JP2023049953A - Active energy ray-curable type resin composition and cured product of the same - Google Patents

Abstract

To provide an active energy ray-curable type resin composition capable of obtaining a cured product having a high curing rate and excellent curl resistance, adhesiveness and solvent resistance.SOLUTION: There is provided an active energy ray-curable type resin composition which comprises a polyglycerol in which the total of the triglycerol concentration and the tetraglycerol concentration is 45 wt.% or more and each concentration of triglycerol and tetraglycerol is in the range of 10 to 70 wt.% and a (meth)acrylate of a polyglycerol alkylene oxide adduct comprising an alkylene oxide.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition and a cured product formed by curing the composition.

Active energy ray-curable resin compositions are fast-curing, highly productive, and can be used without solvents. , paints, inks, optical materials, electronic materials, medical resin materials, laminates, printed circuit boards, resist materials, semiconductor sealants, etc. Polyfunctional (meth)acrylates having three or more (meth)acryloyl groups are often used in active energy ray-curable resin compositions in order to improve functions such as surface hardness and scratch resistance of cured films. (Patent Document 1). However, when these polyfunctional (meth)acrylates are used as coating agents in particular, there is a problem that the curing component has a large cure shrinkage and the cured film tends to curl, and there is also a problem that it is brittle and easily cracked.

Therefore, a method of diluting a polyfunctional (meth)acrylate with a monofunctional (meth)acrylate or a bifunctional (meth)acrylate has been proposed as in Patent Document 2. However, since the cured product made from this resin composition has a low crosslinking density, there is a problem that the original curability of the polyfunctional (meth)acrylate is lowered. Further, Patent Document 3 discloses a method using a urethane (meth)acrylate obtained by reacting a polyfunctional (meth)acrylate with a polyvalent isocyanate. I didn't have enough sexuality.

Furthermore, in recent years, as interest in environmental issues such as global warming has increased, it has become a social trend for chemical manufacturers in particular to use plant-derived materials as an alternative to conventional petroleum-derived materials. has been strongly requested. In particular, in UV inks and UV adhesives that use active energy ray-curable resins, the degree of biomass has been emphasized.

JP-A-06-248008 JP 2009-287017 A JP 2012-229412 A

An object of the present invention is to provide an active energy ray-curable resin composition which has a high curing rate and can give a cured product having excellent curl resistance, adhesion and solvent resistance.

As a result of extensive studies by the present inventors, the total concentration of triglycerin and tetraglycerin is 50% by weight or more, and the concentration of each of triglycerin and tetraglycerin is in the range of 10% to 70% by weight. The inventors have solved the above problems and completed the present invention by an active energy ray-curable resin composition characterized by containing a (meth)acrylate of a polyglycerin alkylene oxide adduct consisting of polyglycerin and alkylene oxide. .

By using the active energy ray-curable resin composition of the present invention, it is possible to obtain a cured product that cures with a small amount of irradiation even in the presence of oxygen, has a high curing rate, and has excellent curl resistance, adhesion, and solvent resistance. be able to.

Hereinafter, the present invention will be described based on embodiments, but the scope of the present invention is not limited to these embodiments, and the present invention also includes forms modified within the scope of the present invention. .

The polyglycerin used in the (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention has a total concentration of triglycerin and tetraglycerin of 45% by weight or more, and each of triglycerin and tetraglycerin The concentration is in the range of 10% by weight to 70% by weight, preferably the sum of the concentration of triglycerin and the concentration of tetraglycerin is 50% by weight or more, and the concentration of each of triglycerin and tetraglycerin is 10% by weight. ~70% by weight. More preferably, the triglycerin concentration is 30% to 55% by weight, and the tetraglycerin concentration is 10% to 40% by weight. Polyglycerin can be obtained by dehydration condensation reaction of glycerin, synthesis using glycidol, epichlorohydrin, glycerin halohydrin and other glycerin analogues, or recovery of synthetic glycerin from glycerin distillation residue, etc. Among them, polyglycerin is generally used. A certain method is obtained by adding a small amount of an alkali catalyst to glycerin, heating it to a high temperature of 200° C. or higher, and polycondensing it while removing the generated water. The reaction is a sequential intermolecular dehydration reaction to produce a high polymer in sequence, resulting in a complex mixed composition of unreacted glycerin, diglycerin, triglycerin, tetraglycerin and the like. From this, unreacted glycerin and diglycerin are removed by distillation, the polyglycerin is further distilled, and the fraction is collected to obtain polyglycerin having the desired composition. In addition, the polyglycerol is derived from biomass resources, and can be mass-produced at low cost, and the active energy ray-curable resin can be produced economically and regularly.

