JP2019151774A - Active energy ray-curable adhesive composition - Google Patents

Abstract

To provide an active energy ray-curable adhesive composition which has a low odor, exhibits excellent curability even under low energy irradiation conditions, and gives a cured film excellent in adhesive force and removability.SOLUTION: The active energy ray-curable adhesive composition contains the following components (A), (B) and (C) as essential components: (A) a compound having two or more ethylenically unsaturated groups; (B) a compound having an aromatic group and one ethylenically unsaturated group; and (C) (C-1) a photopolymerization initiator having a molecular weight of 300 or more excluding an acylphosphine oxide compound and/or (C-2) a photopolymerization initiator containing an acylphosphine oxide compound as an essential component.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable pressure-sensitive adhesive composition, and can be used for various applications such as pressure-sensitive adhesive labels, pressure-sensitive adhesive tapes and special pressure-sensitive adhesive films, and can be preferably used particularly for re-peeling applications. It belongs to these technical fields.
In the present specification, an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate and / or methacrylate is represented as a (meth) acrylate, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. It expresses.
In the present specification, “monofunctional” means a compound having one ethylenically unsaturated group such as a (meth) acryloyl group.

The pressure-sensitive adhesive is used for various labels, tapes, and the like, taking advantage of the function of being peelable after being applied. Among them, adhesives with weak adhesive strength are also called re-peelable adhesives, and since they have a function that can be easily peeled off from the adherend after a certain period of time, they can be used in architecture, automobile manufacturing, electronic equipment, etc. Are widely used as masking tapes and protective films.
As a more specific application of the releasable pressure-sensitive adhesive, there is a releasable pressure-sensitive adhesive processed paper in which the opposite surface of the folding sheet on which general information and confidential information are printed on the overlapping surface is detachable, In recent years, it has been widely used in various notification forms from the viewpoint of automation of creation of notifications and protection of personal information.
This re-peelable pressure-sensitive adhesive paper is provided with a pressure-sensitive re-peelable pressure-sensitive adhesive layer at a predetermined portion of the superposed surface so that the superposed surfaces adhere to each other. When the removable pressure-sensitive adhesive layer is brought into contact with each other and a high pressure is applied, they are adhered to each other during normal handling, and can be removed by peeling.

Adhesives are broadly classified into solvent-based adhesives, emulsion-type adhesives, and solventless-type adhesives depending on their form, but they are a type of solvent-free adhesives because they do not require solvents and can reduce energy costs. Attention has been focused on the active energy ray-curable adhesive.
Unlike solvent-type adhesives and emulsion-type adhesives, active energy ray-curable adhesives can reduce energy costs because they do not require a process to remove solvents such as solvent and water when forming an adhesive layer. In addition, it is an environmentally friendly adhesive because it does not require a solvent. For these reasons, it has recently been used in various fields such as image display devices, home appliances, information equipment, automotive interior / exterior members, building materials, and labels. Has been.

Conventionally, an active energy ray-curable pressure-sensitive adhesive mainly composed of a (meth) acrylic polymer is known. The pressure-sensitive adhesive is a composition containing an organic solvent in order for the (meth) acrylic polymer to use an organic solvent during synthesis or to reduce the viscosity. When forming the organic solvent, it is necessary to remove the organic solvent by drying.
However, since it was difficult to make the residual organic solvent in the adhesive layer, which is a cured film, zero, there was a problem in terms of odor and safety when used as an adhesive tape. Things are sought.

As a solventless composition, a dry resin (meth) acrylic polymer, an unsaturated monomer having one ethylenically unsaturated group (hereinafter referred to as “monofunctional monomer”), and a polyfunctional (meth) acrylate A composition is disclosed (Patent Document 1).
However, even when the coating film is laminated with a release film and UV irradiation is performed while blocking air, the curability decreases due to the inhibition of polymerization by dissolved oxygen in the coating film, and the cured film has a pressure-sensitive adhesive layer. Since unreacted monofunctional monomer remained, there were problems in terms of odor and safety when used as an adhesive tape.

In addition, a solventless composition mainly composed of an acrylic oligomer such as urethane (meth) acrylate is also known.
Patent Document 2 discloses a composition comprising a urethane (meth) acrylate and a compound having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”). By using monofunctional (meth) acrylate, it is easy to have no solvent and low viscosity, and it is easy to adjust the glass transition temperature of the cured film, but the curability decreases due to the influence of polymerization inhibition by dissolved oxygen in the coating film, Since unreacted monofunctional (meth) acrylate remains in the pressure-sensitive adhesive layer, there are problems in terms of odor and safety when used as a pressure-sensitive adhesive tape.

Patent Document 3 discloses a composition comprising hydrogenated polybutadiene-based urethane (meth) acrylate and (meth) acrylate, and Examples 9 and 10 show simple substances remaining as unreacted substances in the pressure-sensitive adhesive layer. A composition that does not contain a functional (meth) acrylate and contains 20% by weight of a bifunctional acrylate such as tripropylene glycol diacrylate (hereinafter referred to as “TPGDA”) or 1,9-nonanediol diacrylate (hereinafter referred to as “NDDA”). Things are disclosed.
However, since the content of TPGDA or NDDA is as small as 20% by weight, the viscosity of the composition was high and the coating property was insufficient. On the other hand, when the content of TPGDA or NDDA is increased, the coating property can be improved by reducing the viscosity of the composition, but there is a problem that the tack does not exist and it cannot be bonded to the adherend.

JP 2007-217674 A JP 2014-5368 A JP 2003-155455 A

  The inventors of the present invention are diligent in finding an active energy ray-curable pressure-sensitive adhesive composition having a low odor, excellent curability even under low energy irradiation conditions, and a cured film obtained having excellent adhesive strength and removability. It was examined.

