composition.
If the amount is more than 1.5 equivalents, the amount of the polyol becomes excessive, the network structure is not so much formed, and it is difficult to obtain a desired resin composition. When the amount is 0.7 to 0.9 mol, a carboxylic acid group remains and a later aluminum chelation reaction easily occurs, which is more preferable.

The method of the esterification reaction is not particularly limited, and may be, for example, a method of simultaneously charging a polyol containing a (meth) acrylate adduct of rosin and a polyol. Usually, the reaction temperature is about 180 to 270 ° C, and the reaction time is about 8 to 20 hours. Since the reaction is a high-temperature reaction, the reaction is desirably performed in an atmosphere of an inert gas such as nitrogen. catalyst,
The use of a coloring inhibitor or the like is optional.

In preparing the active energy ray-curable resin composition from the rosin ester-based resin of the present invention thus obtained and the reactive diluent, the resin composition 5 is usually used.
The reactive diluent is about 95 to 30 parts by weight, preferably 8 to 70 parts by weight, preferably 15 to 60 parts by weight.
It is preferable to use it at a ratio of 5 to 40 parts by weight.

Various reactive diluents can be used. For use in offset inks, ethylene oxide-added bisphenol A diacrylate, trimethylolpropane triacrylate, ethylene oxide-added trimethylolpropane triacrylate, ditriol It is preferable to use methylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.
These reactive diluents are determined in consideration of compatibility with resin components and curability. In addition, the reactive diluents can be used alone or appropriately in combination.

When the resin composition of the present invention is cured by an electron beam or the like, a photoinitiator is not required, but when it is cured by ultraviolet irradiation, a photoinitiator is used. The amount of the photoinitiator to be used is about 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of the resin composition and the reactive diluent. Examples of the photoinitiator include Darocure 1173, Irgacure 651, Irgacure 184, Irgacure 907 (registered trademark of Ciba Specialty Chemicals), benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-Dimethylacetophenone, thioxanthone, alkylthioxanthone, amines and the like.

In the resin composition of the present invention, various known additives such as a polymerization inhibitor, a pigment, a colorant, and a filler are appropriately selected and used according to the purpose, if necessary. can do.

[0023]

According to the present invention, good compatibility with reactive diluents commonly used in active energy ray-curable offset inks such as ditrimethylolpropane tetraacrylate is exhibited, and the curability, adhesion, and resistance to curable inks are improved. Excellent emulsifying properties,
In addition, it is possible to provide a novel resin composition capable of aluminum chelation and imparting the viscoelasticity required for offset inks, and an active energy ray-curable resin composition containing the resin composition. These resin compositions can be applied to various uses such as printing inks, metal inks, paints, adhesives and overprint varnishes.

[0024]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited to only these examples. In each example, all parts and percentages are by weight unless otherwise specified.

Production Example 1 A reactor equipped with a stirrer, a cooling tube, a thermometer, a dropping funnel and a nitrogen inlet tube was charged with 320 parts of Chinese gum rosin and 0.4 part of methquinone (polymerization inhibitor) and heated and melted. Stirring was started, and the temperature was raised to 200 ° C., and then 105.6 parts of propylene oxide-added glycerin triacrylate (trade name: Beam Set 720, manufactured by Arakawa Chemical Industries, Ltd.) was added in an amount of 0. (Corresponding to an acryloyl group content of 7 equivalents) was added dropwise over 1 hour.
Then, react at 220 ° C. for 5 hours and 240 ° C. for 1 hour,
The Diels-Alder addition reaction was completed to obtain a propylene oxide-added glycerin triacrylate adduct of rosin. The acid value was 134.

Preparation Examples 2 to 5 The reaction was carried out in the same manner as in Preparation Example 1 except that the acryloyl group-containing compound used in Preparation Example 1 was changed as shown in Table 1, to obtain a target rosin acrylate adduct.

[0027]

[Table 1]

In Table 1, the product name beam set 710,
Arakawa Chemical Industry Co., Ltd., product name: Beam Set 70
0, manufactured by Arakawa Chemical Industry Co., Ltd .: Trade name TRPGDA,
Manufactured by Daicel UCB Co., Ltd.

