JP7427853B1 - Active energy ray-curable adhesive composition, printed matter and laminate using the same - Google Patents

Abstract

An object of the present invention is to provide an active energy ray-curable adhesive composition that has excellent adhesive properties under low energy conditions and can suppress breakage of cold foil, and a laminate using the same. [Solution] An active energy ray-curable adhesive composition comprising a non-reactive resin (A), an ethylenically unsaturated monomer (B), and a photocleavable photoinitiator (C), The monomer (B) contains 10% by mass or more of a monofunctional monomer (B1) having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B), and is a photocleavable photoinitiator. The agent (C) contains a photocleavable initiator (C1) having a gram extinction coefficient of 1.0 L·g−1·cm−1 or more at a wavelength of 365 nm at 2% by mass based on the total mass of the adhesive composition. An active energy ray-curable adhesive composition containing the above and a laminate using the same. [Selection diagram] None

Description

The present invention relates to an active energy ray-curable adhesive composition suitable for bonding polymeric materials and a laminate using the same. Specifically, the present invention relates to an active energy ray-curable adhesive composition that has excellent workability, suitability for coating and printing, and has adhesive properties with a low amount of energy, and a metal foil stamping laminate using the same.

Generally, adhesive compositions are widely used in various fields such as packaging materials, display materials such as labels, building materials, electronic components, and optical components. Conventional solvent-drying adhesive compositions have poor productivity because it takes time to dry the solvent, and they also have environmental burden issues such as the generation of VOC (volatile organic compounds) and CO2 emissions. Adhesive compositions that are cured by active energy rays such as ultraviolet rays have come into use. This active energy ray-curable adhesive composition can generally be used without a solvent and can be cured in a short time and with little energy, so it has excellent properties in terms of improving productivity and reducing environmental impact. ing.

On the other hand, as the fields and applications in which active energy ray-curable adhesive compositions are used expand, their performance improves, and costs are reduced, there is a need for adhesive compositions that can be cured with low energy consumption and have sufficient adhesive properties. ing.

Furthermore, hot stamping and cold stamping are known as methods of transferring metal foil to an adhesive layer on a film base material to impart metallic luster to packaging materials, labels, and the like. The hot stamping transfer method transfers the metal foil to the base material by pressing the metal foil onto the base material using a heated mold, which is expensive, has low work efficiency, and is not suitable for substrates that are easily affected by heat. could not be applied to materials.

Therefore, in recent years, cold stamping transfer methods that do not require heating have been widely used. In the cold stamping transfer method, first, the metal foil is pressure-bonded to a base material coated with a photocurable adhesive at the location where the metal foil is to be transferred. After the photocurable adhesive is cured, the metal foil is peeled off from the base material, and the metal foil is transferred to the area on the base material where the photocurable adhesive was applied (hereinafter, created using the cold stamping method). The transferred metal foil is also called cold foil). In this way, the cold stamping transfer method does not require heating or applying pressure using a mold, so it is low cost and has good work efficiency, but it does have the problem of being prone to cracks (foil breakage) during the winding process. there were.

As an active energy ray-curable adhesive composition for cold foil, for example, a polyester resin having a weight average molecular weight of 2000 to 5000, an acid value of 40 to 80 (mgKOH/g), and a softening point of 80 to 120°C, a molecular weight of 200 or more, It has been reported that an active energy ray-curable printing ink containing a monofunctional monomer and a photoinitiator with a molar extinction coefficient (dm/mol cm) of 10,000 or less at a wavelength of 313 nm has excellent adhesive properties. (Patent Document 1).

Additionally, it has been reported that a photocurable adhesive for cold foil transfer containing a monomer component having a (meth)acrylate group, an oligomer component having a (meth)acrylate group, and a photopolymerization initiator can suppress cracking of cold foil. (Patent Document 2).

However, the compositions of Patent Documents 1 and 2 have a problem in that sufficient adhesion and crack resistance cannot be obtained under low energy conditions.

Japanese Patent Application Publication No. 2009-024139 JP2020-055987A

An object of the present invention is to provide an active energy ray-curable adhesive composition that has excellent adhesiveness and crack resistance under low energy conditions, and a laminate using the same.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the above problems can be solved by the active energy ray-curable adhesive composition shown below, and have completed the present invention.

