JP5403240B2 - Rosin copolymer, active energy ray-curable resin composition, and cured product - Google Patents

Description

The present invention relates to a novel rosin copolymer, an active energy ray-curable resin composition containing the same, and a cured product thereof.

Resin compositions curable with active energy rays such as ultraviolet rays and electron beams (hereinafter referred to as active energy ray curable resin compositions) are usually reactive diluents, resins, photoinitiators and additives (sensitizers, As a low-pollution and low-energy industrial material, it is used for applications such as coating agents, paints, and printing inks.

As the reactive diluent, the active energy ray-curable resin composition has excellent curability, film hardness, and the like. Therefore, there are many reactive diluents such as dimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and ditrimethylolpropane tetraacrylate. Functional (meth) acrylates are widely used. Further, as the resin, a diallyl phthalate resin is generally awarded particularly as a resin having excellent compatibility with a (meth) acrylate compound having a large number of functional groups.

However, depending only on the diallyl phthalate resin, the formulation of the active energy ray-curable resin composition is limited. In addition, diallyl phthalate resin is not universal, and the active energy ray-curable resin composition using the resin may be difficult to adhere to a plastic substrate such as polyester resin, acrylic resin, or polyolefin. Among these, particularly, the polyolefin base material is excellent in chemical properties, is lightweight, and is inexpensive, and therefore, an active energy ray-curable resin composition having excellent adhesion to the polyolefin base material is very useful.

The present applicant has already proposed a rosin-based bisphenol-type epoxy resin as a resin that can replace diallyl phthalate resin (see Patent Document 1). Taking advantage of the property of pigment dispersibility due to the group, it is considered useful as a vehicle for offset printing ink, for example.

JP-A-6-87946

 The object of the present invention is excellent in compatibility with various reactive diluents (especially polyfunctional (meth) acrylate compounds) (hereinafter, simply referred to as compatibility) and active energy for various plastic substrates (especially polyolefin substrates). It is an object of the present invention to provide a novel rosin resin that can improve the adhesion (hereinafter simply referred to as adhesion) of a cured coating of a linear curable resin composition.

The present inventor was able to replace diallyl phthalate resin, and as a result of diligent research on a novel resin having a rosin residue in the molecule, the following rosin-based copolymer can solve the above problems. It was found that the resin could be sufficient.

That is, the present invention relates to a (meth) acryloyl group-containing rosin derivative (a-1) obtained by subjecting a rosin and a (meth) acryloyl group-containing monovinyl ether compound to a hemiacetal esterification reaction, and styrenes (a-2) ( an active energy ray-curable resin composition comprising a rosin copolymer (A) obtained by copolymerization reaction of a-2) and a polyfunctional (meth) acrylate (B); The present invention relates to a cured product obtained by curing a product.

The rosin copolymer (A) of the present invention is excellent in compatibility with various reactive diluents, particularly polyfunctional (meth) acrylates such as dimethylolpropane tetra (meth) acrylate. Therefore, the rosin copolymer (A) is useful as an inert resin in the active energy ray-curable resin composition or as a viscosity modifier. The rosin copolymer (A) is an anti-misting agent for high-speed coating machines (reverse roll coaters, gravure coaters, offset rotary presses, etc.) of various products (offset printing inks, coating agents, etc.) using the same. It is expected to be useful as well.

The active energy ray-curable resin composition containing the rosin copolymer (A) and the polyfunctional (meth) acrylates (B) is excellent in compatibility with the polyfunctional (meth) acrylates. Excellent adhesion of cured film to various plastic substrates (particularly polyolefin substrates). Therefore, the resin composition is suitable as a paint, an adhesive, a printing ink, a coating agent, particularly a polyolefin base material coating agent.