EXAMPLE 1 700 parts of the rosin acrylate adduct obtained in Production Example 1 and 61.9 parts of diethylene glycol (rosin) (Corresponding to a hydroxyl group content of 0.7 equivalent to 1 equivalent of the carboxylic acid of the acrylate adduct). After heating and melting, stirring is started, and the mixture is
After reacting at 40 ° C. for 2 hours and further at 260 ° C. for 6 hours, the mixture was distilled under reduced pressure at the same temperature for 1 hour at 50 mmHg to obtain a rosin ester resin. The acid value was 28.

Examples 2 to 5 and Comparative Examples 1 to 3 The reaction was carried out in the same manner as in Example 1 except that the acrylate adduct of rosin and the polyol used in Example 1 were changed as shown in Table 2, and the rosin ester was obtained. A system resin was obtained.

[0031]

[Table 2]

In Table 2, the product name: Phantol PL30
5, manufactured by Toho Rika Kogyo Co., Ltd .: Trade name Phan Tol P
L3010, manufactured by Toho Rika Kogyo Co., Ltd.

Example 6 The rosin ester-based resin 40 obtained in Example 1 was placed in a reactor equipped with a stirrer, a cooling pipe, a thermometer and an air introduction pipe.
Part, ditrimethylolpropanetetraacrylate (trade name: Evecryl 140, manufactured by Daicel UCB, Inc .; hereinafter referred to as DTMTPA) 56 as a reactive diluent
Parts and 0.1 part of methoquinone (polymerization inhibitor)
The mixture was stirred and dissolved at 90 ° C. for 1 hour under air bubbling. Then, ethyl acetate aluminum diisopropylate (trade name ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.)
A diluent obtained by diluting 0.8 part (corresponding to 2% of resin) with 4 parts of DTMPTA was slowly added, and the mixture was further kept at 90 ° C. for 3 hours to obtain a gel varnish. (Rosin ester resin /
The ratio (weight ratio) of the reactive diluent is 4/6).

Examples 7 to 10 and Comparative Examples 4 to 6 Table 3 shows the rosin ester-based resin obtained in Example 1, the reactive diluent, and the ratio of the resin to the reactive diluent used in Example 6. A gel varnish was prepared in the same manner as in Example 6, except that the conditions were changed as shown.

[0035]

[Table 3]

In Table 3, the product name beam set 750,
Arakawa Chemical Industries, Ltd .: diallyl phthalate resin,
Manufactured by Daiso Corporation.

(Various Performance Test Methods) The rosin ester-based resins and gel varnishes obtained in the above Examples and Comparative Examples were subjected to performance tests by the following methods.

1. Compatibility: Examples 1-5, Comparative Examples 1-3
And DAP (diallyl phthalate resin, Daiso Corporation)
30 parts) were dissolved in each of the following three types of reactive diluents (70 parts), and the varnish transparency at room temperature was visually determined. Table 4 shows the evaluation results.

Reactive diluent used 1) Bisphenol A tetraethoxydiacrylate (hereinafter abbreviated as BA (EO) DA) <trade name Beamset 750, manufactured by Arakawa Chemical Industries, Ltd.> 2) Trimethylolpropane triacrylate T
3) Ditrimethylolpropane tetraacrylate (hereinafter abbreviated as DTMPTA) <Evecryl 140, manufactured by Daicel UCB Co., Ltd.>

[0040]

[Table 4]

2. Viscoelasticity: E-type viscometer (Tokyo Keiki Co., Ltd.)
) Of Examples 6-10 and Comparative Examples 4-6.
The viscosity at 0 ° C. was measured in the order of 0.5 rpm, 2.5 rpm, and 5 rpm. Further, a viscosity ratio of 0.5 rpm / 5 rpm was calculated. The greater the value of this viscosity ratio, the greater the viscoelasticity. Table 5 shows the evaluation results.

