JPH08295856A - Tacky adhesive tape or sheet - Google Patents

Abstract

PURPOSE: To obtain a tacky adhesive tape or sheet having high tacky adhesive characteristics, creep characteristics, etc., by applying a tacky adhesive layer to one or both surfaces of a void-free resin layer obtained by curing a composition containing respective specific amounts of an acrylate prepolymer and a polymerizable monomer. CONSTITUTION: A tacky adhesive layer preferably composed of an acrylic resin (preferably having a glass transition point of <=-20C and a weight-average molecular weight of 150,000-1,500,000) is applied to one or both surfaces of an essentially void-free resin layer produced by curing a radiation curable resin composition containing (A) 10-90wt.% of an acrylate prepolymer (having a weight-average molecular weight of preferably >=50,000) and (B) 90-10wt.% of a polymerizable monomer [preferably composed mainly of an acrylic acid ester monomer of formula CH2 =CH-COOR<1> (R<1> is a 2-18C straight or branched- chain alkyl, etc.)]. The resin layer preferably has an elongation at break of 300-5,000% and a tensile stress of 0.1-6kg/cm<2> at 200% elongation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a creep property, an adhesive strength and a creep property which can be used for fixing various molded articles such as automobile side moldings, interior materials for construction, exterior materials, electric parts, signboards and displays. The present invention relates to a pressure-sensitive adhesive tape or sheet having excellent adaptability to curved surfaces, and more particularly to a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer (II) on one side or both sides of a specific resin layer (I) substantially free of bubbles.

[0002]

2. Description of the Related Art Conventionally, it has been widely practiced to fix various parts and the like to the surface of various molded articles as described above with a double-sided tape or the like. However, the adhesive strength of the pressure-sensitive adhesive layer is poor, creep properties are poor, curved surface adhesion is difficult, and changes in physical properties due to external factors such as pressure, heat, humidity, and light during formation and storage of the pressure-sensitive adhesive layer. , There are many challenges.
On the other hand, improvement of the adhesive itself, non-woven fabric between the adhesive layer, a method of sandwiching a film or sheet such as a foamed sheet, to contain air bubbles in the adhesive layer, or to contain a hollow body such as a glass balloon. A method of doing so has been proposed.

However, for example, it is not easy to sufficiently satisfy the contradictory properties of the adhesive force and the creep property only by improving the pressure-sensitive adhesive itself, and it is difficult to actually satisfy the industrial demand. The situation.

The method of sandwiching a hard sheet of non-woven fabric or plastic between the pressure-sensitive adhesive layers is not always satisfactory in terms of lack of flexibility, adhesive strength and adaptability to curved surfaces. Also, when sandwiching a foamed sheet, if it is a hard foamed sheet, it has the same drawbacks as when sandwiching a non-woven fabric.For a soft sheet, if the pressure during use is too high, dents occur and restoration of that part occurs. However, there are problems that it becomes difficult and that insufficient adhesion occurs and that peeling occurs at the interface between the foam sheet and the pressure-sensitive adhesive.

Further, in the method in which air bubbles are contained in the pressure-sensitive adhesive layer, as in the case of the foamed sheet sandwich, dents may occur if the pressure applied during use is too high, and water resistance and moisture absorption resistance are high. In many cases, the physical properties of the pressure-sensitive adhesive sheet as such are deteriorated, and when a hollow body such as a glass balloon is contained in the pressure-sensitive adhesive layer, it is difficult to uniformly disperse the hollow body at the time of production, stirring and mixing. Problems such as non-uniform crushing due to unavoidable problems are unavoidable, and therefore it is not easy to obtain a stable quality adhesive tape or sheet.

[0006]

As described above, the various conventional proposals for the pressure-sensitive adhesive tape or sheet have unavoidable drawbacks. The reality is that the sheet is not yet completed. The present invention seeks to solve these problems at the same time.

