JP2003003136A - Adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet having excellent adhesive characteristics and an excellent design. SOLUTION: This adhesive sheet has an adhesive layer comprising a UV- curable adhesive containing an acrylic polymer (A) containing 1-15 mass % α,β-unsaturated carboxylic acid (a) as a copolymer component and having 80,000-350,000 weight average molecular weight and benzophenone and/or its derivative (B) and granules. The aforesaid sheet comprises 100 mass pts. acrylic polymer and 0.1-10 mass pts. benzophenone and/or its derivative. In the aforesaid sheet the acrylic polymer (A) contains 5-50 mass % alkoxy(meth)acrylate (poly) alkylene glycol adduct (b) as a copolymer component. In the aforesaid sheet the acrylic polymer (A) contains 1-40 mass % alkoxy(meth)acrylate alkylene glycol adduct (c) as a copolymer component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive sheet using an ultraviolet-curable pressure-sensitive adhesive, and more specifically,
The present invention relates to a pressure-sensitive adhesive sheet having good adhesiveness, holding power, tackiness and other adhesive properties, and excellent designability (color).

[0002]

2. Description of the Related Art In recent years, due to increasing concern about the environment, pressure-sensitive adhesive compositions containing no organic solvent have been investigated.
For example, so-called hot-melt pressure-sensitive adhesives, which are characterized in that a heat-melted resin is applied onto a base material, have been used in a larger amount.

Rubber hot-melt adhesives are generally used as hot-melt adhesives, but they have the problem that natural deterioration easily occurs due to their low weather resistance, and most of them are Since it is colored, when applied to a transparent substrate, the design of the substrate may be impaired.

Therefore, hot-melt pressure-sensitive adhesives using acrylic resins, which are excellent in weather resistance and transparency, are attracting attention.
For example, JP-A-59-75975 and JP-A-60-
In Japanese Patent No. 23469, etc., an acrylic hot-melt type pressure-sensitive adhesive composition characterized by applying a heat-melted resin onto a substrate is proposed.

However, pressure-sensitive adhesive tapes and the like using these conventional acrylic hot-melt pressure-sensitive adhesive compositions have
The holding power, tackiness, and other adhesive properties were inferior, and the holding power was particularly insufficient in a high-temperature atmosphere.

In order to improve this drawback, for example, it is proposed to crosslink the hot melt-coated acrylic pressure-sensitive adhesive by irradiation with active energy rays (Japanese Patent Laid-Open No. 2-2).
76879, JP-A-3-115481, JP-A-3-115481
119081, JP-A-119082, JP-A-3
-220275, etc.).

[0007]

However, these pressure-sensitive adhesives have an unstable hot melt coating property because they tend to undergo thermal polymerization when they are heat-treated in the solvent removal process during production or the coating process on the substrate. There is a problem such as becoming. As a countermeasure for this improvement, it has been proposed to add an antioxidant or the like to the pressure-sensitive adhesive, but even if it is kept at the coating temperature for several hours, gelation occurs, and further, the pressure-sensitive adhesive tends to be colored. Had.

When a transparent sheet is used as the base material of the pressure-sensitive adhesive sheet in order to impart a design property to the pressure-sensitive adhesive sheet and granules such as pigments are added to these pressure-sensitive adhesives, the granules are uniformly dispersed in the pressure-sensitive adhesive. Since it is not mixed in, color unevenness may occur,
The adhesive properties tended to deteriorate.

It is an object of the present invention to provide an adhesive sheet having excellent adhesive properties and excellent designability (color).

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a specific UV-curable pressure-sensitive adhesive, and the present invention Was completed. That is, the pressure-sensitive adhesive sheet of the present invention contains an acrylic polymer (a weight-average molecular weight of 80,000 to 350,000, containing 1 to 15 mass% of α, β-unsaturated carboxylic acid (a) as a copolymerization component ( A) and benzophenone and / or its derivative (B)
And a pressure-sensitive adhesive layer composed of a granular material and a UV-curable pressure-sensitive adhesive.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The UV-curable pressure-sensitive adhesive used in the present invention contains the α, β-unsaturated carboxylic acid (a) as a copolymerization component in an amount of 1 to 15% by mass and has a weight average molecular weight of 8%.
It has an acrylic polymer (A) of 30,000 to 350,000.

The content of the α, β-unsaturated carboxylic acid (a) as a copolymerization component of the acrylic polymer (A) is 1
It should be in the range of ˜15% by mass. This is because if the content is less than 1% by mass, the adhesive force tends to be insufficient. It is preferably 1.5% by mass or more, and more preferably 2% by mass or more. Also, 15
When the content is more than mass%, the tack of the obtained pressure-sensitive adhesive sheet tends to be inferior. It is preferably 10% by mass or less, and more preferably 8% by mass or less. The above component (a) includes at least one α, β unsaturated double bond in one molecule.
A compound having one or more carboxyl groups is used, and examples thereof include acrylic acid, methacrylic acid, itaconic acid or itaconic acid monoester, fumaric acid or fumaric acid monoester, maleic acid or maleic acid monoester, and the like. These may be used alone or in combination of two or more, if necessary.

The acrylic polymer (A) contains 5 to 50% by mass of a (meth) acrylic acid alkoxy (poly) alkylene glycol adduct (b) represented by the following general formula (I) as a copolymerization component. It is preferably contained in the range.

[Chemical 3] (R ¹ and R ² are hydrogen or a methyl group, and R ³ is 1 carbon atom.
To 12 hydrocarbon substituents, m represents an integer of 2 to 10).

This is because when the content of the component (b) is 5% by mass or more, the pressure-sensitive adhesive has excellent holding power at the time of heating, and in particular, it has a good mixing property with the granular material and a holding power at the time of mixing the granular material. This is because they tend to be excellent. It is more preferably 10% by mass or more, and further preferably 15% by mass or more. Further, by setting the component (b) to 50% by mass or less,
The adhesive strength of the adhesive tends to be good. It is more preferably 45% by mass or less, and further preferably 40% by mass or less.