In order to solve the above problems, the present inventors have found that an active energy ray-curable pressure-sensitive adhesive composition containing a polyfunctional unsaturated compound, an aromatic monofunctional unsaturated compound, and a high molecular weight photopolymerization initiator has a low odor. Thus, the present invention has been completed by finding that the cured film is excellent even under low energy irradiation conditions and that the resulting cured film is excellent in adhesive strength and removability.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, low odor, excellent curability even under low energy irradiation conditions, and the resulting cured film can be excellent in adhesive strength and removability.

The present invention relates to an active energy ray-curable pressure-sensitive adhesive composition (hereinafter sometimes simply referred to as “composition”) containing the following components (A), (B) and (C) as essential components.
-Component (A): Compound having two or more ethylenically unsaturated groups-Component (B): Compound having aromatic group and one ethylenically unsaturated group-Component (C): (C-1) Photopolymerization initiator having a molecular weight of 300 or more excluding the acylphosphine oxide compound and / or (C-2) Photopolymerization initiator containing an acylphosphine oxide compound as an essential component. (A), (B) and (C) Components, active energy ray-curable pressure-sensitive adhesive compositions, and uses will be described.

1. Component (A) The component (A) is a compound having two or more ethylenically unsaturated groups.
By including the component (A), the cured film of the composition has excellent removability.
Examples of the ethylenically unsaturated group in component (A) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, and a (meth) acryloyl group is preferred.
In the following, “◯ functional” means a compound having ○ ethylenically unsaturated groups, and “polyfunctional” means a compound having 2 or more ethylenically unsaturated groups.

As the component (A), polyfunctional (meth) acrylate is preferable.
Specific examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and nonanediol di (meth). Alkylene glycol di (meth) acrylates such as acrylate;
Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate; and di (meth) of alkylene oxide adducts of bisphenol A Di (meth) acrylates of bisphenol compound alkylene oxide adducts such as acrylates and di (meth) acrylates of bisphenol F alkylene oxide adducts.

As the bifunctional (meth) acrylate, an oligomer may be used, and examples thereof include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Among these compounds, urethane (meth) acrylate is preferable and will be described in detail later.

Epoxy (meth) acrylate is a reaction product of an epoxy resin and (meth) acrylic acid.
Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resins. Examples of the bisphenol A type epoxy resin include Epicoat 827 (trade name, the same applies hereinafter), Epicoat 828, Epicoat 1001, Epicoat 1004, etc. manufactured by Japan Epoxy Resin Co., Ltd. Etc. Examples of the novolak type epoxy resin include Epicoat 152 and Epicoat 154.

Polyester (meth) acrylate is a reaction product of polyester polyol and (meth) acrylic acid.
The polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid.
Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol and bis- [hydroxymethyl] -cyclohexane.
Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

Examples of the trifunctional or higher functional (meth) acrylate compound include various compounds as long as the compound has three or more (meth) acryloyl groups. For example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate. , Diglycerin tri or tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, ditrimethylolpropane tri or tetra (meth) acrylate and dipentaerythritol tri, tetra, penta or hexa (meth) acrylate Polyol poly (meth) acrylates such as;
Tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as, and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts.

  Examples of alkylene oxide adducts in the compounds exemplified above include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and the like.

(A) A component may use only 1 type or may use 2 or more types together.
As a glass transition temperature (henceforth "Tg") of the homopolymer of (A) component, it is preferable that it is the range of -80-60 degreeC, and it is more preferable that it is the range of -60-40 degreeC.
In the present invention, Tg means a value measured at a rate of temperature increase of 10 ° C./min using a differential scanning calorimeter (DSC), and at the glass transition temperature intermediate point (Tmg) in the ΔT-temperature curve. Mean value.
As the component (A), urethane (meth) acrylate [hereinafter referred to as “component (A-1)”] is preferable because the adhesive force can be improved.
Hereinafter, the component (A-1) will be described in detail.

1-1. (A-1) component
Examples of the urethane (meth) acrylate as the component (A-1) include a reaction product of polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and a reaction product of organic polyisocyanate and hydroxyl group-containing (meth) acrylate.

As the polyol in the component (A-1), a diol is preferable.
As the diol, a low molecular weight diol, a diol having a polyene skeleton, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.
Examples of the diol having a polyene skeleton include a diol having a polybutadiene skeleton, a diol having a polyisoprene skeleton, a diol having a hydrogenated polybutadiene skeleton, and a diol having a hydrogenated polyisoprene skeleton.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as dicarboxylic acid or an anhydride thereof. Examples of the dicarboxylic acid or anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.
These diols may be used alone or in combination of two or more.

As the organic polyisocyanate, an organic diisocyanate is preferable.
Specific examples of the organic diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate (hereinafter referred to as “HDI”), lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, "IPDI"), 4,4'-methylenebis (cyclohexyl isocyanate) (hereinafter referred to as "H12MDI") and alicyclic diisocyanates such as ω, ω'-diisocyanatodimethylcyclohexane, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane Aromatic diisocyanates such as 4,4′-diisocyanate can be mentioned.
Specific examples of the organic polyisocyanate having three or more isocyanate groups include hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
These diisocyanate compounds may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate and hydroxyhexyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as hydroxyoctyl (meth) acrylate (hereinafter referred to as “hydroxyl-containing monofunctional (meth) acrylate”), trimethylolpropane mono- or di (meth) acrylate, pentaerythritol mono-, di- or Hydroxyl groups such as tri (meth) acrylate, ditrimethylolpropane mono, di or tri (meth) acrylate and dipentaerythritol mono, di, tri, tetra or penta (meth) acrylate and Compounds with more than five (meth) acryloyl group [hereinafter referred to as "hydroxyl group-containing polyfunctional (meth) acrylate"] and the like.
Among the compounds described above, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are excellent in terms of the curability of the composition and the adhesive strength of the cured film. preferable.