The rosin-based copolymer (A) has a cyclic hydrocarbon residue derived from rosins in the molecule, and various functions based on this structure, such as pigment dispersibility and coating gloss. Since the function is expected, it is considered to be useful as a vehicle for offset printing ink, for example. Further, since the rosin copolymer (A) does not have a hydroxyl group in the molecule, when it is used as a vehicle for offset printing ink, the emulsification resistance of the offset printing ink to fountain solution and the printing ink film It is thought that the water resistance of is improved.

1 is a 1H NMR chart of an acryloyl group-containing rosin derivative (a-1-1) of Synthesis Example 1. FIG. Moreover, the part enclosed with a broken-line circle is a cyclic hydrocarbon residue derived from rosins. FIG. 2 is an IR chart of the acryloyl group-containing rosin derivative (a-1-1) of Synthesis Example 1. 3 is a 1H NMR chart of the acryloyl group-containing rosin derivative (a-1-2) of Synthesis Example 2. FIG. In addition, the portion surrounded by a broken-line circle is a cyclic hydrocarbon residue derived from rosins. 4 is an IR chart of the acryloyl group-containing rosin derivative (a-1-2) of Synthesis Example 2. FIG. 5 is a 1H NMR chart of the acryloyl group-containing rosin derivative (a-1-3) of Synthesis Example 3. FIG. In addition, the portion surrounded by a broken-line circle is a cyclic hydrocarbon residue derived from rosins. 6 is an IR chart of the acryloyl group-containing rosin derivative (a-1-3) of Synthesis Example 3. FIG. 7 is a 1H NMR chart of the acryloyl group-containing rosin derivative (a-1-4) of Synthesis Example 4. FIG. In addition, the portion surrounded by a broken-line circle is a cyclic hydrocarbon residue derived from rosins. 8 is an IR chart of the acryloyl group-containing rosin derivative (a-1-4) of Synthesis Example 4. FIG.

The rosin copolymer (A) according to the present invention (hereinafter referred to as the component (A)) is a (meth) acryloyl group-containing rosin derivative formed by reacting rosins and a (meth) acryloyl group-containing monovinyl ether compound with a hemiacetal. (A-1) (hereinafter referred to as component (a-1)) and styrenes (a-2) (hereinafter referred to as component (a-2)) are copolymerized.

As the rosins constituting the component (a-1), various known ones can be used without particular limitation. Specifically, for example, natural rosin [gum rosin, tall oil rosin, wood rosin, etc.], rosin obtained by stabilizing the natural rosin by various known methods [hydrogenated rosin, disproportionated rosin, etc. (Preferably those having 3 or less colors according to JIS K0071-2))], a polymerized rosin obtained by treating the natural rosin or the stabilized rosin by various known methods, and a stabilized treatment of the polymerized rosin. Polymerized rosin etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

Note that rosins include monomeric resin acids such as abietic acid, neoabietic acid, parastrinic acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid, and sandaracopimaric acid. And resin acids such as monomeric resin acid dimers.

  As the (meth) acryloyl group-containing monovinyl ether compound constituting the component (a-1), various known compounds can be used without particular limitation. Specifically, for example, an alkyleneoxy group-containing monovinyl ether compound [(meth) acrylic acid 2- (vinyloxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) ethyl, (meth) acrylic acid 2 -(Vinyloxyethoxy) propyl, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) (meth) acrylate Isopropyl, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, ( 2-methacrylic acid 2- (vinyloxyisopropoxyisopropoxy) ) Ethyl, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, (meta ) 2- (vinyloxyisopropoxyethoxy) isopropyl acrylate, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) Acrylic acid 2- (bi Roxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether, etc.], alkylene group-containing monovinyl ether compounds [(meth) acrylic acid 3-vinyloxypropyl, (meta ) 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acryl 1-vinyloxymethylpropyl acid, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, (meth) Acrylic acid 1 -Methyl-2-vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethyl (meth) acrylate Cyclohexylmethyl, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate], aromatic group-containing monovinyl ether compounds [p-vinyloxymethylphenyl (meth) acrylate Methyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl, etc.]. Among these, in consideration of availability in particular, the alkyleneoxy group-containing monovinyl ether compound is particularly preferably 2- (vinyloxyethoxy) ethyl (meth) acrylate.