Examples of the component (b) include methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytriethylene (meth) acrylate, methoxytripropylene glycol (meth) acrylate and methoxytetraethylene glycol. (Meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, methoxyoctethylene glycol (meth) acrylate, methoxyoctpropylene glycol (meth)
Acrylate, methoxydecaethylene glycol (meth) acrylate, methoxydecapropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxydipropylene glycol (meth) acrylate, ethoxytriethylene (meth) acrylate, ethoxytripropylene glycol (meth) ) Acrylate, ethoxytetraethylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, ethoxyoctethylene glycol (meth) acrylate, ethoxyoctpropylene glycol (meth) acrylate, ethoxydeca ethyleneglycol (meth) acrylate, ethoxydeca Propylene glycol (meth) acrylate, butoxydiethylene glycol Lumpur (meth) acrylate, butoxy dipropylene glycol (meth) acrylate,
Butoxytriethylene glycol (meth) acrylate, butoxytripropylene glycol (meth) acrylate, butoxytetraethylene glycol (meth) acrylate, butoxytetrapropylene glycol (meth) acrylate, butoxyoctoethylene glycol (meth) acrylate, butoxyoctpropylene glycol ( (Meth) acrylate, butoxydecaethylene glycol (meth) acrylate, butoxydecapropylene glycol (meth) acrylate, 2-ethylhexyloxydiethylene glycol (meth) acrylate,
2-ethylhexyloxydipropylene glycol (meth) acrylate, 2-ethylhexyloxytriethylene (meth) acrylate, 2-ethylhexyloxytripropylene glycol (meth) acrylate, 2-
Ethylhexyloxytetraethylene glycol (meth) acrylate, 2-ethylhexyloxytetrapropylene glycol (meth) acrylate, 2-ethylhexyloxyoctoethylene glycol (meth) acrylate, 2-ethylhexyloxyoctopropylene glycol (meth) acrylate, 2-ethylhexyl Oxydecaethylene glycol (meth) acrylate,
2-ethylhexyloxydecapropylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, isooctyloxydipropylene glycol (meth) acrylate, isooctyloxytriethylene glycol (meth) acrylate, isooctyloxytripropylene glycol ( (Meth) acrylate, isooctyloxytetraethylene glycol (meth) acrylate, isooctyloxytetrapropylene glycol (meth) acrylate, isooctyloxyoctoethylene glycol (meth) acrylate, isooctyloxyoctpropylene glycol (meth) acrylate, isooctyl Oxydeca ethylene glycol (meth) acrylate, isooctyl oxydecapro Lene glycol (meth) acrylate, dodecyloxydiethylene glycol (meth) acrylate, dodecyloxydipropylene glycol (meth) acrylate, dodecyloxytriethylene glycol (meth) acrylate, dodecyloxytripropylene glycol (meth) acrylate, dodecyloxytetraethylene glycol (Meth) acrylate, dodecyloxytetrapropylene glycol (meth) acrylate, dodecyloxyoctoethylene glycol (meth) acrylate, dodecyloxyoctopropylene (meth) acrylate, dodecyloxydecaethylene glycol (meth) acrylate, dodecyloxydecapropylene glycol ( Examples thereof include (meth) acrylate.

One or more of these may be appropriately selected and used according to need. Among them, ethoxydiethylene glycol (meth) acrylate, ethoxydipropylene glycol (meth) acrylate, 2-ethylhexyloxydiethylene glycol (meth) acrylate and 2-Ethylhexyloxydipropylene glycol (meth) acrylate is particularly preferable in terms of balance of adhesive strength, holding power, and miscibility with granules.

Further, the acrylic polymer (A) contains a (meth) acrylic acid alkoxyalkylene glycol adduct (c) represented by the following general formula (II) as a copolymerization component in the range of 1 to 40% by mass. Preferably.

[Chemical 4] (R^FourIs hydrogen or a methyl group, R⁵Has 2 carbons
12 alkylene groups, R ⁶Is a hydrocarbon having 1 to 12 carbon atoms
Indicates a substituent)

This is because when the content of the component (c) is 1% by mass or more, the adhesive strength of the adhesive, the holding power during heating, and the balance of tack tend to be improved. More preferably, it is 5 mass% or more. In addition, the component (c) is 4
When the content is 0% by mass or less, the adhesive strength of the adhesive tends to be good. More preferably, it is 30 mass% or less.