As the component (A-1), a compound called a urethane adduct, which is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, can also be used.
In the urethane adduct, examples of the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate include the compounds described above.
Among the above-mentioned compounds, a combination of an organic diisocyanate and a hydroxyl group-containing monofunctional (meth) acrylate is preferable in terms of lowering the viscosity of the composition and excellent cured film adhesion, and more specifically, as an organic diisocyanate. HDI, IPDI, H12MDI, and tolylene diisocyanate are preferable, and the hydroxyl group-containing (meth) acrylate is preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. .

In the urethane adduct, urethane (meth) acrylate obtained by using a hydroxyl group-containing polyfunctional (meth) acrylate as the hydroxyl group-containing (meth) acrylate can also be used.
As the hydroxyl group-containing polyfunctional (meth) acrylate in the urethane adduct, various compounds can be used. Specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane Di, tri (meth) acrylate and dipentaerythritol di, tri, tetra or penta (meth) acrylate are exemplified.
Preferable examples of the urethane adduct include an addition reaction product of HDI and pentaerythritol tri (meth) acrylate, an addition reaction product of IPDI and pentaerythritol tri (meth) acrylate, and the like.

Another preferred compound of the urethane adduct is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing monofunctional (meth) acrylate.
Examples of the hydroxyl group-containing monofunctional (meth) acrylate in the compound include the same compounds as those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the aforementioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Component (A-1) may be produced according to a conventional method.
As the component (A-1), a polyol and an organic polyisocyanate are reacted to produce an isocyanate group-containing compound, a compound obtained by reacting this with a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “compound A1”), and Examples thereof include a compound obtained by reacting a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate at the same time (hereinafter referred to as “compound A2”), and the compound A1 is preferable because the molecular weight is easily controlled.
As a method for producing Compound A1, for example, in the presence of a urethanization catalyst such as dibutyltin dilaurate, the polyol and the organic polyisocyanate used are heated and stirred to cause addition reaction, and further a hydroxyl group-containing (meth) acrylate is added, followed by heating and stirring. In the case of producing the compound A2, a method in which a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate are simultaneously added and heated and stirred in the presence of the same catalyst as described above is exemplified. It is done.
Examples of the method for producing the urethane adduct include a method in which the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate are heated and stirred in the presence of the same catalyst as described above.

As the component (A-1), only one type may be used, or two or more types may be used in combination.
The weight average molecular weight (hereinafter referred to as “Mw”) of the component (A-1) is preferably 1,000 to 60,000, and more preferably 3,000 to 20,000.
Mw in the present invention means a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).
The Tg of the homopolymer (A-1) is preferably in the range of -80 to 60 ° C, more preferably in the range of -60 to 40 ° C.

2. Component (B) The component (B) is a compound having an aromatic group and one ethylenically unsaturated group.
By including the component (B), the cured film of the composition has excellent adhesive strength and removability.
As the component (B), various compounds can be used as long as they are compounds having an aromatic group and one ethylenically unsaturated group, and monofunctional (meth) acrylates are preferred.
As monofunctional (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, o-phenylphenol alkylene oxide adduct (Meth) acrylate, (meth) acrylate of nonylphenol alkylene oxide adduct, and the like can be mentioned.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.

(B) As a component, the compound which has an oxyalkylene unit is preferable at the point which is excellent in adhesive force.
Specific examples of the compound include (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, (meth) acrylate of o-phenylphenol alkylene oxide adduct, and nonylphenol. Examples include (meth) acrylates of alkylene oxide adducts.
The number of repeating oxyalkylene units of the compound is preferably 1 or more, and more preferably a compound having 1 to 5 repetitions.
Furthermore, as (B) component, the compound which has an alkyl group and an oxyalkylene unit is more preferable at the point from which surface tension is low and a composition becomes excellent in coating property.
As an alkyl group, a C1-C12 alkyl group is preferable and a C4-C12 long-chain alkyl group is more preferable.
Furthermore, a compound having a long-chain alkyl group and an oxyalkylene unit having a repeating number of 1 or more is more preferable from the viewpoint of excellent coating properties of the composition. Specific examples of the compound include (meth) acrylates of nonylphenol alkylene oxide adducts.

  As Tg of the homopolymer of (B) component, it is preferable that it is the range of -50-40 degreeC, and it is more preferable that it is the range of -30-20 degreeC.

As the content ratio of the components (A) and (B), a compound having one ethylenically unsaturated group other than the component (B) described later in the total amount of 100% by weight of the components (A) and (B) In the case of blending [hereinafter referred to as “component (D)”], the component (A) is added in an amount of 5 to 50 wt% and (A), (B) and (D) in a total amount of 100 wt%. It is preferable to contain 50 to 95% by weight of component B), more preferably 10 to 30% by weight of component (A) and 70 to 90% by weight of component (B).
By making the content rate of (A) and (B) component into the above-mentioned range, it is preferable at the point which can be excellent in the coating property of a composition, and the adhesive force of a cured film.
In addition, in this invention, a sclerosing | hardenable component is a component hardened | cured with an active energy ray, means (A) component and (B) component, and when mix | blending (D) component mentioned later, (A) The component, the component (B) and the component (D) are meant.

3. Component (C) Component (C) is a photopolymerization initiator having a molecular weight of 300 or more excluding (C-1) acylphosphine oxide compound [hereinafter referred to as “component (C-1)”] and / or (C-1 ) A photopolymerization initiator containing an acylphosphine oxide compound (hereinafter referred to as “component (C-2)”) as an essential component.
In this invention, by using (C) component, it is excellent in the sclerosis | hardenability of the composition, and is excellent in the low odor property of the cured film obtained. Furthermore, the component (C-1) is preferred because the cured film has excellent light stability and little coloring.

As the component (C-1), an α-hydroxyketone compound is more preferable in terms of excellent compatibility with the components (A) and (B) in addition to the above-described performance.
Specific examples of the α-hydroxyketone-based compound include α-hydroxyketone oligomers and polymers, and examples thereof include compounds represented by the following formula (1).