The hemiacetal esterification reaction is not particularly limited, and various known methods can be employed. Specifically, for example, a rosin and a (meth) acryloyl group-containing monovinyl ether compound are usually about 30 to 150 ° C. (preferably 50 in the presence or absence of a catalyst, an organic solvent, and a radical polymerization inhibitor). ˜120 ° C.), usually about 10 minutes to 6 hours (preferably 20 minutes to 5 hours).

The amount of the rosins and the (meth) acryloyl group-containing monovinyl ether compound is not particularly limited, but from the stoichiometric viewpoint, the (meth) acryloyl group-containing monovinyl ether compound with respect to 1 mol of the carboxyl group in the rosin. The vinyl ether group is preferably in the range of usually about 0.5 to 3.0 mol (preferably 1.0 to 2.0 mol). If the amount is less than 0.5 mol, the yield of the target product decreases, whereas if it exceeds 3.0 mol, the residual ratio of unreacted products tends to increase.

As the catalyst, various known catalysts can be used without particular limitation. Specifically, for example, phosphoric acid ester-based acid catalysts [di-n-butyl phosphate, 2-ethylhexyl phosphate, monooctyl phosphate, etc.] and the like can be mentioned. A combination of the above can be used. In addition, the usage-amount of a catalyst is about 0.01-3 weight part normally (preferably 0.1-1.5 weight part) with respect to a total of 100 weight part of rosins and (meth) acryloyl group containing monovinyl ether compound. ).

As the organic solvent, various known solvents can be used without particular limitation. Specifically, for example, aromatic hydrocarbon solvents (benzene, toluene, xylene, ethylbenzene, etc., aromatic petroleum naphtha, tetralin (registered trademark), etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents [ Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, etc.), ether ester solvents (diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, tri Ethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether Methoxybutyl acetate, etc.], glycol ether acetate solvents (ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone) , Isophorone, mesityl oxide, methyl isoamyl ketone, ethyl butyl ketone, ethyl amyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, diisopropyl ketone, etc.), phosphate ester solvents (trimethyl phosphate, triethyl phosphate, tributyl phosphate, etc.) , Other solvents [turpentine oil, Solvesso # 100 (registered trademark of ExxonMobil), Solvesso # 150 (ExxonMobil YK registered trademark), etc.] and the like, which may be used alone or in combination of two or more, of them. The amount of the organic solvent used is not particularly limited, but considering the efficiency of the hemiacetal esterification reaction, the solid content concentration of the reaction system is usually in the range of about 20 to 95% by weight (preferably 30 to 90% by weight). It is good.

As the radical polymerization inhibitor, various known ones can be used without particular limitation. Specifically, for example, quinone polymerization inhibitors (methoquinone, hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, etc.), alkylphenol polymerization inhibitors [2,6-di-tert-butylphenol, 2,4 -Di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, etc.], amine Polymerization inhibitors [alkylated diphenylamine, N, N′-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6 Tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine etc.], copper dithiocarbamate polymerization inhibitors [copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, etc. ], N-oxyl polymerization inhibitors [2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine-N-oxyl, esters of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.]. It can be used alone or in combination of two or more. The addition amount of the radical polymerization inhibitor is usually 0.0005 with respect to the total weight of the rosins and the (meth) acryloyl group-containing monovinyl ether compound from the viewpoint of yield, suppression of polymerization, and economical reasons. It is good to set it as the range of about -0.5 weight% (preferably 0.001-0.1 weight%). Moreover, at the time of this reaction, superposition | polymerization prohibition means, such as air bubbling, can be taken.

Various purification treatments (filtration, distillation, solvent extraction, column separation, reprecipitation, etc.) can be applied to the component (a-1) thus obtained as necessary.