3. Emulsification resistance (water separation): Examples 6-1
0 and 10 parts of each of Comparative Examples 4 to 6 were dissolved in 20 parts of xylene. Glass test tube (inner diameter 18mmX height 180mmX
7.5 parts of distilled water was put into a 1.2 mm-thick, trade name PYREX TEST18, manufactured by Iwaki Glass Co., Ltd., and then 7.5 parts of a xylene solution was put and plugged. This was shaken up and down 20 times to emulsify it, and then allowed to stand to measure the time until the aqueous layer and the organic layer were completely separated. There is a correlation between the water separation property and the emulsification resistance, and the better the water separation property, the better the emulsification resistance when applied to an ink. Table 6 shows the evaluation results.

4. Curability: Examples 6 to 10 and Comparative Example 4
5 parts of Irgacure 184 (registered trademark of Ciba Specialty Chemicals) as a photopolymerization initiator was blended with 100 parts of each of Nos. To 6 and mixed at 60 ° C. An RI tester (0.3 g of ink) was applied to the carton paper, and then a high-pressure mercury air-cooled lamp (120 W / cm, irradiation distance 1)
(0 cm), the belt speed was changed, and ultraviolet irradiation was performed. The maximum belt speed at which the cured film became tack-free was measured. Those with a high speed, that is, those that are cured even with a small irradiation dose, have good curability. Table 6 shows the evaluation results.

5. Misting: 1 g of each of Examples 6 to 10 and Comparative Examples 4 to 6 was placed on a rubber roll of an incometer, and when operated under a condition of 1,200 rpm, the state in which the mist was scattered was visually judged, and 5 levels were used. evaluated. The larger the value, the better the misting properties. Table 6 shows the evaluation results.

6 Adhesion: Examples 6 to 10 and Comparative Example 4
5 parts of Irgacure 184 (registered trademark of Ciba Specialty Chemicals) as a photopolymerization initiator was blended with 100 parts of each of Nos. To 6 and mixed at 60 ° C. Using a 1.5 mil dice-type applicator, apply to an acrylic plate (hereinafter abbreviated as Acr), an ABS plate, and an FRP plate (all manufactured by Nippon Test Panel Co., Ltd.), and apply a high-pressure mercury air-cooled lamp (120 W / cm, irradiation distance of 10 cm, and belt speed of 40 m / min.). A cellophane tape peeling test was performed on each test substrate, and the adhesion between the coating layer and the substrate was evaluated according to the following evaluation criteria. ：: The coating agent layer does not peel off. Δ: The coating agent layer is peeled off by about 50%. X: The coating agent layer is completely peeled off.

[0046]

[Table 5]

[0047]

[Table 6]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C09D 4/00 C09D 4/00 F term (reference) 4J011 PA25 PA29 PA57 PA69 PB30 PC08 QB28 QB29 RA10 RA11 SA90 UA01 UA03 WA05 4J027 AC03 AC06 AH00 AH03 AJ04 AJ08 BA19 BA23 BA24 BA26 BA27 BA28 CB10 CC05 CC06 CD08 4J038 BA231 FA111 FA301 KA06 NA18 PA17 PB13 4J039 AB08 AD21 AF03 AF07 BC20 EA06 EA08 EA10 EA43 FA01 GA02

Claims (6)

[Claims] 1. A rosin ester-based resin obtained by subjecting a rosin to an addition reaction of a polyfunctional (meth) acryloyl group-containing compound and further subjecting the carboxylic acid of the rosin to an esterification reaction with a polyol. 2. The rosin ester resin according to claim 1, wherein the polyfunctional (meth) acryloyl group-containing compound is a tri- to hexafunctional (meth) acryloyl group-containing compound. 3. The rosin ester resin according to claim 1, wherein the polyol is a 2- to 4-functional polyol. 4. The rosin ester-based resin according to claim 3, wherein the polyol is a bifunctional polyol. 5. A method for producing a rosin ester-based resin in which a rosin is subjected to an addition reaction with a polyfunctional (meth) acryloyl group-containing compound, and a carboxylic acid of the rosin is esterified with a polyol. 6. An active energy ray-curable resin composition comprising the rosin ester-based resin according to claim 1 and a reactive diluent.