Examples of the component (c) include methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxy-iso-propyl (meth) acrylate, methoxybutyl (meth) acrylate and methoxy-iso-butyl ( (Meth) acrylate,
Methoxypentyl (meth) acrylate, methoxy-i
Methoxyalkylene glycols such as so-pentyl (meth) acrylate, methoxyhexyl (meth) acrylate, methoxyoctyl (meth) acrylate, methoxy-iso-octyl (meth) acrylate, methoxydecyl (meth) acrylate, methoxydodecyl (meth) acrylate. (Meth) acrylic acid ester, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, ethoxy-iso-propyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxy-iso-butyl (meth) acrylate,
Ethoxypentyl (meth) acrylate, ethoxy-i
Ethoxyalkylene glycols such as so-pentyl (meth) acrylate, ethoxyhexyl (meth) acrylate, ethoxyoctyl (meth) acrylate, ethoxy-iso-octyl (meth) acrylate, ethoxydecyl (meth) acrylate, ethoxydodecyl (meth) acrylate. (Meth) acrylic acid ester, propoxyethyl (meth) acrylate, propoxypropyl (meth) acrylate, propoxy-iso-propyl (meth) acrylate, propoxybutyl (meth) acrylate, propoxy-iso-butyl (meth) acrylate, propoxy -Iso-pentyl (meth) acrylate, propoxyhexyl (meth) acrylate, propoxyoctyl (meth) acrylate, propoxydodecyl (meth) acry Propoxy (meth) acrylic acid esters of alkylene glycol such as Relate, butoxyethyl (meth) acrylate, butoxyethyl (meth)
Acrylate, butoxy-iso-propyl (meth) acrylate, butoxybutyl (meth) acrylate, butoxy-iso-butyl (meth) acrylate, butoxy-iso-pentyl (meth) acrylate, butoxyhexyl (meth) acrylate, butoxyoctyl (meth) ) Acrylate, (meth) acrylic acid ester of butoxyalkylene glycol such as butoxydodecyl (meth) acrylate, pentyloxyethyl (meth) acrylate, pentyloxypropyl (meth) acrylate, pentyloxy-iso-propyl (meth) acrylate, pentyl Oxybutyl (meth) acrylate,
Pentyloxy-iso-butyl (meth) acrylate, pentyloxypentyl (meth) acrylate, pentyloxy-iso-pentyl (meth) acrylate, pentyloxyhexyl (meth) acrylate, pentyloxyoctyl (meth) acrylate, pentyloxydecyl ( (Meth) acrylate, (methyl) acrylate of pentyloxyalkylene glycol such as pentyl oxide decyl (meth) acrylate, hexyloxyethyl (meth) acrylate, hexyloxypropyl (meth) acrylate, hexyloxy-is
o-propyl (meth) acrylate, hexyloxybutyl (meth) acrylate, hexyloxy-iso-
Butyl (meth) acrylate, hexyloxy-iso
-Pentyl (meth) acrylate, hexyloxyhexyl (meth) acrylate, hexyloxyoctyl (meth) acrylate, hexyloxydecyl (meth)
(Meth) acrylic acid ester of hexyloxyalkylene glycol such as acrylate and hexyldecyl (meth) acrylate, 2-ethylhexyloxyethyl (meth) acrylate, 2-ethylhexyloxypropyl (meth) acrylate, 2-ethylhexyloxy-iso-propyl (Meth) acrylate, 2-ethylhexyloxybutyl (meth) acrylate, 2-ethylhexyloxy-iso-butyl (meth) acrylate, 2-ethylhexyloxy-iso-pentyl (meth) acrylate, 2-ethylhexyloxyhexyl (meth) acrylate , 2-ethylhexyloxyoctyl (meth) acrylate, 2-ethylhexyl oxide decyl (meth) acrylate, etc. Cole's (meth) acrylic acid ester, octyloxyethyl (meth) acrylate, octyloxypropyl (meth) acrylate, octyloxy-iso-propyl (meth) acrylate, octyloxybutyl (meth) acrylate, octyloxy-iso-butyl. (Meth) acrylate, octyloxypentyl (meth) acrylate, octyloxy-
(Meth) acryl of octyloxyalkylene glycol such as iso-pentyl (meth) acrylate, octyloxyhexyl (meth) acrylate, octyloxyoctyl (meth) acrylate, octyloxydecyl (meth) acrylate, octyloxidedecyl (meth) acrylate Acid ester, dodecyloxyethyl (meth) acrylate, dodecyloxypropyl (meth) acrylate, dodecyloxy-iso-propyl (meth) acrylate, dodecyloxybutyl (meth)
Acrylate, dodecyloxy-iso-butyl (meth) acrylate, dodecyloxy-iso-pentyl (meth) acrylate, dodecyloxyhexyl (meth) acrylate, dodecyloxyoctyl (meth) acrylate, dodecyloxydecyl (meth) acrylate, dodecyloxy Examples thereof include (meth) acrylic acid esters of dodecyloxyalkylene glycol such as dodecyl (meth) acrylate.

One or more of these may be appropriately selected and used according to need. Among them, methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate are particularly preferable in terms of balance between adhesive strength and holding power. preferable.

The acrylic polymer (A) contains 45 to 94% by mass of a (meth) acrylic ester (d) having a hydrocarbon substituent having 1 to 18 carbon atoms as a copolymerization component.
It is preferable to contain in the range of.

This is because when the content of the component (d) is 45% by mass or more, the adhesive force of the pressure-sensitive adhesive tends to be improved, and when it is 94% by mass or less, the holding force when the pressure-sensitive adhesive is heated, etc. It tends to be good.

Examples of the component (d) include methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate,
Amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-
Nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate,
Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate and the like can be mentioned.

One or more of these may be appropriately selected and used according to need, and among them, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly suitable for obtaining a balance between tackiness and holding power and availability. It is particularly preferable in terms of ease of use.

Furthermore, by appropriately using other component (e) as the copolymerization component of the acrylic polymer (A), the balance of the adhesive property can be improved. The component (e) is 54% by mass or less, more preferably 5
It is preferably used in the range of ˜49% by mass.

Examples of the component (e) include (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol monoacrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 2- (meth) cloyloxyethyl succinate, phthalic acid 2- (meth) acryloyloxyethyl, hexahydrophthalic acid 2
Examples thereof include-(meth) acryloyloxyethyl, diethylaminoethyl (meth) acrylate, N-vinyl 2-pyrrolidone, styrene, vinyl chloride, vinylidene chloride, and acrylonitrile.

Acrylic polymer (A) used in the present invention
The weight average molecular weight of is required to be in the range of 80,000 to 350,000. It has a weight average molecular weight of 80,
If it is less than 000, the cohesive force after ultraviolet irradiation is insufficient,
This is because the obtained pressure-sensitive adhesive sheet tends to have poor holding power in a high temperature atmosphere. It is preferably 90,000 or more, more preferably 95,000 or more. Also, 3
If it exceeds 50,000, the melt viscosity tends to increase, and the handleability during hot melt coating or the like tends to deteriorate. It is preferably 330,000 or less, more preferably 300,000 or less.