  Specific examples of the styrenes constituting the component (a-2) include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, chlorovinyltoluene and the like. These can be used singly or in combination of two or more.

Moreover, when (a-2) component contains acryloylmorpholine, since compatibility with (A) component and the below-mentioned (B) component (especially tetrafunctional (meth) acrylate) becomes favorable, it is preferable.

  The component (a-2) includes α, β unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid half ester, itaconic acid, itaconic anhydride, etc.), alkyl group (Meth) acrylic acid alkyl esters having about 1 to 18 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl ( Other monomers such as (meth) acrylate, stearyl (meth) acrylate, etc.] can be contained.

The content of styrenes in the component (a-2) is usually about 60 to 95% by weight, and the content of acryloylmorpholine and / or other monomers is usually about 5 to 40% by weight.

In the component (A), the weight ratio of the component (a-1) to the component (a-2) is not particularly limited, but it is usually preferably about 30/70 to 70/30 from the viewpoint of adhesion. .

The component (A) can be obtained by copolymerizing the (a-1) component and the (a-2) component (specifically, radical polymerization reaction). Specifically, in the presence of various polymerization initiators and, if necessary, a chain transfer agent, the (a-1) component and the (a-2) component are usually at a temperature of 100 to 150 ° C. for 30 to 3 hours. What is necessary is just to make it react to the extent. In addition, the said organic solvent can also be used as needed.

Various known initiators can be used without particular limitation as the polymerization initiator. Specifically, for example, inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.), organic peroxides (t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, etc.), Azo compounds [2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, etc.] and the like, and these may be used alone or in combination of two or more. Can be used. The amount used is usually about 0.01 to 5% by weight when the component (A) is 100% by weight (in terms of solid content).

The chain transfer agent can be used for the purpose of adjusting the molecular weight of the component (A), and various known ones can be used without particular limitation. Specific examples include dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like. These may be used alone or in combination of two or more. The amount used is usually about 0.01 to 5% by weight when the component (A) is 100% by weight (in terms of solid content).

  (A) Although the physical property of a component is not specifically limited, Usually, a softening point is about 70-150 degreeC, a weight average molecular weight is about 1,000-30,000, and an acid value (mgKOH / g) is about 0-30. is there.

  The active energy ray-curable resin composition of the present invention contains (A) component and polyfunctional (meth) acrylates (B) (hereinafter referred to as (B) component).

The component (B) specifically refers to a (meth) acrylate compound having at least two (meth) acryloyl groups in the molecule, preferably 3 to 4. Specifically, for example, bifunctional (meth) acrylate [hexamethylene glycol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( ) Acrylate, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, 1,9-nonanediol di (meth) acrylate, bisphenol A tetraethylene glycol diacrylate, etc.], trifunctional (meth) acrylate [ Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, ethylene oxide modified glycerol triacrylate, propylene oxide modified glycerol triacrylate, epsilon caprolactone modified trimethylolpropane tri (meth) acrylate, etc.], tetrafunctional (meth) Acrylate [ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate Etc.] (meth) acrylates having 5 or more functionalities [dipentaerythritol hexa (meth) acrylate etc.] and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, trifunctional (meth) acrylates and / or tetrafunctional (meth) acrylates are particularly trimethylolpropane tri (meth) acrylate and ditrimethylolpropanetetra (meta) from the viewpoint of coating film hardness during curing. ) At least one selected from the group consisting of acrylate and pentaerythritol tetra (meth) acrylate is preferred. In addition to the component (B), the component (a-1) and / or the component (a-2) may be used as a reactive diluent as necessary.

  The active energy ray-curable resin composition of the present invention can be obtained by mixing the component (A) and the component (B) by various known methods. In addition, although content of (A) component and (B) component is not specifically limited, From a viewpoint of the hardness and adhesiveness of a cured film, it is about 30 / 70-70 / 30 normally as solid content weight ratio. Is preferred.