Thus, in view of the above-mentioned drawbacks, the object of the present invention is to provide a high degree of adhesive property, creep property, adaptability to curved surface, etc.
An object of the present invention is to provide a pressure-sensitive adhesive tape or sheet which has stable adhesive physical properties against external factors such as heat, humidity, and light and has good productivity.

[0008]

The present invention provides a pressure-sensitive adhesive layer (I) on one side or both sides of a resin layer (I) which is substantially free of bubbles.
In the adhesive tape or sheet provided with (I), the resin layer (I) is the following (A) and (B),

(A) Acrylate prepolymer 10 to 90
Wt% and

(B) An object of the present invention is to provide an adhesive tape or sheet characterized by being a cured resin layer of a radiation curable resin composition containing 90 to 10% by weight of a polymerizable monomer. It is what

The present invention will be described in detail below.

In the pressure-sensitive adhesive tape or sheet of the present invention, examples of the acrylate prepolymer (A) used in the resin layer (I) include urethane acrylate prepolymer and polyester acrylate prepolymer.

The urethane acrylate prepolymer is obtained by reacting a terminal isocyanate urethane prepolymer obtained by reacting a polyisocyanate compound and a polyol compound with a (meth) acrylate containing a hydroxyl group, or Those obtained by reacting a polyol compound with a terminal isocyanate urethane prepolymer obtained by reacting an isocyanate compound with a (meth) acrylate containing a hydroxyl group can be used.

Examples of the above polyisocyanate compound include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), 1, Aromatic diisocyanate compounds such as 3- or 1,4-xylylene diisocyanate and 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI); for example, 1,4-tetramethylene diisocyanate and 1,6-hexa Aliphatic or alicyclic diisocyanate compounds such as methylene diisocyanate, isophorone diisocyanate, hydrogenated products of the above aromatic diisocyanate compounds, dimer acid diisocyanates; dimers or trimers of these diisocyanates; and these diisocyanates, for example, ethylene glycol, propylene Glycol, polyethylene glycol Call (hereinafter PE
Abbreviated as G), polypropylene glycol (hereinafter sometimes abbreviated as PPG), polytetramethylene glycol, glycerol, an adduct with a divalent or trivalent polyol such as trimethylolpropane; and the like. .

Examples of the above-mentioned polyol compound include polyester polyol, polyether polyol, polyester ether polyol and the like.

Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- or 1,3-propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1 , 6-hexylene glycol, glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, and other polyhydric alcohols; and, for example, adipic acid, terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid , Succinic acid, sebacic acid, mesaconic acid, citraconic acid, glutaric acid, pyromellitic acid, trimellitic acid, dodecanedicarboxylic acid and other polyvalent carboxylic acids; or, for example, dimethyl adipate, dimethyl terephthalate, dimethyl phthalate, Mar acid dimethyl, alkyl esters of polycarboxylic acids such as dimethyl maleate; and condensation products of, and is raised and lactone polymers.

Examples of the polyether polyol include PEG, PPG, polytetramethylene glycol, and PEG / PPG block polymer, and examples of the polyester ether polyol include alkylene oxide such as ethylene oxide in the polyester polyol. Examples thereof include those which are added and those which have a hydroxyl group at the terminal obtained by condensing a polyether polyol and the above polycarboxylic acid.

These polyol compounds preferably have a molecular weight of 500 or more, particularly 1000 to 4000.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Examples thereof include hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like.

Although the urethanization reaction in the production of the urethane acrylate prepolymer proceeds even without a catalyst, for example, a tertiary amine such as triethylamine, for example, an organometallic compound such as dibutyltin dilaurylate or dibutyltin diacetate. Alternatively, known catalysts such as tin chlorides may be used. Further, the reaction temperature of this urethanization reaction is preferably from room temperature to 100 ° C, particularly 50 to 8 ° C.
0 ° C is preferred.

As the polyester acrylate which can be used in the present invention, a polyester compound which is a reaction product of the above polyvalent carboxylic acid or its alkyl ester with a polyhydric alcohol or the above polyether polyol,
It is obtained by a reaction with a (meth) acrylic acid compound.