Acrylic polymer (A) used in the present invention
Can be produced by a polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or a suspension polymerization method. The polymerization initiation method can also be arbitrarily selected from a method using a thermal polymerization initiator such as a peroxide or an azo compound, a method using a photopolymerization initiator and ultraviolet irradiation, and a method using electron beam irradiation. If necessary, a chain transfer agent or a plasticizer may be added during the polymerization. Further, as the method for volatilizing the solvent or water, a method such as heating can be used.

The UV-curable adhesive used in the present invention is
It has benzophenone and / or its derivative (B). This is used as an initiator of the photopolymerization reaction during UV irradiation, and hydrogen is removed from the surrounding components,
There, radicals are generated. The component (B) is
0.1 to 100 parts by mass of the acrylic polymer (A)
It is preferably used in the range of 10 parts by mass.

This is because when the amount of the component (B) used is 0.1 parts by mass or more, the effect as a photopolymerization initiator is obtained, and the adhesive sheet tends to have excellent holding power. This is because. Preferably, it is 0.5 parts by mass or more. Further, when the amount of the component (B) used is 10 parts by mass or less, the adhesive force and tack of the adhesive sheet tend to be good. It is preferably 5 parts by mass or less.

Examples of the component (B) include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone and 4-benzoyl-.
4'-methyl-diphenyl sulfide, 4-morpholino benzophenone, 4,4'-diphenoxy benzophenone, 4-hydroxy benzophenone, 2-carboxy benzophenone etc. can be mentioned. One or more of these may be appropriately selected and used according to need, and among them, benzophenone and methyl o-benzoylbenzoate are preferable in terms of availability and cost.

To the UV-curable pressure-sensitive adhesive used in the present invention, if necessary, a compound capable of removing intermolecular hydrogen by UV rays, other than the component (B), can be added as a photopolymerization initiator. For example, α-hydroxyacetophenone, α-hydroxyacetophenone oligomer, benzyl dimethyl ketal and the like can be mentioned.

The ultraviolet-curable pressure-sensitive adhesive used in the present invention may further contain various additives such as a tackifier, if necessary.

As a method for producing the UV-curable pressure-sensitive adhesive used in the present invention, for example, the component (B) is added to the solution of the acrylic polymer (A) produced by the solution polymerization method, and after sufficient stirring , A method of heating under reduced pressure to remove the solvent, a method of making the acrylic polymer (A) into a powder, and adding the component (B) to the powder and mixing them. In either method, it is desirable to sufficiently stir and mix the components (A) and (B) to obtain a uniform composition.

The ultraviolet-curable pressure-sensitive adhesive used in the present invention has a melt viscosity at 150 ° C. of 80,000 mPas.
It is preferably s or less. Melt viscosity 80,000
By setting the pressure to mPas or less, the resin temperature at the time of coating can be lowered, so that the discoloration and deterioration of the resin due to heat can be reduced and the load on the manufacturing apparatus can be reduced. More preferably, 60,000 mPa
s or less.

The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer composed of the above-mentioned ultraviolet-curable pressure-sensitive adhesive and particles. By including the granular material in the pressure-sensitive adhesive layer formed on the substrate, it becomes possible to impart excellent designability to the pressure-sensitive adhesive sheet.

As a method of mixing the particulate matter with the UV-curable adhesive, for example, the particulate matter is added as it is to the acrylic polymer (A) produced by the solution polymerization method and the solvent is removed by heating under reduced pressure. Examples thereof include a method of mixing while performing, and a method of mixing particles with the ultraviolet curable pressure-sensitive adhesive obtained by the above method. Alternatively, the UV-curable adhesive may be heated to have an appropriate viscosity, and then the particulate matter may be mixed before coating on the substrate. By mixing in this way, the particulate matter can be uniformly contained in the UV-curable pressure-sensitive adhesive, and the pressure-sensitive adhesive layer in which the particulate matter is uniformly present can be formed on the pressure-sensitive adhesive sheet.

The content of the particulate matter in the pressure-sensitive adhesive layer is not particularly limited and can be determined in consideration of the designability of the pressure-sensitive adhesive layer. Usually, the content of the particulate matter is 3 to 85% by mass. It is contained in the range of. Further, in consideration of the adhesive performance of the adhesive layer, it is preferable that the granular material is contained in the range of 8 to 75% by mass.

The granular material used in the present invention is not particularly limited as long as it can withstand heating and mechanical load during mixing with an adhesive or forming an adhesive layer on an adhesive sheet. , For example, yellow ocher, tail belt, low senna, roanba, kassel earth, chalk, gypsum, burnt senna, burnt amber, lapis lazuli, azurite, malachite, ornament, cinnabar, coral powder, gourd powder, cobalt blue, cerulean blue, cobalt violet, Cobalt Green, Zinc White, Titanium White, Light Red, Chrome Oxide Green, Mars Black, Villijan, Yellow Ocher, Alumina White, Cadmium Yellow, Cadmium Red, Vermilion, Lithopone, Ultramarine, Tal , White carbon, clay, mineral violet, rose cobalt violet, silver white, calcium carbonate, gold powder, bronze powder,
Aluminum powder, ivory black, peach black, lamp black, carbon black, Prussian blue, aureoline, mica titanium, mudder rake, pink mudder, gamboge, dragon blood, cochineal, kermes rake, chilian purple, sepia, bitumen, alizarin rake, rhodamine Lake, Quinoline Yellow Lake, Lake Red C, Brilliant Carmine 6B,
Permanent Red 2B, First Yellow, Disazo Yellow, Naphthol Red, Chromophthal Yellow, Chromophthal Red, Nickel Azo Yellow, Benzimidazolone Yellow, Phthalocyanine Blue, Phthalocyanine Green, Thioindigo, Perylene Red,
Examples thereof include pigments such as dioxazine violet, quinacridone red-anthraquinone, perinone, isoindolinone, and azomethine.