In addition, when the active energy ray-curable resin composition of the present invention is cured with ultraviolet rays, it can further contain a photopolymerization initiator (hereinafter referred to as component (C)). Examples of the component (C) include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, etc. Gerare These may be used alone or in combination of two or more, of them. (C) The usage-amount of a component is about 1-10 weight part normally with respect to 100 weight part (solid content conversion) of an active energy ray curable resin composition.

  The active energy ray-curable resin composition of the present invention contains additives such as various pigments, colorants, photosensitizers, antioxidants, light stabilizers, and leveling agents in addition to the organic solvents described above. It can also be made.

  The cured product of the present invention is obtained by applying the active energy ray-curable resin composition of the present invention to various substrates and curing it with active energy rays such as ultraviolet rays and electron beams.

  As the substrate, various known materials can be used without particular limitation. Specifically, for example, a plastic substrate (polyolefin, polycarbonate, polymethyl methacrylate, polystyrene, polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), paper ( Art paper, cast coated paper, foam paper, PPC paper, high-quality coated paper, craft paper, polyethylene laminated paper, glassine paper, and the like. Among these, a plastic substrate, particularly a polyolefin substrate is preferable from the viewpoint of adhesion.

Examples of the coating method include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Further, the coating amount is not particularly limited, but usually, the weight after drying is about 0.1 to 30 g / m ² , preferably about 1 to ²⁰ g / m ² .

Examples of the ultraviolet light source include a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp. The amount of light, light source arrangement, and conveyance speed are not particularly limited. For example, when a high-pressure mercury lamp is used, the conveyance speed is usually 5 to 50 m / min for one lamp having a light amount of about 80 to 160 W / cm. Degree. In the case of an electron beam, the acceleration voltage is usually about 10 to 300 kV and the conveyance speed is usually about 5 to 50 m / min.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Synthesis of (a-1) Component>
Synthesis example 1
In a 300 ml flask equipped with a water pipe, 150 g of hydrogenated rosin (mainly containing dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid as resin acids) manufactured by Arakawa Chemical Industries, Ltd., 0.23 g of methoquinone, phenothiazine 0.23 g was charged and the reaction system was heated to 120 ° C. with stirring to melt them. Next, 82.9 g of 2- (vinyloxyethoxy) ethyl acrylate was dropped into the reaction system in 15 minutes from the dropping funnel, and then 2-ethylhexyl phosphate (trade name “AP-8”, Daihachi Chemical Industry Co., Ltd.). Co., Ltd.) 0.15 g was charged and kept at 100 ° C. for 1 hour to obtain an acryloyl group-containing rosin derivative (a-1-1).

Synthesis example 2
Into a 300 ml flask equipped with a water pipe, a hydride of acrylic acid-modified rosin manufactured by Arakawa Chemical Industries (mainly acrylopimaric acid, hydride of acrylopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydro 130 g (including abietic acid), 0.23 g of methoquinone and 0.23 g of phenothiazine were charged, and the reaction system was heated to 140 ° C. with stirring to melt them. Next, 102.4 g of 2- (vinyloxyethoxy) ethyl acrylate was added dropwise to the reaction system in 15 minutes from the dropping funnel, and then 0.15 g of AP-8 was charged, and the mixture was kept at 100 ° C. for 1 hour, and acryloyl A group-containing rosin derivative (a-1-2) was obtained.

Synthesis example 3
A 300 ml flask equipped with a water pipe is charged with 120 g of polymerized rosin manufactured by Arakawa Chemical Industries, Ltd., 0.23 g of methoquinone, and 0.23 g of phenothiazine. The temperature of the reaction system is raised to 160 ° C. with stirring. Melted. Next, 55.8 g of 2- (vinyloxyethoxy) ethyl acrylate was added dropwise to the reaction system taking 15 minutes from the dropping funnel, then 0.15 g of AP-8 was added, and the mixture was kept at 100 ° C. for 1 hour, and acryloyl A group-containing rosin derivative (a-1-3) was obtained.