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents a number of 2 to 5. In addition, n means the average number of repetitions of the above unit.
R ² is preferably a lower alkyl group such as a methyl group, an ethyl group and a propyl group as the alkyl group.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone.
The said compound is marketed, for example, ESACURE KIP 150 (made by IGM Resins) and ESACURE ONE (made by IGM Resins) are mentioned.
ESACURE KIP 150 and ESACURE ONE are compounds represented by the above formula (1), wherein R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, n is a number from 2 to 3, and [(204.3 × n + 16 .0) or (204.3 × n + 30.1)].
Note that ESACURE ONE contains the same components as ESACURE KIP 150, but is a purified high-purity product.

  Examples of other α-hydroxy ketone compounds include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) phenoxy] phenyl} -2-methylpropan-1-one (commercially available product). As ESACURE KIP-160 manufactured by IGM Resins, Inc. In the following, parentheses indicate the same meaning) and (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl- And propionyl) -benzyl] -phenyl} -2-methylpropan-1-one (BASF Irgacure 127).

Examples of the compound other than the α-hydroxyketone compound include 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid.
The said compound is marketed and Irgacure 754 (made by BASF) is known. Irgacure 754 is a mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester.
Also, SPEDDCURE 7005 (molecular weight 1200 or more, manufactured by Lambson Japan), which is an oligomer type benzophenone photopolymerization initiator, oligomer type thioxanthone photopolymerization initiator (molecular weight 1500 or more, manufactured by Rambson Japan), ( 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (ESACURE 1001M manufactured by IGM Resins), 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butanone-1 (Irgacure 369 manufactured by BASF) and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) Butanone-1 (Irgacure 379 manufactured by BASF) It can be mentioned.

  The acylphosphine oxide compound of component (C-2) includes bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethylpentylphosphine oxide.

The component (C) has the components (C-1) and (C-2) as essential components, and if necessary, a photopolymerization initiator other than the components (C-1) and (C-2) [ Hereinafter, “component (C-3)” can be used in combination.
Specific examples of the component (C-3) include benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-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, etc. Less than acetophenone compounds;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4 Benzophenone compounds such as 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4′-dimethylaminobenzophenone;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]- And thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, and camphorquinone.

Also, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured film, or when using an ultraviolet absorber or a pigment together For the purpose of improving the curability of the composition, it is preferable to use a plurality of compounds selected from thioxanthone compounds and α-aminoalkylphenone compounds in combination.
Preferable examples of the compound in this case include 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like as the thioxanthone compound, and as the α-aminoalkylphenone compound, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one and the like.

  As for the content rate of (C) component, 0.1-15 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.5-10 weight part. By making the ratio of the component (C) 0.1 parts by weight or more, the active energy ray curability of the composition can be improved and the adhesiveness can be excellent, and by being 15 parts by weight or less, The internal curability of the cured film can be improved, and the adhesion with the substrate can be improved.

4). The active energy ray-curable pressure-sensitive adhesive composition present invention, the (A), regarding (B) and (C) an active energy ray-curable pressure-sensitive adhesive composition as a component of the essential components.
Furthermore, the composition of the present invention is preferably used as an active energy ray-curable pressure-sensitive adhesive composition for re-peeling because the composition is excellent in coatability and curability and the cured film is excellent in adhesive strength and re-peelability. be able to.
As the peel strength when used for re-peeling applications, the cured film of the composition has a film thickness of 40 μm, and when a polyethylene terephthalate film is used as the substrate and a glass plate is used as the adherend, 23 ° C., 50% It is preferable that the 180 ° peel strength (peel rate: 300 mm / min) under the RH condition is 0.01 to 5.0 N / 25 mm. The composition having the peel strength within the range can be easily peeled after being attached to the adherend.

As a viscosity of a composition, it is preferable that it is 50-500,000 mPa * s, and it is more preferable that it is 100-50,000 mPa * s.
In the present invention, the viscosity means a value measured at 25 ° C. using an E-type viscometer (cone plate viscometer).

  The composition of the present invention comprises the components (A), (B) and (C) as essential components, but various components can be blended depending on the purpose.

  Specific examples of the other components include component (D) [compound having one ethylenically unsaturated group other than component (B)] and organic solvent [hereinafter referred to as “component (E)”]. Can be mentioned.

Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

4-1. Component (D) The component (D) is a compound having one ethylenically unsaturated group other than the component (B), and is blended for the purpose of imparting various physical properties to the cured film of the composition.
Examples of the ethylenically unsaturated group in component (D) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, and a (meth) acryloyl group is preferred.

As the component (D), monofunctional (meth) acrylate is preferable.
Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meta ) (Meth) acrylates having alicyclic groups such as acrylates;
Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethoxyethyl (meth) acrylate;
Glycol mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, and hexanediol mono (meth) acrylate;
Mono (meth) acrylate of diethylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polyethylene glycol, and polypropylene glycol Poly (alkylene glycol) mono (meth) acrylates such as mono (meth) acrylates of
And (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate.

The monofunctional (meth) acrylate may be a compound having various functional groups.
Examples of the compound having a carboxyl group include (meth) acrylic acid, a modified polycaprolactone of (meth) acrylic acid, a Michael addition type multimer of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and phthalic anhydride Examples include acid adducts and carboxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and succinic anhydride adducts.

  Examples of the compound having a hydroxyl group include (meth) acrylate having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth). Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate, hydroxyhexyl (meth) acrylate, and hydroxyoctyl (meth) acrylate.

  Examples of (meth) acrylate having an imide group include (meth) acrylate having a maleimide group. Examples of the compound having a maleimide group include (meth) acrylate having a hexahydrophthalimide group and (meth) acrylate having a tetrahydrophthalimide group. Specific examples of the (meth) acrylate having a hexahydrophthalimide group include N- (meth) acryloyloxyethyl hexahydrophthalimide. Examples of (meth) acrylate having a tetrahydrophthalimide group include N- (meth) acryloyloxyethyl tetrahydrophthalimide.