Examples of the (meth) acrylic acid compound include acrylic acid having a carboxyl group, methacrylic acid; (meth) acrylate having a hydroxyl group, and (meth) acryloyl isocyanate having an isocyanate group.

Although the esterification reaction in the production of the polyester acrylate prepolymer proceeds even without a catalyst, for example, organometallic compounds such as dibutyltin dilaurylate and dibutyltin diacetate, or tin chlorides,
Known catalysts such as organotin oxides may be used. The reaction temperature of the esterification reaction is preferably 80 to 300 ° C, and particularly 1
00 to 200 ° C is preferable.

The weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the acrylate prepolymer (A) in the present invention is usually 50,000 or more, preferably 70,000 to 300,000. When the value of Mw is at least the lower limit value, the resulting resin layer (I) has a good balance between tensile elongation and cohesive force, which is preferable.
In coating the composition for forming the resin layer (I), good workability and good viscosity can be obtained, which is preferable.

The weight average molecular weight in the present invention means
It is the value obtained by analysis by gel permeation chromatography (GPC) method and by the molecular weight calibration curve of standard polystyrene.

As the polymerizable monomer (B) in the present invention, the following general formula (1): CH ₂ ═CH—COOR ¹ (1)

(In the formula, R ¹ is a linear or branched alkyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms, a linear or branched alkenyl group having 12 to 18 carbon atoms, and a carbon atom having 6 to 8 carbon atoms. Indicates a cycloalkyl group or an aralkyl group having 7 to 12 carbon atoms)

Acrylic ester monomer (b
It is preferable to use the one containing -1) as the main component.
When such an acrylic acid ester monomer (b-1) is used as the polymerizable monomer (B), the obtained resin layer (I) has suitable flexibility and tensile elongation, which is preferable. Particularly, it is preferable to use an acrylic acid ester monomer having R ¹ having 2 to 8 carbon atoms because the radiation-polymerizable property can be further improved.

Such an acrylic acid ester monomer (b-
Specific examples of the group R ¹ of 1) include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, n-octyl group, Linear or branched alkyl group such as i-octyl group, 2-ethylhexyl group, i-nonyl group, lauryl group, stearyl group; alkenyl group such as oleyl group; cycloalkyl group such as cyclohexyl group;
An aralkyl group such as a benzyl group; and the like.

Specific examples of such a monomer (b-1) include ethyl acrylate, n-propyl acrylate and i-
Propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, n-nonyl acrylate, n- Examples thereof include acrylic acid ester monomers such as dodecyl acrylate, t-dodecyl acrylate, stearyl acrylate, oleyl acrylate, cyclohexyl acrylate, and benzyl acrylate. In the present invention, one kind or two or more kinds of monomers can be appropriately selected and used from these acrylic acid ester monomers.

In the present invention, among these acrylic acid ester monomers, the glass transition point of a homopolymer (hereinafter,
It is particularly preferable to use an acrylic acid ester monomer whose Tg may be abbreviated as -10) or less. Specific examples of such acrylic acid ester monomers include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-ocicle acrylate, i-octyl acrylate,
2-ethylhexyl acrylate, i-nonyl acrylate, n-nonyl acrylate, n-dodecyl acrylate and the like can be mentioned.

In the present invention, the glass transition point (T
g) means the value measured by the following method.

Measurement of glass transition point In a cylindrical cell made of aluminum having a thickness of about 0.05 mm and having an inner diameter of about 5 mm and a depth of about 5 mm, about 10 mg of a polymer solution or dispersion was weighed as a sample. The sample dried at 100 ° C for 2 hours is used as a measurement sample. Seiko Electronics Co., Ltd. “SSC-5000
Type "Differential Scanning Calorimeter
meter) at a temperature rise rate of 10 ° C / min from -150 ° C.