That is, the present invention provides an active energy ray-curable adhesive composition containing a non-reactive resin (A), an ethylenically unsaturated monomer (B), and a photocleavable photoinitiator (C), which The unsaturated monomer (B) contains 10% by mass or more of a monofunctional monomer (B1) having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B), and is a photocleavable monomer. The photoinitiator (C) is a photocleavable initiator (C1) having a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm in an amount of 2% relative to the total mass of the adhesive composition. The present invention relates to an active energy ray-curable adhesive composition containing at least % by mass.

Further, the ethylenically unsaturated monomer (B) contains 70% by mass or more of a monomer having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B) according to claim 1. The present invention relates to an active energy ray-curable adhesive composition.

The present invention also relates to the active energy ray-curable adhesive composition according to claim 1 or 2, wherein the non-reactive resin (A) has a glass transition temperature (Tg) of 0°C or higher.

The present invention also relates to the above-mentioned active energy ray-curable adhesive composition used in flexographic printing.

The present invention also relates to a printed matter obtained by printing the active energy ray-curable adhesive composition on a base material.

The present invention also relates to a laminate in which metal foil is adhered to the printed matter.

According to the present invention, it is possible to provide an active energy ray-curable adhesive composition having excellent adhesiveness and crack resistance under low energy conditions, and a laminate using the same.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

In the following description, (meth)acrylate, (meth)acryloyl, and (meth)acrylic mean methacrylate and/or acrylate, methacryloyl and/or acryloyl, methacrylic and/or acrylic, respectively. Preferred compositions of the active energy ray-curable printing ink used in the present invention include the following compositions.

The active energy ray-curable adhesive composition of the present invention contains a non-reactive resin (A), an ethylenically unsaturated monomer (B), and a photocleavable photoinitiator (C), and comprises an ethylenically unsaturated monomer (C). The unsaturated monomer (B) contains 10% by mass or more of a monofunctional monomer (B1) having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B), and is a photocleavable monomer. The photoinitiator (C) is a photocleavable initiator (C1) having a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm in an amount of 2% relative to the total mass of the adhesive composition. Contains more than % by mass. By blending the non-reactive resin (A), good adhesion to various base materials is achieved, expanding the range of base material selection. By blending a monofunctional monomer (B1) with a glass transition temperature (Tg) of 0° C. or higher as the ethylenically unsaturated monomer (B), good adhesion and crack resistance are obtained, and the photocleavable photoinitiator Since (C) has a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm, it can be cured even with a low energy amount and adhesive properties can be obtained.

Examples of the non-reactive resin (A) include resins that are commonly used in the ink, paint, and adhesive industries and do not contain reactive functional groups such as unsaturated double bonds. . Specifically, silicone resin, polyester resin, fluororesin, petroleum resin, coumaron resin, phenol resin, urethane resin, urea resin, epoxy resin, cellulose resin, terpene resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, Examples include butyral resin and ketimine resin. These resins may be used alone or in combination of two or more.
Among these, polyester resins are preferred from the viewpoint of solubility in the ethylenically unsaturated monomer (B), adhesiveness, price, etc., and these resins may be used alone or in combination of two or more types. Further, the non-reactive resin (A) is preferably contained in an amount of 10 to 40% by mass, more preferably 15 to 35% by mass, in the total mass of the active energy ray-curable adhesive composition.

Commercially available polyester resins include, for example, Byron 220 (Mn = 2000, Tg = 53°C), Byron GK130 (Mn: 7000, Tg: 15°C), Byron GK590 (Mn: 7000, manufactured by Toyobo). Tg: 15°C), Byron GK680 (Mn: 6000, Tg: 10°C), Byron GK810 (Mn: 6000, Tg: 46°C), Byron GK780 (Mn = 11000, Tg = 36°C), Byron GK890 (Mn = 11000, Tg=17°C). Manufactured by Unitika: Elitel UE3210 (Mn: 20000, Tg: 45°C), Elitel UE3220 (Mn: 25000, Tg: 5°C), Elitel UE3300 (Mn: 8000, Tg: 45°C), Elitel UE9200 (Mn: 15000, Tg: 65°C). Manufactured by SK Chemical Company: Skybon ES403 (Mn: 9000, Tg: 40°C), Skybon ES460M (Mn: 7000, Tg: 37°C), Skybon ES601 (Mn: 6000, Tg: 18°C), Skybon ES710 (Mn: 10000) , Tg: 37°C), Skybon ES750 (Mn: 8000, Tg: 35°C), and the like.