For the composition analysis of polyglycerin, about 0.5 g of a polyglycerin sample and about 0.05 g of methyl palmitate (first grade reagent; Kishida Chemical) as an internal standard substance were accurately weighed, and about 1 g of pyridine (special grade reagent; Kishida Chemical) was added. Dissolve these in 8 ml, then inject 0.2 ml of TMS-HT (reagent; Tokyo Chemical Industry Co., Ltd.) into 20 μl of this solution, react in a warm bath, and then determine by subjecting 1 μl of the supernatant to the following analysis. can.

Gas chromatograph: GC2014 (manufactured by Shimadzu Corporation)
Column: OV-1 (manufactured by GL Science, inner diameter 3 mm, length 1.5 m)
Column temperature: 100°C to 350°C (heating rate 10°C/min)
Carrier gas: helium (50 ml/min)
Injection part temperature: 350°C
Detector temperature: 350°C
Detector: FID

The polyglycerin used in the (meth)acrylate of the polyglycerol alkylene oxide adduct of the present invention preferably has an average degree of polymerization of 2.5 to 4.5 calculated from the hydroxyl value, and preferably 2.5 to 3.5. more preferred. As used herein, the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value is a value calculated by a terminal analysis method, and is calculated from (Formula 1) and (Formula 2).
(Formula 1) molecular weight = 74n + 18
(Formula 2) Hydroxyl value = 56110 (n + 2)/molecular weight The hydroxyl value is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerin, and free hydroxyl groups contained in 1 g of polyglycerin are acetylated. milligrams of potassium hydroxide required to neutralize the acetic acid required for The number of milligrams of potassium hydroxide is calculated according to the Japan Oil Chemists' Society compilation, "Japan Oil Chemists' Society Establishment, Standard Oil Analysis Test Method, 2013 Edition". R-PG and PGL-S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) can be used as commercially available polyglycerin.

The alkylene oxide used in the (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention preferably has 2 to 4 carbon atoms. Examples thereof include ethylene oxide, propylene oxide, butylene oxide and the like, with ethylene oxide and propylene oxide being preferred. Moreover, these alkylene oxides may be used alone or in combination of two or more. The average number of alkylene oxide additions is preferably more than 0 and 20 or less, more preferably 10 or less per hydroxyl group of polyglycerin as a raw material. When the average number of alkylene oxide additions per hydroxyl group of polyglycerin is within this range, a cured product having a high curing rate and high surface hardness can be obtained.

There are no particular restrictions on the method for producing the (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention. For example, an arbitrary amount of alkylene oxide is added to a specific polyglycerin by a known method, the resulting polyglycerol alkylene oxide adduct is heated and stirred with (meth)acrylic acid, and the water produced is removed from the system. A dehydration esterification method in which an esterified product is obtained by reacting while extracting, and a polyglycerin alkylene oxide adduct is heated and stirred with a lower alcohol (meth)acrylic acid ester, and the resulting lower alcohol is extracted out of the system and reacted. A transesterification method for obtaining an esterified product can be mentioned.

The (meth)acrylate of the (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention is preferably obtained by esterifying two or more of the hydroxyl groups of the polyglycerin alkylene oxide adduct with (meth)acrylic acid. More preferably, one or more of them are esterified with (meth)acrylic acid. When two or more are esterified with (meth)acrylic acid, a (meth)acrylate with sufficient curability is obtained.