As the granular material, a zinc sulfide-based, calcium sulfide-based, aluminate chloride-based, or the like phosphorescent pigment can be used. As a specific example, Reebright B-10 showing blue / blue-green emission colors (peak wavelength of 490 nm),
15, 25 (strontium aluminate type, manufactured by Reed Co., Ltd.), and Reebright YG-10, 15, 25 (strontium aluminate type, manufactured by Reed Co., Ltd.) showing a yellowish green emission color (peak wavelength of 510 nm). You can

Among them, the general formula (M _0.9995 ~
_{0.998 Eu 0.0005 ~ 0.00 2) Al} 2
O ₄ ((M _0.9995 to _0.998 Eu)
_0.0005 to _0.002 ) _O.n (A1 _{1- ba} )
B _b Q _a ) ₂ O ₃ [wherein M is at least one element selected from the group consisting of Sr, Ca, Mg and Ba, and Q is La, Ce, Pr, Nd, Sm, G
d, Tb, Dy, Ho, Er, Tm, Yb, Y, Lu,
At least one element selected from the group consisting of Mn and Bi. a is 0.0005 to 0.002, b is 0.001 to 0.35, and n is an integer of 1 to 8], and the phosphorescent pigment that is a fired product has good afterglow brightness and afterglow time. preferable.

This phosphorescent pigment is 200 to 450 n at room temperature.
When the ultraviolet ray and / or the visible ray is blocked after irradiating the ultraviolet ray and / or the visible ray of m, various colors of green, blue, purple, or yellow are emitted with high brightness. In the above general formula, the numerical values given to M and Eu are the number of moles showing the content ratio of the element. In this general formula, Eu is an activator, and the content ratio of Eu is 0.0005 to 0.0.
It is preferably in the range of 02 mol. When the content ratio of Eu is more than 0.002 mol, the concentration quenching phenomenon occurs and the light emitting property tends to be low. On the other hand, if the amount is less than 0.0005 mol, the number of luminescent centers is insufficient and the luminescent property tends to be weak.

In the phosphorescent pigment used in the present invention, Q in the general formula used as an addition activator is Dy, N.
It is preferable that it is at least one element selected from the group consisting of d, Bi and Mn, and Dy is particularly preferable from the viewpoint of afterglow.

Further, the phosphorescent pigment used in the present invention is not limited to have long afterglow performance due to interaction between the activator (Eu) and the additional activator (Q), and also has high brightness. To be At this time, the emission peak wavelength is M in the above general formula.
Since various colors can be obtained by changing the type or the amount, various emission colors can be obtained.

The amount of boron in the phosphorescent pigment used in the present invention is preferably b = 0.001 to 0.35.
When b is less than 0.001, the expression of long afterglow luminescence performance by the crystal tends to be low. Also,
When the amount of boron is more than 0.35, the long afterglow property tends to decrease because the amount of boron oxide-based products increases in the fired body.

Luminescent material comprising a fired body represented by the above general formula
Specific examples of the pigment include those that block ultraviolet rays and / or visible rays.
Emits green light in the wavelength range of 515 to 525 nm after disconnection
Rupicarico CP-05 ((Sr_0.9995Eu_0.0005) Al
₂ O_Four ・ (Sr_0.9995Eu_{0. 0005}) O ・ (Al
_{1-0.01-0.0005} B_0.01Dy_0.0005)₂ O_3,Chemtech
Co., Ltd.), blue with a wavelength range of 485 to 495 nm
Emitting light of Picarico CP-10 ((Sr_0.9995Eu
_0.0005) Al₂ O_Four ・ (Sr_0.9995Eu_0.0005) O ・ 2
(Al_{1-0. 01-0.0005} B_0.01Dy_0.0005)₂ O₃, Chemi
Manufactured by Tech Co., Ltd., in the wavelength range of 420 to 440 nm.
Pico Calico CP-20 ((Sr_0.09992 
Ca _0.89928 Eu_0.0008) Al₂ O_Four ・ (Sr_0.09992 
Ca_0.89928 Eu_0.0008) O ・ (Al_{1-0.01-0.0016} B
_0.01Dy_0.0008Nd_0.0008)₂ O₃, Chemtech Co., Ltd.
), Emitting yellow light in the wavelength range of 560 to 580 nm
Picarico CP-30 ((Sr_0.7996Ca_0.1999Eu
_0.0005) Al₂ O_Four ・ (Sr_0.7996Ca_0.1999Eu
_0.0005) O ・ (Al_1-0.02-0.002B_0.02Dy_0.002 )₂ 
O₃, Chemitech Co., Ltd.). This
These phosphorescent pigments are very hard and their hardness is
The Mohs hardness is 6.2 to 7.5.

An example of the pressure-sensitive adhesive sheet of the present invention is shown in FIG.
And the layered structure shown in FIG. Figure 1
The pressure-sensitive adhesive sheet of No. 2 is one in which the pressure-sensitive adhesive layer 3 containing the particulate matter 5 and the separator layer 4 are sequentially formed on one surface of the base material layer 2, and the printing layer 1 is formed on the other surface. In the pressure-sensitive adhesive sheet of FIG. 2, the printed layer 1, the pressure-sensitive adhesive layer 3 containing the granular material 5, and the separator layer 4 are sequentially formed on one surface of the base material layer 2.

In order to impart excellent designability to the pressure-sensitive adhesive sheet of the present invention by the pressure-sensitive adhesive layer 3 containing the particulate matter 5,
The base material layer 2 is polyethylene terephthalate (PET),
Polystyrene (PS), oriented polypropylene (OPP)
It is particularly preferable to be composed of a transparent or translucent material such as However, when the adherend of the pressure-sensitive adhesive sheet of the present invention is a transparent or translucent material and the adhesive layer 3 containing the particulate matter 5 is viewed through the adherend, the base material layer 2 is transparent or translucent. Does not have to be. In addition, the thickness, size, and
The shape and the like are selected according to the application of the pressure-sensitive adhesive sheet of the present invention, and are not particularly limited.