Synthesis example 4
In a 300 ml flask equipped with a water pipe, 150 g of hydrogenated rosin (mainly containing dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid as resin acids) manufactured by Arakawa Chemical Industries, Ltd., 0.23 g of methoquinone, phenothiazine 0.23 g was charged, and the reaction system was heated to 160 ° C. with stirring to melt them. Next, 82.9 g of 2- (vinyloxyethoxy) ethyl methacrylate was added dropwise to the reaction system taking 15 minutes from the dropping funnel, and then 0.15 g of AP-8 was charged and kept at 100 ° C. for 1 hour, methacryloyl A group-containing rosin derivative (a-1-4) was obtained.

¹ H NMR chart (measuring instrument: GEMINI-300 (manufactured by VARIAN)), 300 MHz, CDCl3) and IR chart (measuring instrument: AVATAR−) of each of the derivatives (a-1-1) to (a-1-4) 330 (manufactured by Thermo, single reflection ATR) is shown in FIGS.

<Manufacture of (A) component>
Example 1
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 90 parts of xylene was charged and the temperature was raised to about 133 ° C. Then, from the dropping funnel, 25 parts of acryloyl group-containing rosin derivative (a-1-1), 75 parts of styrene, 2,2′-azobis (2-methylbutyronitrile) (trade name “ABN-E”, (stock) A mixture of 3.5 parts and 10 parts of xylene was added dropwise over 1.5 hours. Subsequently, after cooling the reaction system to room temperature, 400 parts of hexane was added and stirred for 30 minutes. Subsequently, the rosin copolymer was separated by decantation and dried at 100 ° C. for 2 hours and then at 90 ° C. for 2 hours. A rosin copolymer (A-1) having a softening point of 105.5 ° C., a weight average molecular weight of 8,600, and an acid value of 3.5 was obtained.

Example 2
In the same reaction vessel as in Example 1, 90 parts of xylene was charged and the temperature was raised to about 133 ° C. Next, from a dropping funnel, a mixed solution composed of 25 parts of acryloyl group-containing rosin derivative (a-1-1), 65 parts of styrene, 10 parts of acryloylmorpholine, 3.5 parts of ABN-E and 10 parts of xylene was added for 1.5 hours. It was dripped over. Subsequently, after cooling the reaction system to room temperature, 400 parts of hexane was added and stirred for 30 minutes. Subsequently, the rosin copolymer was separated by decantation and dried at 100 ° C. for 2 hours and then at 90 ° C. for 2 hours. A rosin copolymer (A-2) having a softening point of 97.5 ° C., a weight average molecular weight of 9,400, and an acid value of 4.0 was obtained.

Example 3
In the same reaction vessel as in Example 1, 90 parts of xylene was charged and the temperature was raised to about 133 ° C. Next, from the dropping funnel, 15 parts of acryloyl group-containing rosin derivative (a-1-1), 10 parts of acryloyl group-containing rosin derivative (a-1-2), 65 parts of styrene, 10 parts of acryloylmorpholine, ABN-E3.5 A mixture of 10 parts and xylene was added dropwise over 1.5 hours. Subsequently, after cooling the reaction system to room temperature, 400 parts of hexane was added and stirred for 30 minutes. Subsequently, the rosin copolymer was separated by decantation and dried at 100 ° C. for 2 hours and then at 90 ° C. for 2 hours. A rosin copolymer (A-3) having a softening point of 99.5 ° C., a weight average molecular weight of 13,400, and an acid value of 4.5 was obtained.