The (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention is characterized by having a biomass degree of 20% or more. As a result, the greenhouse gas emissions of the active energy ray-curable resin composition can be reduced. Moreover, a high degree of biomass can also reduce the amount of fossil resource-based materials such as petroleum used, which is significant in terms of sustainable use of resources. The biomass degree is preferably 25% or more. When more importance is placed on reducing greenhouse gases, the biomass degree may be 30% or more. Although the upper limit of the biomass degree is 100%, it may be about 50% or less in consideration of the properties of the active energy ray-curable resin composition. In this specification, the term "biomass degree" refers to the weight ratio of the biomass material to the weight of the (meth)acrylate of the polyglycerin alkylene oxide adduct. The biomass degree of the (meth)acrylate of the polyglycerin alkylene oxide adduct is obtained by obtaining the biomass degree of the raw material that constitutes it, and multiplying this by the weight ratio of the compound (the weight ratio of the member to the total weight). It can be calculated by determining the total biomass amount of the wood (total value of the above values) and dividing it by the total weight of the (meth)acrylate of the polyglycerin alkylene oxide adduct.

In addition, "biomass material" refers to a material derived from renewable organic resources. Typically, it refers to materials derived from biological resources that can be sustainably reproduced in the presence of sunlight, water, and carbon dioxide. Therefore, materials derived from fossil resources that are depleted by post-mining use are excluded. The biomass material may be, for example, the renewable organic resource itself, or a material obtained by chemically or biologically synthesizing the organic resource.

The above biomass materials emit CO ₂ by combustion or the like _. resulting in virtually no _CO2 increase in In the technology disclosed herein, based on the idea as described above, the biomass material is regarded as carbon-neutral in that it does not substantially increase or decrease carbon by circulating in the global environment in a relatively short period of time. Then, based on the above idea, by using the above biomass material at a predetermined ratio or more, it is possible to reduce the emission of CO ₂ , which is a representative component of greenhouse gases.

The method for producing the active energy ray-curable resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing multiple components with an apparatus such as a mechanical stirrer or a magnetic stirrer.

The active energy ray-curable resin composition of the present invention can be cured by a known method using an active energy ray. Examples of active energy rays include rays such as ultraviolet rays, visible rays and infrared rays, and electromagnetic waves such as electron beams, X-rays and gamma rays. Curing by ultraviolet irradiation is preferable from the viewpoints of curing speed, cost of equipment, versatility and the like. . Light sources for curing by ultraviolet irradiation include high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, and LEDs.

When the active energy ray-curable resin composition of the present invention is cured by UV irradiation, it is necessary to use a photopolymerization initiator. Any known photopolymerization initiator may be used, for example, benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, alpha- Hydroxyacetophenones, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, monoacylphosphine oxide, etc. benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzophenone, methylbenzophenone, 4,4'-bisdiethylaminobenzophenone, 4-benzoyl-4'-methyl Benzophenones such as diphenyl sulfide, thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2-isopropylthioxanthone, and the like. These may be used alone or in combination of two or more.

When it is necessary to use a photopolymerization initiator, the amount used is 0.1% by weight to 15% by weight, preferably 0.5% by weight to 10% by weight, based on the total amount of the active energy ray-curable resin. be.

Moreover, when using a photoinitiator, it can be used individually or in combination with 2 or more types of photosensitizers. Examples of photosensitizers include triethanolamine, triisopropanolamine, 4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethyl (n-butoxy)ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and the like.

The active energy ray-curable resin composition of the present invention is characterized by containing a (meth)acrylate of a polyglycerol alkylene oxide adduct, and other ethylenically unsaturated One or two or more compounds having a group can be blended.

Among the compounds having ethylenically unsaturated groups that can be blended in the active energy ray-curable resin composition of the present invention, specific examples of monofunctional compounds having one ethylenically unsaturated group include methyl (meth ) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, alkyl (meth) acrylate such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Alicyclic alkyl (meth) acrylates, aralkyl (meth) acrylates such as benzyl (meth) acrylate, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ( Dimeric or higher oligomers that are Michael addition reaction products of unsaturated carboxylic acids such as meth)acrylic acid, crotonic acid, and cinnamic acid, ω-carboxypolycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth) acrylates, carboxyl group-containing (meth)acrylates such as monohydroxyethyl succinate (meth)acrylate, alkoxysilyl group-containing (meth)acrylates, vinyl monomers such as N-vinylpyrrolidone and N-vinylcaprolactam, triethylene glycol vinyl ethers such as divinyl ether and hydroxyethyl vinyl ether;

Among the compounds having ethylenically unsaturated groups, specific examples of bifunctional compounds having two ethylenically unsaturated groups include di(meth)acrylate of ethylene glycol, di(meth)acrylate of tetraethylene glycol, tri Glycol di(meth)acrylates such as propylene glycol di(meth)acrylate and the like can be mentioned.