  Examples of the component (D) other than the monofunctional (meth) acrylate include radical polymerizable vinyl compounds such as (meth) acrylamide compounds and N-vinyl compounds.

(D) It is preferable that the content rate of a component contains 0 to 45 weight% in 100 weight% of total amounts of a sclerosing | hardenable component, More preferably, it is 0 to 20 weight%.
By making the content rate of (D) component into 45 weight% or less, especially when (D) component is a polyfunctional ethylenically unsaturated compound, it can prevent that a cured film becomes weak.

4-2. (E) Component Although the composition of the present invention is most preferably solventless, it can contain an organic solvent of component (E) for the purpose of improving the coating property to the substrate.

Specific examples of the component (E) include aromatic compounds such as benzene, toluene and xylene; ester compounds such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone. .
Among these, an aromatic compound is more preferable in terms of excellent solubility of the components (A) and (B).

  The content ratio of the component (E) is preferably 0 to 1,000 parts by weight, more preferably 0 to 500 parts by weight, and more preferably 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, it is part by weight. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

4-3. Other components Other components other than the above-described components (D) and (E) can be blended in the composition of the present invention.
Specific examples include sensitizers, polymerization inhibitors, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and plasticizers.
Hereinafter, these components will be described.

1) Sensitizer A sensitizer is blended for the purpose of further enhancing the photoreactivity of the composition.
Examples of the sensitizer include aliphatic amines and aromatic amines such as diethylaminophenone, ethyl dimethylaminobenzoate, and isoacyl dimethylaminobenzoate. In order to reduce migration from the cured coating film, a high molecular weight type amine can also be used.
As a content rate of a sensitizer, it is preferable that it is 0-5 weight part with respect to 100 weight part of solid content of a composition, and it is more preferable that it is 0-3 weight part.

2) Polymerization inhibitor The polymerization inhibitor is blended for the purpose of improving the thermal stability and photoreactivity of the composition.
Specific examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of the organic polymerization inhibitor include phenol compounds such as hydroquinone, tert-butyl hydroquinone and hydroquinone monomethyl ether, quinone compounds such as benzoquinone, galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4 Stable radicals such as -hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium and the like. Specific examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate and iron sulfate. Specific examples of the organic salt polymerization inhibitor include N-nitroso-N-phenylhydroxylamine / aluminum salts, nitroso compounds such as ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.

Among these, a stable radical and a nitroso compound are preferable because the coloring of the adhesive is small and the composition can be prevented from being thickened or gelled to increase the stability.
The ratio of the polymerization inhibitor in the curable component is 0.0001 to 1% by mass, more preferably 0.0005 to 0.5% by mass. By making the proportion of the polymerization inhibitor 0.0001% by mass or more, the thermal stability and light stability of the composition can be improved, and by making it 1% by mass or less, the photocurability of the composition is excellent. It will be.

3) Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a cured film, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of phenolic antioxidants include hindered phenols such as 2,6-di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is.
By setting the content of the antioxidant to 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, by setting the content to 5 parts by weight or less, the curability and adhesion are improved. be able to.

4) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a content rate of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. By making the content ratio of the ultraviolet absorber 0.01 parts by weight or more, the light resistance of the cured film can be improved, while by making it 5 parts by weight or less, the curability of the composition is improved. It can be excellent.

5) Silane coupling agent A silane coupling agent is mix | blended in order to improve the interface adhesive strength of a cured film and a base material.
The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldi Tokishishiran, 3-mercaptopropyltrimethoxysilane, and the like.

What is necessary is just to set suitably the content rate of a silane coupling agent according to the objective, 0.1-10 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 1-5 weight part. .
By setting the content ratio of the silane coupling agent to 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, by setting the content to 10 parts by weight or less, changes in the adhesive strength with time are prevented. be able to.

6) Surface modifier A surface modifier may be added to the composition of the present invention for the purpose of enhancing the leveling property at the time of coating, the purpose of enhancing the slipperiness of the cured film, and the like.
Examples of the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a coating film as it is the said range.

7) Plasticizer The composition of the present invention may be blended as necessary for the purpose of adjusting the tackiness of the cured film.

  Plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, and dioctyl phthalate; aliphatic dibases such as dimethyl adipate, dibutyl adipate, dioctyl adipate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, and diethyl succinate Acid esters and aliphatic polybasic acid esters such as tributyl acetylcitrate; orthophosphate esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; glyceryl triacetate and 2-ethylhexyl acetate Acetates; Phosphites such as triphenyl phosphite and dibutyl hydrogen phosphite; Natural resins such as rosin resins and terpene resins; Derivatives; and polyesters, acrylic polymers (e.g., manufactured by Toagosei Co. Arufon UP-1000), polyethers and inert compounds such as petroleum resins.

  The content of the plasticizer may be appropriately set according to the purpose, but is preferably 1 to 90% by weight, more preferably 5 to 80% by weight in the composition.

5). Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
Specific examples include a method of applying a composition to a substrate and irradiating and curing an active energy ray, and a method of further irradiating and curing an active energy ray after being bonded to another substrate.
The coating range for the substrate may be appropriately selected according to the purpose, and may be partially coated or entirely coated.

  The base material may be a sheet or film having releasability (hereinafter referred to as “release material”) in addition to a material for adhesion (hereinafter referred to as “adhered body”).

Examples of the material of the adherend include metals such as polymers, paper, glass, ceramics, steel plates and aluminum, vapor deposition films of metals and metal oxides, and silicon.
Polymers include cellophane, polyester such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polycarbonate, urea / melamine resin, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, poly Examples include vinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol, triacetyl cellulose, hydroxypropyl cellulose, polyethersulfone, copolymers of the above polymers, liquid crystal polymers, and fluororesins. These polymers are preferably in the form of a film or a sheet.
Examples of the paper include fine paper, coated paper, art paper, imitation paper, thin paper, and thick paper.