The weight average molecular weight of the non-reactive resin (A) is preferably in the range of 1,000 to 30,000, more preferably 2,000 to 20,000.

The glass transition temperature (Tg) of the non-reactive resin (A) is preferably 0°C or higher because crack resistance is further improved, and more preferably 30°C or higher.

The ethylenically unsaturated monomer (B) is not particularly limited as long as it is a monomer having an ethylenically unsaturated double bond, but monofunctional or polyfunctional (meth)acrylate monomers, (meth)acrylamide monomers, vinyl monomers, allyl monomers, etc. monomers, etc. These may be used alone or in combination of two or more. The ethylenically unsaturated monomer (B) is preferably contained in an amount of 50 to 95% by mass, more preferably 55 to 90% by mass, in the total mass of the active energy ray-curable adhesive composition.

The ethylenically unsaturated monomer (B) contains 10% by mass or more of a monofunctional monomer (B1) having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B), and It is preferable that the content is at least % by mass. The upper limit of the content is not particularly limited, and may be 100% by mass based on the total mass of the ethylenically unsaturated monomer (B).

The glass transition temperature (Tg) means the Tg of a homopolymer, and is measured, for example, by differential scanning calorimetry (DSC), and is heated from -60°C to 200°C at a rate of 20°C/min, and then at -100°C/min. It is determined from the peak detected when the temperature is cooled for 1 minute and then raised again from -60°C to 200°C at a rate of 20°C/min.

As the monofunctional monomer (B1) having a glass transition temperature (Tg) of 0°C or higher,
Manufactured by KJ Chemicals: ACMO (acryloylmorpholine, Tg=145), DEAA (diethylacrylamide, Tg=81°C), HEAA (hydroxyethylacrylamide, Tg=98°C). Manufactured by SARTOMER: SR257 (stearyl acrylate, Tg = 35°C), SR506 (isobornyl acrylate, Tg = 97°C), SR339A (2-phenoxyethyl acrylate, Tg = 35°C), SR217NS (4-t-butylcyclohexyl acrylate, Tg=35°C). Manufactured by Osaka Organic Chemical Industry Co., Ltd.: Viscoat 155 (cyclohexyl acrylate, Tg = 15°C), Viscoat 160 (benzyl acrylate, Tg = 6°C), Viscoat 196 (3,3,5-trimethylcyclohexyl acrylate, Tg = 52°C), Viscoat 200 (cyclic trimethylolpropane formal acrylate, Tg = 27°C).
Manufactured by Kyoeisha Chemical Co., Ltd.: Light Ester E (ethyl methacrylate, Tg = 65°C), Light Ester NB (n-butyl methacrylate, Tg = 20°C), Light Ester IB (isobutyl methacrylate, Tg = 48°C), Light Ester TB ( ter-butyl methacrylate, Tg = 107°C), light ester THF (1000) (tetrahydrofurfuryl methacrylate, Tg = 60°C), light ester HO-250 (N) (2-hydroxyethyl methacrylate, Tg = 55, light ester Examples include DM (dimethylaminoethyl methacrylate, Tg=18°C), light ester DE (diethylaminoethyl methacrylate, Tg=20°C), etc. Monofunctional monomers having a glass transition temperature (Tg) of less than 0°C are used in the present invention. It can be used as appropriate as long as the purpose is not impaired.

Monofunctional ethylenically unsaturated monomers have the effect of significantly reducing the viscosity of active energy ray-curable adhesive compositions, regardless of the glass transition temperature, and improve the adhesion and smoothness of coated and printed films. preferable. The monofunctional ethylenically unsaturated monomer is preferably contained in an amount of 10 to 75% by mass, more preferably 20 to 70% by mass, in the total mass of the active energy ray-curable adhesive composition.

Furthermore, it is preferable to include 70% by mass or more of a monomer having a glass transition temperature (Tg) of 0°C or higher based on the total mass of the ethylenically unsaturated monomer (B), since this further improves crack resistance. % or more is more preferable. The upper limit of the content is not particularly limited, and may be 100% by mass based on the total mass of the ethylenically unsaturated monomer (B).