Example 4
In the same reaction vessel as in Example 1, 90 parts of xylene was charged and the temperature was raised to about 133 ° C. Next, from the dropping funnel, 15 parts of acryloyl group-containing rosin derivative (a-1-1), 10 parts of acryloyl group-containing rosin derivative (a-1-3), 65 parts of styrene, 10 parts of acryloylmorpholine, ABN-E3.5 A mixture of 10 parts and xylene was added dropwise over 1.5 hours. Subsequently, after cooling the reaction system to room temperature, 400 parts of hexane was added and stirred for 30 minutes. Subsequently, the rosin copolymer was separated by decantation and dried at 100 ° C. for 2 hours and then at 90 ° C. for 2 hours. A rosin copolymer (A-4) having a softening point of 101.5 ° C., a weight average molecular weight of 14,000, and an acid value of 3.0 was obtained.

Example 5
In the same reaction vessel as in Example 1, 90 parts of xylene was charged and the temperature was raised to about 133 ° C. Next, from a dropping funnel, a mixed solution composed of 25 parts of acryloyl group-containing rosin derivative (a-1-4), 65 parts of styrene, 10 parts of acryloylmorpholine, 3.5 parts of ABN-E and 10 parts of xylene was added for 1.5 hours. It was dripped over. Subsequently, after cooling the reaction system to room temperature, 400 parts of hexane was added and stirred for 30 minutes. Subsequently, the rosin copolymer was separated by decantation and dried at 100 ° C. for 2 hours and then at 90 ° C. for 2 hours. A rosin copolymer (A-5) having a softening point of 98.0 ° C., a weight average molecular weight of 9,000, and an acid value of 3.0 was obtained.

Comparative Example 1
In a reaction vessel similar to that in Example 1, 90 parts of xylene were charged and heated to about 133 ° C. Subsequently, a mixed liquid consisting of 65 parts of styrene, 25 parts of stearyl methacrylate, 10 parts of acryloylmorpholine, 3.5 parts of ABN-E and 8.7 parts of xylene was dropped from the dropping funnel over 1.5 hours. Next, a mixed solution consisting of 0.5 parts of ABN-E and 1.3 parts of xylene was dropped from another dropping funnel over 1 hour. Next, the temperature of the reaction system was raised to 160 ° C., then the pressure was reduced to 60 Torr, and the reduced pressure state was maintained for 1 hour. Next, by releasing the reduced pressure, a copolymer (i) having a softening point of 94.5 ° C., a weight average molecular weight of 11,800, and an acid value of 0.5 and having no rosin residue was obtained.

In the table, St represents styrene, ALM represents acryloylmorpholine, SMA represents stearyl methacrylate, Sp represents the softening point, Mw represents the weight average molecular weight, and AV represents the acid value (mgKOH / g).

<Preparation of active energy ray-curable resin composition>
Example 6
In the same reaction vessel as in Production Example 1, 40 parts of rosin copolymer (A-1) (in terms of solid content) and 30 parts of ditrimethylolpropane tetraacrylate (hereinafter referred to as DTMPTA), trimethylolpropane triacrylate (hereinafter referred to as the following) 30 parts) (referred to as TMPTA) was added, the temperature was raised to 90 ° C. and held for 30 minutes. Next, 5 parts of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by Ciba Japan Co., Ltd.) was added and held for 10 minutes to prepare an active energy ray-curable resin composition.

Examples 7-10
A reaction vessel similar to Production Example 1 was charged with 40 parts of rosin copolymer (A-1) (in terms of solid content) and 60 parts of DTMPTA, heated to 90 ° C. and held for 30 minutes. Next, 5 parts of Irgacure 184 was added and held for 10 minutes to prepare an active energy ray-curable resin composition for Example 7. Moreover, the active energy ray hardening-type resin composition for Examples 8-10 was prepared similarly except having changed the raw material to be used into what is shown in Table 2.

Examples 11-15
In a reaction vessel similar to Production Example 1, 40 parts of rosin copolymer (A-1) (in terms of solid content) and 60 parts of TMPTA were charged, heated to 90 ° C. and held for 30 minutes. Next, 5 parts of Irgacure 184 was added and held for 10 minutes to prepare an active energy ray-curable resin composition for Example 11. Moreover, the active energy ray hardening-type resin composition for Examples 12-15 was similarly prepared except having replaced the raw material to be used with what is shown in Table 2.