The amount of the acrylic acid ester monomer (b-1) used in the polymerizable monomer (B) is
In the total 100% by weight of (B), for example, 50% by weight or more, preferably 70 to 99.8% by weight, particularly preferably 80 to 99% by weight is suitable. By adjusting the amount of the monomer (b-1) to be used in this range, suitable flexibility and tensile elongation can be obtained.

As the polymerizable monomer (B) in the present invention, if necessary, one radical polymerization is carried out in the molecule together with the acrylic acid ester monomer (b-1) of the general formula (1). A monomer having at least one functional group in addition to the unsaturated group (hereinafter, may be referred to as a functional monomer) (b-2) can be used.

Examples of such a functional monomer (b-2) include acrylic acid, methacrylic acid, crotonic acid,
Unsaturated carboxylic acids such as citraconic acid, itaconic acid, maleic acid, and fumaric acid; for example, amide group- or substituted amide group-containing monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide; Epoxy group-containing monomers such as glycidyl (meth) acrylate, glycidyl (meth) allyl ether, and glycidyl vinyl ether; for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) ) A hydroxyl group-containing monomer such as acrylate; for example, dimethylaminoethyl
Monomers having amino groups or substituted amino groups such as (meth) acrylate and diethylaminoethyl (meth) acrylate; for example, active silicon such as vinyltrichlorosilane, vinyltriethoxysilane, and 3- (meth) acryloxypropylmethoxysilane. Contained monomers; for example, divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl-i-cyanurate, ethylene glycol di (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanedioldi (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trialkoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol trimethylolpropa Tri (meth) acrylate, diethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, allyl
A monomer group having two or more ethylenically unsaturated groups such as (meth) acrylate (hereinafter sometimes referred to as polyunsaturated monomer);

The amount of the functional monomer (b-2) used in the polymerizable monomer (B) is 10 in total of the polymerizable monomer (B).
In 0% by weight, for example, 25% by weight or less, preferably 0.2 to 20
Amounts by weight, particularly preferably about 1 to 10% by weight, can be exemplified. If the amount of the monomer (b-2) used is not more than the upper limit,
The resin layer (I) to be formed is preferable because it does not lose the suitable flexibility or the tensile elongation is too small. On the other hand, it is formed by setting the amount used to be the lower limit or more. It is preferable since the cohesive force of the resin layer (I) can be improved and the adhesiveness with the pressure-sensitive adhesive layer (II) can be improved.

The polymerizable monomer (B) in the present invention includes the acrylic acid ester monomer (b-1) of the general formula (1) and a functional group monomer (b In addition to -2), if necessary, a comonomer (b-3) copolymerizable with these monomers (b-1) and (b-2) can be used.
Examples of such a comonomer (b-3) include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate. , I-octyl methacrylate, 2-ethylhexyl methacrylate, i-
Nonyl methacrylate, n-dodecyl methacrylate, i-
Dodecyl methacrylate, stearyl methacrylate,
Methacrylic acid ester monomers such as oleyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate; for example, saturated fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, “vinyl versatate” (trade name); C1-C18 linear or branched alkyl esters of unsaturated dicarboxylic acids such as dibutyl malate, dibutyl fumarate, dibutyl itaconate, dioctyl malate, dioctyl fumarate, dioctyl itaconate; for example, styrene, α- Examples thereof include aromatic vinyl monomers such as methylstyrene, vinyltoluene, and ethylvinylbenzene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and the like.

The amount of the functional group-containing monomer (b-3) used in the polymerizable monomer (B) is 10 in total of the polymerizable monomer (B).
In 0% by weight, an amount of about 50% by weight or less, preferably about 30% by weight or less is suitable. Since the use of the comonomer (b-3) may vary depending on the type of the comonomer, the amount used cannot be determined unambiguously, but with a suitable balance between flexibility and tensile elongation and these. Since it is useful for adjusting the balance with the cohesive force and the like as desired, it can be appropriately selected within the above range amount so as to meet such purpose. If the amount of the comonomer (b-3) used is not more than the upper limit of the range amount, suitable flexibility will not be impaired and tensile elongation will not be too small. When (b-3) is used, it is preferable to appropriately select and use the amount within the range.