Typical examples of difunctional or higher functional monomers with a glass transition temperature (Tg) of 0°C or higher include HDDA (1,6-hexanediol diacrylate, Tg = 105°C, bifunctional), and TPGDA (tripropylene). Glycol diacrylate, Tg = 110°C, bifunctional), Aronix M-350 (EO-modified trimethylolpropane triacrylate, Tg = approximately 90°C, trifunctional), MIRAMERM370 (tris 2-hydroxyethyl isocyanurate triacrylate, Tg = 272°C, trifunctional) DPHA (dipentaerythritol hexaacrylate, Tg>250°C, hexafunctional), and the like. Further, there is no particular limitation as long as the glass transition temperature (Tg) is 0° C. or higher, and the monomers can be appropriately selected from the following known monomers and the like. Further, a difunctional or higher functional monomer having a glass transition temperature (Tg) of less than 0° C. can be used as appropriate within a range that does not impair the object of the present invention.

Examples of the ethylenically unsaturated monomer having two or more functionalities include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, and other alkylene glycols. Di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate (numbers represent molecular weight), tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxy Pivalyl hydroxypivalate di(meth)acrylate, Hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, Di(meth)acrylate of alkylene oxide (2 mol) adduct of bisphenol, Ethylene oxide of glycerin (3 mol) ) Difunctional monomers such as di(meth)acrylate adducts, di(meth)acrylate adducts of propylene oxide (3 mol) of diglycerin, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactonate tri (meth)acrylate, tri(meth)acrylate of glycerin adduct with ethylene oxide (3 mol), di(meth)acrylate of propylene oxide (3 mol) adduct of glycerin, ethylene oxide (3 mol) adduct of trimethylolpropane Trifunctional monomers such as tri(meth)acrylate, tri(meth)acrylate of propylene oxide (3 mol) adduct of trimethylolpropane, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactonate tetra(meth)acrylate , diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Examples include monomers having four or more functional groups.
The content of the bifunctional or higher ethylenically unsaturated monomer is preferably 65% by mass or less, more preferably 45% by mass or less based on the total mass of the active energy ray-curable adhesive composition.

The photocleavable photoinitiator (C) generates radicals by irradiation with active energy rays such as electron beams, ultraviolet rays, and visible light, and starts the crosslinking reaction and polymerization reaction of the ethylenically unsaturated monomer (B). The photocleavable photoinitiator is preferably contained in an amount of 2 to 10% by mass, more preferably 3 to 7% by mass, in the total mass of the active energy ray-curable adhesive composition. The photocleavable photoinitiators may be used alone or in combination of two or more.

The photocleavable photoinitiator (C) has excellent curability and adhesiveness because it has a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm. In addition, the gram extinction coefficient as used in the present invention is also simply called the extinction coefficient, and the absorbance is (As), the sample thickness (thickness inside the cell) is b (cm), and the sample concentration is c (g/g/cm). l), it is defined as gram extinction coefficient (as) = (As)/(b・c) (Chemistry Dictionary 1, p. 950, published February 5, 1970, Kyoritsu Co., Ltd. (See Publishing Co., Ltd.). For example, it is preferable to use a quartz cell with an internal thickness of 1 cm, and the measurement method is as follows: It can be measured by the method described in Kagaku Dojin Co., Ltd., published on the 1st.

As the photocleavable photoinitiator (C1) having a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (1.3 L・g ⁻¹・cm ⁻¹ ), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (2.2L・g ⁻¹・cm ⁻¹ ), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butanone-1 (5.0 L·g ⁻¹ ·cm ⁻¹ ), and the like. Initiators other than the photocleavable photoinitiator (C1) can be used as appropriate within a range that does not impair the purpose of the present invention.

[Additive]
In addition to the non-reactive resin (A), the ethylenically unsaturated monomer (B), and the photocleavable photoinitiator (C), the active energy ray-curable adhesive composition of the present invention contains, as additives, Known materials may be included as appropriate. For example, polymerization inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, sensitizers, optical brighteners, curing agents, coupling agents, plasticizers, leveling agents, surface conditioning agents, antifoaming agents, base materials Examples include wetting agents, adhesion promoters, antistatic agents, colored pigments, extender pigments, pigment dispersants, organic solvents, and water.

[solvent]
The active energy ray-curable adhesive composition of the present invention preferably does not substantially contain an organic solvent or water. "Substantially free" means 3% or less, more preferably 1% or less, based on the total mass of the active energy ray-curable adhesive composition.