  Examples of the release material include a material obtained by subjecting the polymer mentioned as the adherend to a release treatment. Specific examples of the mold release treatment include silicone treatment, fluorine treatment, and long-chain alkyl treatment. In addition, it is possible to use a polymer having a small surface free energy as it is untreated, and specific examples include polyethylene, polypropylene, cycloolefin polymer, and fluororesin.

  The coating method may be appropriately set according to the purpose, and may be appropriately set according to the purpose. The bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma Examples of the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, a micro gravure coater, and an ink jet.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).
Irradiation energy may be appropriately set according to the type and composition of the active energy ray, and varies depending on the thickness and illuminance of the coating film. For example, when using a high-pressure mercury lamp, the irradiation energy is in the UV-A region. preferably ^{10~2,000mJ / cm 2, 10~1,000mJ / cm} 2 is more preferable.

6). Adhesive Sheet The composition of the present invention can be preferably used for the production of an adhesive sheet.
The pressure-sensitive adhesive sheet may be produced by a conventional method, for example, by applying the composition to a substrate and then irradiating with active energy rays.

When the composition is a solventless type, the composition is applied to a substrate. When the composition is an organic solvent or the like, the composition is applied to a substrate and then dried to evaporate the organic solvent or the like.
By irradiating an active energy ray with respect to the sheet | seat in which a composition layer is formed in a base material, the adhesive sheet comprised from a base material / cured film is obtained. The active energy ray is usually irradiated from the composition layer side, but can also be irradiated from the substrate side.

The coating amount of the composition of the present invention may be appropriately selected according to the application to be used, but the film thickness after drying the organic solvent or the like is preferably 1 to 100 μm, preferably 5 to 50 μm. More preferably.

When the composition contains an organic solvent or the like, it is dried after coating to evaporate the organic solvent or the like.
What is necessary is just to set drying conditions suitably according to the organic solvent etc. to be used, and the method of heating to the temperature of 40-150 degreeC etc. are mentioned.

  Irradiation conditions such as irradiation energy in active energy ray irradiation may be appropriately set according to the composition to be used, the substrate, the purpose, and the like, and may be in accordance with the same conditions as described above.

7). Applications The pressure-sensitive adhesive sheet formed from the composition of the present invention can be used for various applications such as pressure-sensitive adhesive labels, pressure-sensitive adhesive tapes and special pressure-sensitive adhesive films. In particular, examples of preferred applications include re-peeling applications.

  Specific examples of adhesive labels include trademark labels, quality labeling labels, content labeling labels, returnable labels, nameplates, etc. for product display, weighing labels, hand labels, price tags, price tags, price labels, instruction labels, inspections Certificate label, warranty label, tamper-proof label, distribution diagram label, scale plate label, PL law warning label, etc. for explanation and warranty, sticker (for window, vehicle, shop front, etc.), mark / decoration label, stamp , Seals, emblems, posters, multi-layer labels, etc. for promotion / promotion, form labels, computer labels, POS labels, process / inventory management labels, etc., double-sided / single-sided tag labels, mailing labels, home delivery slips For labels such as labels and addresses, seals for seals, seals for cap seals, etc., guide sign labels, traffic sign labels, facility sign labels, etc. For recycling inside / labeling, toiletry-related labels, home appliance labels, OA equipment labels, etc., other index labels (for stationery, Blu-ray discs, etc.), color sample labels, toys (seal), teaching materials, etc. There is.

  Adhesive tape includes nameplate tape, metal building material tape, automotive tape, surface protection, semiconductor manufacturing process tape, electronic component transport tape, protection / masking tape, fixing / adhesion tape, electrical insulation For general electrical masking such as coating masking tape, curing masking tape, etc., for electrical and electronic equipment such as tape for tape, binding / repair tape, conductive tape, display / sealing on EPS (expanded polystyrene beads fused product) cases General bundling and fixing applications such as sealing and packaging for cardboard packaging tape, office use, other automotive decoration tape, photoengraving tape, splicing tape, double-sided tape, cellophane tape, OPP tape, etc. Can be mentioned.

  Special adhesive films include outdoor advertising films, outdoor stripes for automobiles, marking films, etc., posters, interior films, general wall coverings such as interior materials, elevator interior films, counter decoration films, furniture decoration films, vehicle interior films , Interior decoration such as vending machine decoration film, cash corner decoration film, table decoration film, etc., for short-term decoration such as wind display film, sticker, marking film, etc., for interior lighting signage such as outdoor durable film, etc. For films, safety reflective films (for automobiles, shoes, helmets, etc.), for automobiles, etc. as window films to be applied while wet with water or soapy water, other prisms, hologram films, daylight films and luminescent films Etc. The.

The composition of the present invention can be preferably used for re-peeling because the composition is excellent in coatability and curability and the cured film is excellent in adhesive strength and re-peelability.
Specific examples of re-peeling applications include office use and physical distribution management labels for products, etc., for labels that can be repeatedly applied.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “parts” means parts by weight.

1. Examples 1 to 9 and Comparative Examples 1 to 4
1) Production of active energy ray-curable pressure-sensitive adhesive composition The compounds shown in Table 1 were stirred and mixed at the ratios shown in Tables 1 and 2 to produce active energy ray-curable compositions.
The obtained composition was used and evaluated as described later. The results are shown in Table 3.
The numbers in Tables 1 and 2 mean the number of copies.
Moreover, the symbol in Table 1 and Table 2 means the following.