The proportion of the acrylate prepolymer (A) and the polymerizable monomer (B) contained in the resin layer (I) in the present invention is such that the total of the components (A) and (B) is 100% by weight. Against
It is necessary that the acrylate prepolymer (A) is 10 to 90% by weight, preferably 20 to 80% by weight, and the polymerizable monomer (B) is 10 to 90% by weight, preferably 20 to 80% by weight. If the content of the acrylate prelimer (A) exceeds the upper limit and is too large, it becomes difficult to coat at room temperature, which is not preferable, and if it is less than the lower limit and the amount is too small, flexibility and tensile elongation are insufficient. It is not preferable because it disappears.

The resin layer (I) in the present invention is prepared by curing a radiation-curable resin composition containing an acrylate prepolymer (A) and a polymerizable monomer (B) by irradiation with radiation. It is formed. Examples of the radiation include ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, γ rays, and X rays, but they have problems of equipment, ease of handling, and storage stability. The use of ultraviolet rays or electron beams is preferable, and the use of ultraviolet rays is particularly preferable, from the standpoint of the ability to use other materials.

When ultraviolet rays are used as the radiation, the radiation-curable resin composition of the present invention contains an ultraviolet polymerization initiator (hereinafter, referred to as the acrylate-based prepolymer (A) and the polymerizable monomer (B)). (Sometimes abbreviated as UV initiator).

Examples of the UV initiators include diacetyl, bibenzoyl, benzophenone, ω-bromoacetophenone, α-hydroxycyclohexyl phenyl ketone, chloroacetone, benzoquinone, anthraquinone,
2-ethylanthraquinone, 2-chloroanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin-i-butyl ether, chlorothioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, and the like. The amount used may be, for example, about 0.01 to 15 parts by weight based on 100 parts by weight of the total of the acrylate prepolymer (A) and the polymerizable monomer (B).

The resin layer (I) in the present invention is, if necessary, for example, a phthalate ester system such as dioctyl phthalate, a phosphate ester system such as tricresyl phosphate, a plasticizer such as process oil; Organic or inorganic colorants such as titanium oxide, carbon black and phthalocyanine blue; inorganic fillers such as clay, talc, calcium carbonate, silica, aluminum hydroxide, glass powder, glass balloons; known additives such as preservatives You may add a thing.

The thickness of the resin layer (I) is generally 50 to 5000.
It is suitable that the thickness is μm, preferably about 100 to 3000 μm.

In the present invention, the breaking elongation of the resin layer (I) is 300 to 5000%, preferably 500 to 3000%. When the elongation at break is not less than the lower limit value, there is no trouble such as insufficient adhesive strength of the obtained adhesive tape or sheet, and the curved surface adaptability is excellent and the object of the present invention can be achieved. It is preferable because it is possible. On the other hand, if it is at most the upper limit value, generally good creep performance can be maintained, which is preferable.

The tensile strength of the resin layer (I) at an elongation of 200% (hereinafter, sometimes referred to as 200% modulus) is, from the viewpoint of good flexibility and good cohesive force of the resin layer (I),
Usually 0.1~6kg / cm ^2, the breaking strength of preferably well in the range of 0.5 to 5 kg / cm ^2, further resin layer (I), the resin layer
It is preferably at least 200% tensile strength of (I).

The resin layer (I) used in the present invention is characterized by containing substantially no bubbles. When air bubbles are contained, the surface smoothness of the obtained adhesive tape or sheet tends to be impaired, and therefore the adhesive strength is insufficient, or the adhesive tape is likely to be affected by the external environment such as absorbing water or absorbing moisture, resulting in long-term adhesive properties. It becomes difficult to keep it stable, and
If the pressure applied during use is too strong, a dent is formed, which makes it difficult to restore that part, which may cause various problems such as partial adhesion failure. Note that the above-mentioned "substantially free of bubbles" does not exclude the presence of bubbles to the extent that these problems cannot occur.