[viscosity]
The viscosity of the active energy ray-curable adhesive composition of the present invention at 25° C. is preferably 100 to 3000 mPa·s, more preferably 200 to 2000 mPa·s. When the viscosity at 25° C. is within the above range, coating/printing suitability and adhesiveness are well balanced. The viscosity can be measured using a cone-plate viscometer (cone diameter: 20 mm, cone angle: 1 degree) at a shear rate of 100 s ⁻¹ in an environment of 25° C.

For printing the active energy ray-curable adhesive used for metal foil stamping (foil transfer) by the cold stamping method of the present invention, any generally known printing method can be used, such as spraying, showering, dipping, etc. , roll coater, die coater, spin coater, dispenser, inkjet printing, gravure printing, flexographic printing, screen printing, and other wet coating methods, and flexographic printing is particularly preferred.

[Curing method]
The method for curing the active energy ray-curable adhesive composition of the present invention is not particularly limited, and any known method can be used. For example, it can be cured by irradiation with alpha rays, gamma rays, electron beams, X-rays, ultraviolet rays, visible light, or infrared rays. Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable. The peak wavelength of ultraviolet rays is preferably 150 to 450 nm.

[Curing method with ultraviolet rays]
The method for curing the active energy ray-curable adhesive composition of the present invention with ultraviolet rays is not particularly limited, and known methods can be used, such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, Metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc. can be used. The integrated light amount may be 10 to 3000 mJ/cm ² , preferably 30 to 1000 mJ/cm ² . After irradiation with ultraviolet rays, heating can be performed as necessary to improve adhesion.

[Laminated body]
A layer of the active energy ray-curable adhesive composition of the present invention is formed on a base material by coating and printing, a metal foil is laminated, and the layers are laminated by a cold stamping method in which the active energy ray curable adhesive composition is cured and bonded by irradiation with active energy rays. You get a body. The film thickness when coating/printing the active energy ray-curable adhesive composition is usually preferably 1 to 50 μm, more preferably 1 to 10 μm.

[Base material]
The substrate on which the active energy ray-curable adhesive composition of the present invention is coated and printed is not particularly limited, and known materials can be used. For example, paper such as paper, cardboard, art paper, coated paper, synthetic paper, PET (polyethylene terephthalate), PVC (polyvinyl chloride), PC (polycarbonate), PE (polyethylene), PP (polypropylene), OPP (polymers), etc. Examples include plastic films such as axially oriented polypropylene). The film thickness of the base material is not particularly specified, and the surface to be coated or printed may be corona treated. Further, the surface may be coated with acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resin.

As the metal foil, a foil made of a metal such as copper, aluminum, nickel, iron, gold, silver, stainless steel, tungsten, chromium, titanium, or tin, or a foil made of an alloy of two or more of these metals can be used. In terms of foil price, copper, aluminum, and nickel foils are suitable. Furthermore, since the active energy rays are irradiated from above the foil, the transmittance of the active energy rays is also taken into consideration.

Hereinafter, the present invention will be explained in detail with reference to Examples, but the following Examples do not limit the scope of the present invention in any way.

[Preparation of active energy ray-curable adhesive composition: Example 1]
As the non-reactive resin (A), 20% by mass of Vylon GK680 (polyester resin, solid content 100% by mass), as the ethylenically unsaturated monomer (B), 20% by mass of ACMO (4-acryloylmorpholine), Aronix M- While heating 54% by mass of 350 (EO-modified trimethylolpropane triacrylate) at 80° C., the mixture was dissolved and mixed with disper stirring (1000 rpm). 6% by mass of Omnirad TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) was mixed into the mixture as a photocleavable photoinitiator (C) to prepare an active energy ray-curable adhesive composition.

[Preparation of active energy ray curable adhesive composition: Examples 2 to 9, Comparative Examples 1 to 5]
Examples 2 to 9 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1, except that the raw materials and amounts listed in Table 1 were changed. Note that the numbers in Table 1 indicate mass %.

[Method for producing laminate]
The obtained active energy ray-curable adhesive composition was coated on an easily adhesive PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4360) as a base material using bar coater #3 (adhesive film thickness about 5 μm). . Thereafter, a metal foil (manufactured by Murata Kinpaku Co., Ltd., GNC-F silver) as a laminating material was pasted together using a hand laminating roller. Furthermore, ultraviolet rays were irradiated from the metal foil side using a conveyor-type UV irradiation device (manufactured by I-Graphics, high-pressure mercury lamp, output 80 W/cm, conveyor speed 80 m/min, lamp height 11 cm), and the adhesive composition was was cured to produce a laminate. The integrated light amount in the UVA region measured with UV POWER PUCK II manufactured by EIT was as small as 15 mJ/cm ² , which is a low energy amount.