The pressure-sensitive adhesive layer 3 is made of the above-mentioned UV-curable pressure-sensitive adhesive, and its thickness is usually in the range of 100 μm or less, but is not particularly limited. Granules 5
Are those appropriately selected from the above-mentioned granular materials. The particle size of the particles is not particularly limited, and even if the diameter of the particles is larger than the thickness of the pressure-sensitive adhesive layer, there is no particular problem as long as it does not hinder the formation of the pressure-sensitive adhesive layer.

The separator layer 4 is composed of a film or sheet which can be easily peeled off even when it is attached to the pressure-sensitive adhesive layer. Examples of the separator layer 4 include a polyethylene terephthalate (PET) film coated with a silicon-based release agent, but any material that can be easily peeled off by sticking the pressure-sensitive adhesive used in the present invention can be used. However, it is not particularly limited.

The print layer 1 is a layer in which a design, characters, etc. are printed on the base material layer 2 with ink or the like. The printing layer 1 is
Any structure may be used as long as it does not impair the design of the pressure-sensitive adhesive layer 3. The print layer 1 may not exist depending on the method of use.

When the adherend of the pressure-sensitive adhesive sheet of FIGS. 1 and 2 is a transparent or translucent material and the printed layer 1 is viewed through the adhered material, the printed layer 1 is printed so that the printed pattern is normal. It is desirable to print the design so-called reverse printing so that it looks like. In this case, the base material layer 2 of the pressure-sensitive adhesive sheet in FIG. 1 needs to be made of a transparent or translucent material.

In FIG. 2, since the printing layer 1 exists between the base material layer 2 and the adhesive layer 3 and does not come into direct contact with the outside,
The printing layer 1 is less likely to be damaged by rubbing or the like. Further, in FIG. 2, the printed layer 1 is in contact with the pressure-sensitive adhesive layer 3, but since the UV-curable pressure-sensitive adhesive used in the present invention does not substantially contain a solvent, the pressure-sensitive adhesive sheet of the present invention is not manufactured. Also, the printed layer 1 is hardly damaged by the adhesive layer 3 during storage.

The pressure-sensitive adhesive sheet of the present invention has a mixture of the above-mentioned UV-curable pressure-sensitive adhesive and granules on a substrate, usually 20 to 1
After coating at 60 ° C., preferably 100 to 150 ° C.,
It can be manufactured by irradiating ultraviolet rays having a wavelength range of 200 to 450 nm. Examples of the coating method of the mixture of the pressure-sensitive adhesive and the granular material include direct coating on the base material and transfer coating for transferring the pressure-sensitive adhesive layer to the base material by bonding to the base material after coating on the separator. It is possible to select it as needed.

FIG. 3 shows an example of a pressure-sensitive adhesive sheet manufacturing apparatus of the present invention. After printing the base material, a mixture of the pressure-sensitive adhesive and the granular material is applied to the base material, and the separator is directly applied. It is an example of a work. The adhesive sheet manufacturing apparatus 10 includes a printing machine 11, a base material roll 12, a coating machine 13, a separator roll 14, an ultraviolet lamp 15, a cutter 16, and an adhesive sheet 17. First, a base material roll 12
The printing layer 1 is supplied from the above and printing is performed thereon by the printing machine 11 to form the printing layer 1 on the base material layer 2. Then, a mixture of the ultraviolet curable adhesive and the granular material 5 is applied onto the printing layer 1 by the coating machine 13, and the adhesive layer 3 is formed by irradiating ultraviolet rays using the ultraviolet lamp 15. Further, a separator is supplied from the separator roll 14 to form the separator layer 4 on the pressure-sensitive adhesive layer 3. Then, the adhesive sheet 1 is cut by the cutter 16 into a predetermined sheet shape.
7 is obtained.

FIG. 4 shows an example of a pressure-sensitive adhesive sheet manufacturing apparatus of the present invention, in which a separator is coated with a mixture of a pressure-sensitive adhesive and granules, and then a base material is bonded thereto, and the pressure-sensitive adhesive layer is transferred onto the base material. This is an example of transfer coating. This adhesive sheet manufacturing apparatus 20
Is a base material roll 12, a coating machine 13, a separator roll 1
4, UV lamp 15, cutter 16, adhesive sheet 17
It consists of First, the separator is supplied from the separator roll 14, the mixture of the ultraviolet curable adhesive and the particulate matter 5 is applied on the separator layer 4 by the coating machine 13, and the ultraviolet rays are irradiated using the ultraviolet lamp 15. The pressure-sensitive adhesive layer 3 is formed. Further, a pre-printed substrate is supplied from the substrate roll 12 to form the substrate layer 2 having the printed layer 1 on the pressure-sensitive adhesive layer 3. Then, the adhesive sheet 17 is obtained by cutting into a predetermined sheet shape with the cutter 16.

The coating machine 13 is not particularly limited and, for example, a hot melt coater or the like can be used. Further, the mixture of the UV-curable pressure-sensitive adhesive used here and the particles can be coated with a solvent, if necessary.

The light source of the ultraviolet lamp 15 may be appropriately selected and used, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an arc lamp and a gallium lamp.

The method for producing the pressure-sensitive adhesive sheet of the present invention is not limited to the above method. For example, it is not always necessary to form the printed layer 1 on the base material layer 2, but after the printed layer 1 is formed on the base material layer 2, an adhesive layer is formed on the base material layer 2 on the opposite side of the printed layer 1. It is also possible to form 3. In addition, the separator layer 4 on which the pressure-sensitive adhesive layer 3 is formed in advance
It is also possible to manufacture a double-sided pressure-sensitive adhesive tape by sticking both sides of the base material layer 2 together. Further, the adhesive tape may be processed to have a cut or the like so as to be easily separated.

In such a pressure-sensitive adhesive sheet of the present invention, since the ultraviolet-curable pressure-sensitive adhesive used has a high activity with respect to ultraviolet rays, it can be cured with a low amount of ultraviolet rays. For this reason, it is possible to suppress the damage to the base material due to the irradiation of ultraviolet rays during the production of the pressure-sensitive adhesive sheet, and it is possible to increase the speed of the irradiation line, so that the production cost can be reduced. Further, this ultraviolet-curable pressure-sensitive adhesive has good thermal stability and excellent hot-melt coatability, so that the productivity of the pressure-sensitive adhesive sheet is good.