Among the compounds having ethylenically unsaturated groups, specific examples of polyfunctional compounds having 3 or more ethylenically unsaturated groups include glycerin, diglycerin, trimethylolpropane, pentaerythritol, tris(2-hydroxyethyl). Oligomers such as (meth)acrylates, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, etc., which are alkylene oxide adducts of polyhydric alcohols such as isocyanurate, ditrimethylolpropane, dipentaerythritol, and xylitol. mentioned.

The active energy ray-curable resin composition of the present invention contains organic solvents such as methyl ethyl ketone, ethanol, toluene, hexane, ethyl acetate, and methyl cellosolve, polyester elastomers, polyurethane elastomers, and acrylic polymers as long as the effects of the present invention are not impaired. Non-reactive polymer resins such as polydiallyl phthalate, reactive polymer resins such as polydiallyl isophthalate, leveling agents, antifoaming agents, silane coupling agents, antioxidants, UV absorbers, pigments/dyes, light Additives such as stabilizers, polymerization inhibitors, antistatic agents and flame retardants, inorganic fillers such as calcium carbonate, talc, silica and zirconium compounds, cellulose fibers, carbon fibers and the like can be added.

The form of the cured product obtained by curing the active energy ray-curable resin composition of the present invention is not particularly limited, and can be selected from various forms such as coating films, films, and three-dimensional objects formed by known methods. When used by coating on a substrate, it can be applied to various substrates such as plastics, metals, inorganic materials, wood, paper, and composite substrates thereof.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, "parts" in the examples are based on weight. In addition, ethylene oxide is abbreviated as "EO" in the examples.

<Synthesis of polyglycerin EO acrylate>
Purified glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and sodium hydroxide as a catalyst were added to a four-necked flask equipped with a thermometer and a stirrer, and reacted at 250°C under a nitrogen stream to obtain polyglycerin. . Then, this composition was distilled under reduced pressure, and the average degree of polymerization was 3. The specific composition was about 25% diglycerin and below, about 52% triglycerin, about 18% tetraglycerin, about 4% pentaglycerin, Polyglycerin A was obtained with about 1% hexaglycerin or higher. Next, polyglycerin A and potassium hydroxide as a catalyst were added, and an addition reaction was carried out while blowing ethylene oxide gas to obtain a polyglycerin EO adduct. Furthermore, a reaction vessel equipped with a thermometer, a stirrer, a Dean-Stark apparatus, and an air blowing tube was charged with 382.68 g (0.81 mol) of polyglycerin-EO adduct, 600 g of toluene, 30.00 g of p-toluenesulfonic acid, and hydroquinone monomethyl. 0.60 g of ether, 0.24 g of cupric chloride, 0.60 g of sodium hypophosphite monohydrate, and 376.52 g (5.22 mol) of acrylic acid were charged, and the mixture was brought to a toluene reflux atmosphere while stirring while blowing air. The temperature was raised, and the dehydration esterification reaction was carried out over about 5 hours. After completion of the reaction, 446.09 g of polyglycerin-EO adduct acrylate (hereinafter referred to as "A1") was obtained by successively washing with alkaline water and washing with water, and distilling off toluene from the organic layer under reduced pressure. Similarly, A2 and A3 shown in Table 1 were obtained by changing the type of polyglycerin and the average number of EO additions. The polyglycerin B used in A3 is polyglycerin with an average degree of polymerization of 4 (total concentration of triglycerin and tetraglycerin is about 34% by weight).