(1) Component (A) M1200: Non-yellowing type polyester skeleton urethane acrylate (Mw 4,500), “Aronix M-1200” (trade name) manufactured by Toagosei Co., Ltd.
UN6200: Non-yellowing polyether skeleton urethane acrylate (Mw 6,500), “Art Resin UN-6200” (trade name) manufactured by Negami Kogyo Co., Ltd.
UN353: Non-yellowing polyester skeleton urethane acrylate (Mw 5,000), “Art Resin UN-353” (trade name) manufactured by Negami Kogyo Co., Ltd.
UN7600: Non-yellowing polyester skeleton urethane acrylate (Mw 11,500), “Art Resin UN-7600” (trade name) manufactured by Negami Kogyo Co., Ltd.
OT1001: Non-yellowing polyester skeleton urethane acrylate (Mw 40,000) isobornyl acrylate (hereinafter referred to as “IBXA”) 50% by weight diluted product, “Aronix OT-1001” (trade name) manufactured by Toagosei Co., Ltd. . In Table 2, urethane acrylate corresponding to component (A) and IBXA corresponding to component (D) are shown separately.

(2) Component (B) · M111: Nonylphenol ethylene oxide modified (n = 1) acrylate, liquid surface tension = 35.8 mN / m, “Aronix M-111” (trade name) manufactured by Toagosei Co., Ltd.
M113: Nonylphenol ethylene oxide modified (n = 4) acrylate, liquid surface tension = 35.7 mN / m, “Aronix M-113” (trade name) manufactured by Toagosei Co., Ltd.
M101A: phenol ethylene oxide modified (n = 2) acrylate, liquid surface tension = 44.6 mN / m, “Aronix M-101A” (trade name) manufactured by Toagosei Co., Ltd.

(3) Component (C) E-ONE: Poly {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one}, “ESACURE ONE” manufactured by IGM Resins (Product name)
KIP160: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) phenoxy] phenyl} -2-methylpropanone, “ESACURE KIP-160” (trade name) manufactured by IGM Resins
SBPI 718: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, “SB-PI 718” (trade name) manufactured by Sojyo Corporation
SBPI 719: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, “SB-PI 719” (trade name) manufactured by Sojyo Sangyo Co., Ltd.

(4) (C) 'component -SBPI 714: 1-hydroxycyclohexyl phenyl ketone, "SB-PI 714" (trade name) manufactured by Sojyo Sangyo Co., Ltd.

(5) Component (D) M5700: 2-hydroxy-3-phenoxypropyl acrylate, cured product Tg = 17 ° C., “Aronix M-5700” (trade name) manufactured by Toagosei Co., Ltd.
BC190: ethyl carbitol acrylate, cured product Tg = −67 ° C., “Biscoat # 190” (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
・ HBA: 4-hydroxybutyl acrylate, cured product Tg = −80 ° C., manufactured by Osaka Organic Chemical Industry Co., Ltd.

2) Composition evaluation method
(1) Viscosity Viscosity of the compositions obtained in Tables 1 and 2 was measured at 25 ° C. using an E-type viscometer. The results are shown in Table 3.
(2) Coatability Polyethylene terephthalate film [Toyobo Co., Ltd., Cosmo Shine A4300 (thickness: 50 μm) having a width of 300 mm and a length of 300 mm so that the composition obtained in Tables 1 and 2 has a film thickness of 40 μm. . Hereinafter, it is applied to an “applicator” to form a coating film, and the coating property at this time was evaluated according to the following three levels. The results are shown in Table 3.
○: The film thickness of the coating film is uniform and in-plane.
(Triangle | delta): The film thickness of a coating film has small variation within a surface.
X: The film thickness of the coating film varies widely in the surface and is non-uniform.

3) Evaluation method of cured film
◆ Manufacture of pressure-sensitive adhesive sheet 2) A release PET film (300 mm wide x 300 mm long, manufactured by Toray Film Processing Co., Ltd., BKE ( Thickness 38 μm). Hereinafter, this is referred to as “release PET”.
Next, a conveyor-type ultraviolet irradiation device (160 W / cm high-pressure mercury lamp, lamp height 10 cm, UV-A region irradiation intensity 1,200 mW / cm ² manufactured by Eye Graphics Co., Ltd. (from UV POWER PUCK manufactured by Heraeus Co., Ltd.) Measured value) is used to perform UV irradiation of 200 mJ / cm ² of irradiation energy in the UV-A region from the release PET side by passing through a 7 m / min conveyor (hereinafter referred to as “irradiation condition 1”). An adhesive sheet was obtained.
The release PET of the obtained pressure-sensitive adhesive sheet was peeled off and evaluated as described later.
Using the same UV irradiation device as above, the laminate laminated by the same method as above is passed through a 36 m / min conveyor with a higher conveyor speed than irradiation condition 1, thereby releasing PET. Further, UV irradiation with an irradiation energy of 40 mJ / cm ^{2 in} the UV-A region was performed (hereinafter referred to as “irradiation condition 2”) to obtain an adhesive sheet.
The release PET of the obtained pressure-sensitive adhesive sheet was peeled off and evaluated as described later.
The results are shown in Table 3.

(1) The acryloyl group reaction rate of the composition before curable curing and the cured film cured under irradiation condition 1 was measured by infrared absorption spectrum measurement [μ-ATR method]. As an infrared absorption spectrum measuring apparatus, Spectrum 100 manufactured by PerkinElmer Japan Co., Ltd. was used.
Using the obtained ultraviolet absorption spectrum, the acryloyl group reaction rate was calculated by the following formula (1).
Acryloyl group reaction rate = {1- (B2 / A2) / (B1 / A1)] × 100 (1)
A1: peak height of 1724 cm ^-1 derived from -C = O of composition B1: peak height of 1405cm ^-1, which derived from -CH = CH ₂ in the composition A2: from -C = O of cured film peak height of 1724 cm ^-1 B2: Following a similar process, the peak height above 1405cm ^-1 derived from -CH = CH ₂ of the cured film, an acryloyl group reaction rate of the cured film obtained by curing the irradiation condition 2 It was measured.