Comparative Examples 2 and 3
A reaction vessel similar to Production Example 1 was charged with 40 parts of copolymer (ii) (in terms of solid content) and 60 parts of DTMPTA, heated to 90 ° C. and held for 30 minutes. Next, 5 parts of Irgacure 184 was added and held for 10 minutes to prepare an active energy ray-curable resin composition for Comparative Example 2. Further, an active energy ray-curable resin composition for Comparative Example 3 was prepared in the same manner except that the raw materials used were changed to those shown in Table 2.

Comparative Examples 4 and 5
In a reaction vessel similar to Production Example 1, 40 parts of diallyl phthalate resin (trade name “Daiso Dup”, manufactured by Daiso Corporation) and 60 parts of DTMPTA are charged, and the temperature is raised to 90 ° C. for 30 minutes. Retained. Next, 5 parts of Irgacure 184 was added and held for 10 minutes to prepare an active energy ray-curable resin composition for Comparative Example 4. Further, an active energy ray-curable resin composition for Comparative Example 5 was prepared in the same manner except that the raw materials used were changed to those shown in Table 2.

<Evaluation of compatibility>
The compatibility of the component (A) and the component (B) in each active energy ray-curable resin composition was visually evaluated according to the following criteria.
○: Insoluble matter cannot be confirmed in the composition ×: Insoluble matter can be confirmed in the composition

<Production of cured film>
Using a bar coater (# 2), the active energy ray-curable resin composition of Example 6 was applied to art paper so that the film thickness was about 3 to 6 μm. ) Model UB-022-5B-60, conditions: high pressure mercury lamp 120 W / cm, irradiation distance 10 cm, conveyor speed 10 m / min) were used to produce a cured coating. Moreover, it replaced with the art paper and the cured film was created similarly using the polypropylene film (Brand name "pyrene film-OT P2161" thickness 20 micrometers, Toyobo Co., Ltd. product). Cured films were similarly prepared for the active energy ray-curable resin compositions of Examples 7 to 15 and Comparative Examples 3 to 5. In addition, about the active energy ray hardening-type resin composition of the comparative example 2, since compatibility was unsatisfactory, the cured film was not produced.

<Evaluation of adhesion>
For each of art paper and polypropylene (PP), an adhesive tape was applied to the cured coating, and 10 reciprocations were rubbed with a finger, and the degree of resin peeling when peeled at once was evaluated based on the following evaluation criteria. In the table, “-” means not evaluated.
○: 70% or more of the cured film remains.
X: The cured coating is completely peeled off.

Claims (6)

A rosin and a (meth) acryloyl group-containing monovinyl ether compound are subjected to a hemiacetal esterification reaction, and a (meth) acryloyl group-containing rosin derivative (a-1) and a styrene (a-2) are copolymerized. An active energy ray-curable resin composition comprising a rosin copolymer (A) and a polyfunctional (meth) acrylate (B). The active energy ray-curable resin composition according to claim 1, wherein the rosins are at least one selected from the group consisting of hydrogenated rosins, α, β unsaturated carboxylic acid-modified rosins, and polymerized rosins. The active energy ray-curable resin composition according to claim 1 or 2, wherein the (meth) acryloyl group-containing monovinyl ether compound is an alkyleneoxy group-containing monovinyl ether compound. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the styrene (a-2) further contains acryloylmorpholine. The active energy ray-curable resin composition according to claim 1, wherein the polyfunctional (meth) acrylates (B) are a trifunctional (meth) acrylate compound and / or a tetrafunctional (meth) acrylate compound. Hardened | cured material formed by hardening | curing the active energy ray hardening-type resin composition in any one of Claims 1-5.

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