Table 2 shows the results of evaluating the viscosity and water solubility of the acrylate of the polyglycerin-EO adduct obtained above and DPHA (dipentaerythritol hexaacrylate), which is a general-purpose polyfunctional acrylate.

<Viscosity>
Using an E-type rotational viscometer (HBDV-II+ProCp, manufactured by Brookfield), the viscosities of polyglycerin-EO adducts acrylates (A1) to (A3) and DPHA at 25° C. were measured.

<Water solubility>
Water was added to the acrylates (A1) to (A3) of the polyglycerol-EO adducts and DPHA, and the maximum amount of added water that could maintain the transparency of the appearance was determined according to the following criteria.
(criterion)
A: 5% water can be dissolved.
○: 5% of water can be dissolved, but slightly dull.
x: 5% of water cannot be dissolved, and separation and dullness are observed.

<Example 1>
Polyglycerol EO adduct acrylate (A1) 100 parts, 1-hydroxycyclohexylphenyl ketone (Irgacure 184: manufactured by BASF Japan, hereinafter referred to as "Irg184") as a photopolymerization initiator 5 parts are uniformly stirred and mixed to activate energy. A ray-curable resin composition was obtained.

<Example 2>
In the same manner as in Example 1 except that the acrylate (A2) of the polyglycerin EO adduct shown in Table 1 was used instead of the acrylate (A1) of the polyglycerin EO adduct in Example 1, the active energy ray-curable A resin composition was obtained.

<Reference example>
In the same manner as in Example 1 except that the polyglycerin EO adduct acrylate (A3) shown in Table 1 was used instead of the polyglycerol EO adduct acrylate (A1) in Example 1, the active energy ray-curable A resin composition was obtained.

<Comparative example>
An active energy ray-curable resin composition was obtained in the same manner as in Example 1, except that DPHA was used instead of the acrylate (A1) of the polyglycerin-EO adduct of Example 1.

The active energy ray-curable resin compositions obtained in Examples 1 and 2, Reference Examples, and Comparative Examples were evaluated for curability and physical properties of cured products by the following methods. The active energy ray-curable resin compositions obtained in Examples 1 and 2, Reference Examples, and Comparative Examples were coated on a polyethylene terephthalate film (hereinafter referred to as “PET film”) with a bar coater so that the film thickness in each evaluation was obtained. A belt conveyor type UV irradiation device (product name: Eye Grantage ECS-401GX, manufactured by Eye Graphics Co., Ltd.) equipped with a high-pressure mercury lamp is used in an air atmosphere at an irradiation amount of 500 mJ/cm ² and an illuminance of 100 mW. /cm ² to obtain a cured product. After curing the resulting cured product in an environment of 23° C. and 50% RH for 12 hours or more, surface hardness, curl resistance, adhesion, solvent resistance and water contact angle were evaluated. Table 3 shows the results.

<Curing rate>
The curing rate (hereinafter referred to as “final curing rate”) when the active energy ray-curable resin composition is UV-cured is measured by Fourier transform infrared spectroscopy (hereinafter referred to as “FT-IR”). It was obtained from the change in the absorption peak of the C=C stretching vibration peak (near 1635 cm ^-1 ). For the FT-IR measurement, a Fourier transform infrared spectrometer (Spectrum 100, manufactured by PerkinElmer Japan Co., Ltd.) equipped with a reflectance measurement accessory was used. From the obtained FT-IR spectrum, the final cure rate was determined by (Equation 3) and (Equation 4) using the absorption peak of the C═O stretching vibration peak (around 1740 cm ⁻¹ ) of the ester group as a reference.
(Formula 3) Absorption peak area ratio = C = C stretching vibration peak area / C = O stretching vibration peak area (Formula 4) Final hardening rate (%) = {1-(a/b)} x 100
a: Absorption peak area ratio at an integrated dose of 100 mJ/cm ² b: Absorption peak area ratio at an integrated dose of 0 mJ/cm ²

<Surface hardness>
Surface hardness was evaluated by pencil hardness according to JIS K5600. The coating film surface of the cured product prepared so as to have a film thickness of 10 μm was scratched with a pencil under a load of 750 g, and the pencil hardness was defined as the hardest without scratching. Lumirror 100-S10 (manufactured by Toray Industries, Inc., thickness 100 μm) was used as the PET film.