(2) Using the test body obtained under the adhesive strength irradiation condition 1, the adhesive strength was measured according to JIS Z 0237: 2009.
Specifically, a glass plate was used as the adherend, and 180 ° peel strength (peel rate: 300 mm / min) was measured under the conditions of 23 ° C. and 50% RH.
The peel strength was measured using an Instron 5564 universal material tester manufactured by Instron Japan Company Limited.

(3) For the specimens obtained under re-peelable irradiation conditions 1 and 2, the surface state of the glass plate after peeling PET under the same conditions as in the adhesive strength measurement of (2) above was visually observed, and the following Evaluation was carried out at two levels.
○: No adhesive residue is observed on the surface of the glass plate.
X: Adhesive residue is seen on the surface of the glass plate.

(4) Using the test body obtained under odor irradiation condition 1, the glass plate after measuring the adhesive strength of (2) was peeled off, and the odor of the adhesive layer was sniffed, and the following three levels were evaluated. .
○: There is no odor.
Δ: Slight odor.
X: There is a strong odor.

(5) 20 g of the composition before photostability curing was put in a 100 cc polycup and allowed to stand directly under the straight tube 32 type UV cut fluorescent lamp × 2 lamps (light source distance 2 m). Thereafter, visual observation was performed every hour, and the time until a gelled product was partially generated was measured.

4) Evaluation results As is apparent from the results of Examples 1 to 9, the composition of the present invention has a low odor, excellent curability, excellent curability even under low energy irradiation conditions, and further obtained cured film. It was excellent in adhesive strength and removability.
In addition, as the component (B), the compositions of Examples 1 to 5, 8 and 9 containing M111 and M113, which are compounds having a long-chain alkyl group and an oxyalkylene unit having a repeating number of 1 or more, It was also excellent in workability. In addition, the compositions of Examples 1 to 7 containing the component (C-1) as the component (C) were excellent in light stability.
On the other hand, the composition of Comparative Example 1 that does not contain the component (A) is low in odor, excellent in curability, and excellent in the adhesive strength of the resulting cured film, but in any of the irradiation conditions 1 and 2 However, the re-peelability was lowered. Moreover, although the composition of the comparative example 2 which does not contain (B) component is low odor, it is excellent in sclerosis | hardenability, and the removability of the cured film obtained is excellent, adhesive force and coating property have fallen. . Moreover, although the composition of the comparative example 3 which does not contain (B) component is excellent in the adhesive force of the cured film obtained, it has an odor and the sclerosis | hardenability in the irradiation condition 2 which is low irradiation energy will fall. The removability was lowered in both cases of irradiation conditions 1 and 2. Moreover, although the composition of the comparative example 4 containing the photoinitiator different from (C) component is excellent in the adhesive force of the cured film obtained, it has a little odor, and the sclerosis | hardenability in irradiation conditions 2 and removability Has fallen.

  The active energy ray-curable pressure-sensitive adhesive composition of the present invention can be used for various applications such as pressure-sensitive adhesive labels, pressure-sensitive adhesive tapes and special pressure-sensitive adhesive films, and can be preferably used particularly for re-peeling applications.

Claims (13)

An active energy ray-curable pressure-sensitive adhesive composition containing the following components (A), (B) and (C) as essential components.
-Component (A): Compound having two or more ethylenically unsaturated groups-Component (B): Compound having aromatic group and one ethylenically unsaturated group-Component (C): (C-1) Photopolymerization initiator having a molecular weight of 300 or more excluding the acylphosphine oxide compound or / and (C-2) a photopolymerization initiator containing an acylphosphine oxide compound as an essential component The active energy ray hardening-type adhesive composition of Claim 1 in which the said (A) component contains urethane (meth) acrylate. The active energy ray-curable pressure-sensitive adhesive composition according to claim 1, wherein the component (B) is a compound having an oxyalkylene unit. The active energy ray-curable pressure-sensitive adhesive composition according to claim 3, wherein the component (B) is a compound having a long-chain alkyl group and an oxyalkylene unit having a repeating number of 1 or more. The active energy ray-curable adhesive according to any one of claims 1 to 4, wherein the component (C) includes a photopolymerization initiator having a molecular weight of 300 or more excluding the (C-1) acylphosphine oxide compound. Agent composition. The active energy ray-curable pressure-sensitive adhesive composition according to claim 5, wherein the component (C-1) contains an α-hydroxyketone compound. In a total amount of 100% by weight of the components (A) and (B), the component (A) is contained in an amount of 5 to 50% by weight and the component (B) is contained in an amount of 50 to 95% by weight. The active energy ray hardening-type adhesive composition of any one of Claims 1-6 containing 0.1-15 weight part of said (C) component with respect to 100 weight part of total amounts. Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-7 containing the following (D) component.
-Component (D): Compound having one ethylenically unsaturated group other than component (B) In a total amount of 100% by weight of the components (A), (B) and (D), the component (A) is 5 to 50% by weight, the component (B) is 50 to 95% by weight, and the component (D) The activity according to claim 8, comprising 0 to 45% by weight and comprising 0.1 to 15 parts by weight of the component (C) with respect to 100 parts by weight of the total amount of the components (A), (B) and (D). Energy ray-curable pressure-sensitive adhesive composition. When the cured film of the composition has a film thickness of 40 μm, a polyethylene terephthalate film as the substrate and a glass plate as the adherend, 180 ° peel strength (peel rate: 300 mm) at 23 ° C. and 50% RH / min) is 0.01-5.0N / 25mm, The active energy ray hardening-type adhesive composition of any one of Claims 1-9. The active energy ray hardening-type adhesive composition for re-peeling containing the composition of any one of Claims 1-10. The adhesive film or sheet | seat comprised from a base material and the adhesive layer which consists of an active energy ray cured film of the composition of any one of Claims 1-11. The manufacturing method of the adhesive film or sheet | seat which irradiates an active energy ray after applying the composition of any one of Claims 1-11 to a base material.