[Adhesiveness]
The adhesion (adhesion) of the aluminum part foil-stamped onto the base material was evaluated based on the following criteria by visually checking whether the foil adhered to the base material when the release paper was peeled off after UV irradiation.
〔evaluation〕
◎: No change (the foil does not come off at all.)
○: Slight peeling (less than 5%) was observed.
△: Peeling was observed in some parts (5 to less than 50%).
x: Peeling was observed in part (50% or more) or in the whole.

[Crack resistance]
The crack resistance (adhesion) of the aluminum part foil stamped on the base material was determined by visually observing the occurrence of cracks after foil stamping and wrapping it around a φ8 mm rod with the foil transfer side facing up. evaluated.
〔evaluation〕
◎: No cracks were visually observed.
○: Only minute cracks were observed.
×: Large cracks were confirmed.
-: Not evaluated due to insufficient adhesion.

Information on each raw material in Table 1 is as follows.
Non-reactive resin (A)
・Byron GK680: Manufactured by Toyobo, polyester resin, Tg 10℃
・Vylon 220: manufactured by Toyobo Co., Ltd., polyester resin, Tg 53°C
Ethylenically unsaturated monomer (B)
・ACMO: Manufactured by KJ Chemical Co., Ltd., 4-acryloylmorpholine, homopolymer Tg 145°C
・SR217NS: Manufactured by SARTOMER, 4-t-butylcyclohexyl acrylate, homopolymer Tg 35°C
・Viscoat 155: Osaka Organic Chemical Industry Co., Ltd., cyclohexyl acrylate, homopolymer Tg 15°C
・TPGDA: manufactured by Daicel Allnex, tripropylene glycol diacrylate, homopolymer Tg 55°C
・Aronix M-350: manufactured by Toagosei Co., Ltd., EO modified trimethylolpropane triacrylate, homopolymer Tg approximately 90°C
・Aronix M-101A: manufactured by Toagosei Co., Ltd., phenoxydiethylene glycol acrylate, homopolymer Tg - 8°C
photoinitiator
・Omnirad TPO: IGM Resins B. V. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, gram extinction coefficient at 365 nm: 1.3 L・g ⁻¹・cm ⁻¹
・SB-PI799: Manufactured by Sort, 2,4-diethylthioxanthone, gram extinction coefficient at 365 nm 16.4 L・g ⁻¹・cm ⁻¹
・DAIDO UV-CURE174: manufactured by Daido Kasei Kogyo Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone, gram extinction coefficient at 365 nm 0.0L・g ^-1・cm ^-1

As shown in Table 1, Examples 1 to 9 using the active energy ray-curable adhesive composition of the present invention exhibited excellent adhesion and crack resistance under low energy conditions.

Claims (4)

An active energy ray-curable adhesive composition containing a non-reactive resin (A), an ethylenically unsaturated monomer (B), and a photocleavable photoinitiator (C), and having a viscosity of 200 to 3000 mPa·s A method for producing a laminate in which a printed matter is flexographically printed on a base material, a metal foil is laminated to the printed material, and the product is cured and bonded by irradiation with active energy rays, the method comprising:
The active energy ray curable adhesive composition contains 15 to 40% by mass of the non-reactive resin (A) in the total mass of the active energy ray curable adhesive composition,
The ethylenically unsaturated monomer (B) contains 10% by mass or more of a monofunctional monomer (B1) having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B), and is resistant to light. The cleavable photoinitiator (C) is a photocleavable initiator (C1) having a gram extinction coefficient of 1.0 L·g ⁻¹ ·cm ⁻¹ or more at a wavelength of 365 nm based on the total mass of the adhesive composition. A method for producing a laminate containing 2% by mass or more. The laminate according to claim 1, wherein the ethylenically unsaturated monomer (B) contains 70% by mass or more of a monomer having a glass transition temperature (Tg) of 0° C. or higher based on the total mass of the ethylenically unsaturated monomer (B). How the body is manufactured. The method for producing a laminate according to claim 1 or 2, wherein the non-reactive resin (A) has a glass transition temperature (Tg) of 0°C or higher. The method for producing a laminate according to claim 1 or 2, wherein the non-reactive resin (A) is a polyester resin.