<Curl resistance>
A cured product having a film thickness of 10 μm was cut into a piece of 100 mm×100 mm and placed on a horizontal table with the coating surface facing upward, and the raised heights of the four corners were measured. The average value was calculated, and the curl property was determined according to the following criteria. Cosmoshine A4300 (manufactured by Toyobo Co., Ltd., thickness: 100 μm) was used as the PET film.
(criterion)
◎: Average height is less than 3 mm ○: Average height is 3 mm or more and less than 10 mm △: Average height is 10 mm or more and less than 20 mm ×: Average height is 20 mm or more

<Adhesion>
In accordance with JIS K5600, a cutter knife was used to make 100 grid cuts of 1 mm square on the surface of the cured product prepared to have a film thickness of 10 μm. Subsequently, a cellophane tape (manufactured by Nichiban Co., Ltd.) was pasted on the 100 square grid cuts, and the tape was peeled off after 1 minute. At this time, the number of non-peeled grids was confirmed using a fluorescence microscope (BZ-X800, manufactured by KEYENCE CORPORATION) and judged according to the following criteria. Cosmoshine A4300 (manufactured by Toyobo Co., Ltd., thickness: 100 μm) was used as the PET film.
(criterion)
○: The number of remaining grids is 80 squares or more ×: The number of remaining grids is less than 80 squares

<Solvent resistance>
In accordance with JIS K5600, methanol (manufactured by Kishida Chemical Co., Ltd.), acetone (manufactured by Kishida Chemical Co., Ltd.), methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd.) on the coating surface of the cured product prepared so that the film thickness is 10 μm Co., Ltd.), ethyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd.), and toluene (manufactured by Kishida Chemical Co., Ltd.). It was visually confirmed and judged according to the following criteria. Cosmoshine A4300 (manufactured by Toyobo Co., Ltd., thickness: 100 μm) was used as the PET film.
(criterion)
〇: No change in appearance under all conditions △: Traces of droplets remain under some conditions ×: Whitening and cracks occur under some or all conditions

<Water contact angle>
Using a surface tensiometer (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.), 1.0 μL of water droplets are dropped on the coating surface of the cured product prepared so that the film thickness is 10 μm. The contact angle was obtained by the θ/2 method after 1 minute from the start. Lumirror 100-S10 (manufactured by Toray Industries, Inc., thickness 100 μm) was used as the PET film.

From the evaluation results of Examples 1 and 2 in Table 3, the cured product obtained from the active energy ray-curable resin composition comprising the (meth)acrylate of the polyglycerin alkylene oxide adduct of the present invention is a poly with an average degree of polymerization of 4. Curability, curl resistance, adhesion and solvent resistance equal to or better than those of Reference Examples using glycerin can be obtained. In particular, it can be seen that the curing rate is about 2.5 times higher than that of the comparative example, and the curl resistance is also good. In addition, as can be seen from Table 2, it has a low viscosity, so it is possible to achieve both excellent handling properties and physical properties of the cured coating film.

Claims (5)

Polyglycerin consisting of polyglycerin and alkylene oxide, wherein the total concentration of triglycerin and tetraglycerin is 45% by weight or more, and the concentration of each of triglycerin and tetraglycerin is in the range of 10% by weight to 70% by weight An active energy ray-curable resin composition comprising a (meth)acrylate of an alkylene oxide adduct. 2. The active energy ray-curable resin composition according to claim 1, wherein the (meth)acrylate of said polyglycerin alkylene oxide adduct has a biomass degree of 20% or more. 3. The active energy ray-curable resin composition according to claim 1, wherein the alkylene oxide of the (meth)acrylate of the polyglycerol alkylene oxide adduct has 2 to 4 carbon atoms. The average addition number of alkylene oxide of (meth)acrylate of the polyglycerin alkylene oxide adduct is more than 0 and 10 or less per hydroxyl group of polyglycerin according to any one of claims 1 to 3. An active energy ray-curable resin composition. A cured product formed by curing the active energy ray-curable resin composition according to any one of claims 1 to 4.