That is, the pressure-sensitive adhesive sheet of the present invention is excellent in productivity, has good pressure-sensitive adhesive properties such as pressure-sensitive adhesive strength, holding power, and tack, and particularly excellent in holding power in a high temperature atmosphere. In addition, it has more excellent designability. Further, in the pressure-sensitive adhesive sheet of the present invention, since the ultraviolet curable pressure-sensitive adhesive used has high transparency, the design of the particulate matter in the pressure-sensitive adhesive layer can be sufficiently brought out.

The adherend to which the pressure-sensitive adhesive sheet of the present invention is applied is not particularly limited, and iron, aluminum,
It can be adhered to a metal plate such as stainless steel or a resin plate such as acrylic resin. Examples of the use of the pressure-sensitive adhesive sheet of the present invention include, but are not particularly limited to, general labels such as liquor and shampoo bottles, various material applications, pressure-sensitive adhesive labels for automobile interior materials, and the like. .

[0063]

EXAMPLES Hereinafter, the present invention will be described more specifically by showing examples. [Production Example of Acrylic Polymer (A-1)] 32 parts by mass of ethyl acetate, 18 parts by mass of 2-propanol, and acryl in a reactor equipped with a reflux device, a thermometer, a stirrer, a dropping device, and a nitrogen introducing tube. Acid 5 parts by mass, n-butyl acrylate 90
75 parts by mass of a mixture composed of 0.03 parts by mass of tetrahydrofurfuryl methacrylate, 5 parts by mass of tetrahydrofurfuryl methacrylate, and 0.03 parts by mass of peroxide-based polymerization initiator (manufactured by NOF CORPORATION, Niper BMT-K40) are charged and stirred. Heated to reflux temperature under nitrogen atmosphere. Then, while heating the reaction solution at a reflux temperature under a nitrogen atmosphere, the rest of the mixture was added using a dropping apparatus over 90 minutes, and further heated for 2 hours. Then, while heating the reaction solution at a reflux temperature under a nitrogen atmosphere, an ethyl acetate solution of azobisisobutyronitrile (5
(Mass%) 2 parts by mass was added 4 times and after heating for 2 hours, the heating and the introduction of nitrogen were terminated to obtain an acrylic polymer solution (A-1).

[Acrylic polymer solution (A-2) to (A
Production Example of -6)] The production was performed in the same manner as in the above Production Example except that the solvent composition and the monomer composition in the Production Example of the acrylic polymer (A-1) were changed as shown in Table 1. Acrylic polymer solutions (A-2) to (A-6) were obtained.

[Production Example of Acrylic Polymer Solution (A-7)] In the production example of the acrylic polymer (A-1), the solvent composition and the monomer composition were changed as shown in Table 1 to carry out peroxide oxidation. 0.01 parts by mass of a physical polymerization initiator (NIPPER BMT-K40, manufactured by NOF CORPORATION), a solvent, and a mixture of monomers are all charged into a reaction apparatus and heated to a reflux temperature under a nitrogen atmosphere while stirring, and further. Acrylic polymer solution (A-7) was obtained in the same manner as in the above Production Example except that the mixture was heated at a reflux temperature for 2 hours under a nitrogen atmosphere.

The above acrylic polymers (A-1) to (A-
The physical properties of 7) were measured by the following methods, and the results were described in Table 1 (1) Weight average molecular weight By gel permeation chromatography (GPC), the polystyrene equivalent weight average molecular weight was measured.

[0067]

[Table 1]

The symbols in Table 1 mean the following compounds. Moreover, the compounding quantity of each composition is all a mass part. AA: acrylic acid, MAA: methacrylic acid, M4PO
A: methoxytetraethylene glycol acrylate,
EH2EOA: 2-ethylhexyloxydiethylene glycol acrylate, MEOA: methoxyethyl acrylate, EEOA: ethoxyethyl acrylate, P
EOA: propoxyethyl acrylate, MA: methyl acrylate, BA: n-butyl acrylate, EH
A: 2-ethylhexyl acrylate, THFMA: tetrahydrofurfuryl methacrylate, AN: acrylonitrile

[Examples 1 to 5 and Comparative Examples 1 to 3] The acrylic polymer (A-1 to A-7) solutions obtained in the above production examples were added with
The photopolymerization initiator and the granules having the compounding ratios shown in Tables 2 and 3 were added, and after sufficiently stirring and mixing, the solvent was removed by heating under reduced pressure at 130 ° C. to remove the ultraviolet curable adhesive and the granules. A mixture was obtained.

[0070]

[Table 2]

[0071]

[Table 3]

The symbols in Tables 2 and 3 mean the following compounds. Moreover, the compounding quantity of each composition is all a mass part. BP: benzophenone, OBM: o-benzoyl methyl benzoate, A: silica particles (R-972 manufactured by Nippon Aerosil Co., Ltd.), B: zinc sulfide phosphorescent pigment (manufactured by Nemoto Special Chemical Co., Ltd., product number: GSS), C : Luminescent pigment (Chemtech Co., Ltd., Picarico CP-05)

Using a hot melt coater, each of the heat-melted mixtures described above was printed on the printed layer of a transparent PET film having a thickness of 38 μm, which was printed on the back surface,
It was applied to a thickness of 25 μm and cooled to room temperature to form an adhesive layer. This pressure-sensitive adhesive layer was irradiated with ultraviolet rays in the air (irradiation energy of 500 mJ / cm ² ) to cure the pressure-sensitive adhesive layer, and thus a pressure-sensitive adhesive sheet was obtained. Table 4 shows the evaluation results of the properties of the obtained pressure-sensitive adhesive sheet.

[Comparative Example 4] 100 parts by mass of the acrylic polymer solution (A-7) obtained in the above Production Example was added to Coronate L5.
5E (manufactured by Nippon Polyurethane Company, ethyl acetate solution of polyisocyanate) 1.0 part by mass, and 100 parts by mass of zinc sulfide-based phosphorescent pigment (manufactured by Nemoto Special Chemical Co., Ltd., product number: GSS) were added and sufficiently stirred and mixed. After that, an adhesive was applied on the printed layer of a transparent PET film having a thickness of 38 μm, which was printed on the back surface, so that the thickness of the adhesive layer after drying was 25 μm, and the oven was heated at 100 ° C. The mixture was put in 5 minutes and dried and cured to obtain an adhesive sheet. Table 4 shows the evaluation results of the properties of the obtained pressure-sensitive adhesive sheet. The adhesive property of the obtained adhesive sheet was good, but the printed layer was eroded by the solvent in the adhesive and the printed pattern became unreadable. Further, the phosphorescent pigment was biased toward the printing layer side and could not be uniformly present in the pressure-sensitive adhesive layer.

[0075]

[Table 4]

(1) Coating Property The coating state and the like when coated with a hot melt coater were evaluated.

(2) Holding power According to JIS Z0237, a pressure-sensitive adhesive paper test piece having a width of 25 mm and a length of 250 mm was placed on a stainless steel plate (SUS304) which had been previously polished with water-resistant abrasive paper (# 280), and a 2 kg rubber roller was attached. It is reciprocated once and pressure-bonded so that the adhered area is (25 × 25) mm ² and left in an atmosphere of 80 ° C. for 30 minutes, then 1 k is applied to one end of the adhesive paper test piece.
A load of g was applied, a stainless steel plate was placed so that a force was applied to the adhesive surface in the shearing direction, and the time until it dropped was measured.

(3) Adhesive force According to JIS Z0237, a pressure-sensitive adhesive paper test piece having a width of 25 mm and a length of 250 mm was placed on a stainless steel plate (SUS304) which had been previously polished with water-resistant abrasive paper (# 280), and a 2 kg rubber roller was attached. It was reciprocated once for pressure bonding, and after 30 minutes, the strength when peeled in the 180 ° direction at a speed of 300 mm / min was measured.

(4) Tack Measured according to JIS Z0237 at a temperature of 23 ± 2 ° C. by a ball rolling method.

(5) Appearance The appearance of the adhesive tape and the presence or absence of color unevenness were visually determined.

As shown in Examples 1 to 5, the pressure-sensitive adhesive sheet of the present invention had excellent adhesive properties and an excellent appearance. On the other hand, the pressure-sensitive adhesive sheets that did not satisfy the conditions of the present invention were not compatible with the pressure-sensitive adhesive properties and the appearance, as shown in Comparative Examples 1 to 4.

[0082]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a pressure-sensitive adhesive tape which is excellent in designability as well as having excellent productivity, good adhesive strength, holding power, tackiness and the like. Yes, it is very useful industrially.

[0083]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of an adhesive sheet.

FIG. 2 is a cross-sectional view showing an example of an adhesive sheet.

FIG. 3 is an apparatus configuration diagram showing a method for producing an adhesive sheet.

FIG. 4 is an apparatus configuration diagram showing a method for producing an adhesive sheet.

[Explanation of symbols]

1 printing layer 2 Base material layer 3 Adhesive layer 4 Separator layer 5 Granules 11 printing machines 12 Base material roll 13 coating machine 14 Separator roll 15 UV lamp 16 cutter 17 Adhesive sheet

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 133/14 C09J 133/14 171/00 171/00 F term (reference) 4J004 AA10 AB01 AB07 CA06 CB03 CC02 CE02 GA01 4J027 AC03 AC04 AC06 BA04 BA05 BA06 BA07 BA08 BA09 BA10 BA11 BA12 BA13 BA14 BA15 CB03 CB09 CC02 CC05 CC06 CD09 4J040 DF011 DF021 DF061 DG001 HB18 JB08 KA11 LA06 4J100 AJ02R AJ08R AJ09R AL08P AL08Q AL44R AL46R BA02P BA04P BA04Q BA05P BA05Q BA06P BA06Q BA08P CA05 JA03

Claims (5)

[Claims] 1. An acrylic polymer (A) having a weight average molecular weight of 80,000 to 350,000, containing 1 to 15% by mass of an α, β-unsaturated carboxylic acid (a) as a copolymerization component, Benzophenone and / or its derivative (B)
A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer comprising a UV-curable pressure-sensitive adhesive having the above and a granular material. 2. The ultraviolet-curable pressure-sensitive adhesive comprises benzophenone and / or 100 parts by mass of an acrylic polymer (A).
Or containing 0.1 to 10 parts by mass of the derivative (B),
The pressure-sensitive adhesive sheet according to claim 1. 3. The acrylic polymer (A) further contains 5 to 50% by mass of a (meth) acrylic acid alkoxy (poly) alkylene glycol adduct (b) represented by the following general formula (I) as a copolymerization component. Claim 1 which contains
Or the pressure-sensitive adhesive sheet according to 2. [Chemical 1] (R ¹ and R ² are hydrogen or a methyl group, and R ³ is 1 carbon atom.
To 12 hydrocarbon substituents, m represents an integer of 2 to 10). 4. The acrylic polymer (A) further comprises
Alkoxy (meth) acrylate represented by general formula (II)
Alkylene glycol adduct (c) as a copolymerization component
It contains 1 to 40% by mass.
The pressure-sensitive adhesive sheet described in any way. [Chemical 2] (R^FourIs hydrogen or a methyl group, R⁵Has 2 carbons
12 alkylene groups, R ⁶Is a hydrocarbon having 1 to 12 carbon atoms
Indicates a substituent) 5. The pressure-sensitive adhesive sheet according to claim 1, wherein the granular material is a pigment.