The adhesive resin used for forming the adhesive layer (II) in the present invention is not particularly limited, and examples thereof include acrylic resin, natural or synthetic rubber resin, olefin resin, Silicon resin, urethane resin, epoxy resin, etc. can be mentioned.

As the above acrylic resin, for example,
Butyl acrylate, 2-ethylhexyl acrylate,
Acrylic ester (co) polymers mainly composed of acrylic acid esters such as n-octyl acrylate; examples of natural or synthetic rubber resins include natural rubber, butadiene polymer, styrene-butadiene copolymer, styrene-isoprene. Copolymer, acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer, isoprene rubber, chloroprene rubber, butyl rubber, etc .; Examples of the olefin resin include ethylene-vinyl acetate copolymer, ethylene-vinyl propionate Examples thereof include copolymers, propylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and the like.

Of these adhesive resins, acrylic resins are preferably used from the viewpoint of excellent weather resistance and the like. The Tg of the acrylic resin is generally -20 ° C or lower and -30 ° C.
The following is preferred. Also, its Mw is 15 to 1.5 million,
Particularly, it is preferably 25 to 1,000,000.

The Mw of the adhesive resin is the resin layer
In the same manner as the Mw of the acrylic prepolymer (A) in (I), the Tg of the adhesive resin is the Tg of the homopolymer of the polymerizable monomer (B) in the resin layer (I). The value measured by the same method as.

As the acrylic resin preferably used in the present invention, as described above, for example, ethyl acrylate, n-propyl acrylate, n-butyl acrylate,
n-hexyl acrylate, n-octyl acrylate, i-
Octyl acrylate, 2-ethylxyl acrylate,
Acrylic esters such as n-nonyl acrylate and i-nonyl acrylate (hereinafter sometimes referred to as the main monomer)
(Co) polymer of

Alternatively, using these main monomers as main component amounts,
If necessary, other acrylic acid ester (eg, methyl acrylate, t-butyl acrylate, etc.), methacrylic acid ester (eg, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl) Methacrylate, etc.), saturated fatty acid vinyl ester [eg, vinyl formate, vinyl acetate, vinyl propionate, “vinyl versatate” (trade name), etc.], aromatic vinyl monomer (eg, styrene, α-methylstyrene, vinyl) Toluene etc.), vinyl cyanide monomer (acrylonitrile, methacrylonitrile etc.), halogenated vinyl monomer (eg vinyl chloride, vinylidene chloride etc.), olefinic monomer (eg ethylene, propylene, n-butene) , Butadiene, isoprene, chloroprene Etc.) and the like main monomer and a copolymerizable monomer (hereinafter sometimes referred to as a comonomer).

Further, if necessary, a reactive acrylic acid ester-based copolymer obtained by copolymerizing the functional monomer with the main monomer and the comonomer may be used.

Examples of such a functional monomer include unsaturated carboxylic acids exemplified in the polymerizable monomer (B),
Amide group- or substituted amide group-containing monomer, epoxy group-containing monomer, hydroxyl group-containing monomer, amino group- or substituted amino group-containing monomer, active silicon-containing monomer, polyunsaturated monomer, etc. Can be mentioned.

The acrylic resin which can be used in the present invention is, for example, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or radiation polymerization by ultraviolet rays, electron beams, etc., ionic polymerization, addition polymerization, polycondensation, etc. It can be manufactured by a conventionally known method.

In the pressure-sensitive adhesive tape or sheet of the present invention, when the pressure-sensitive adhesive layers (II) are provided on both sides of the resin layer (I), the pressure-sensitive adhesive layers on each surface are formed of the same type or different pressure-sensitive adhesive resins. However, it is not necessarily limited thereto, and different types of adhesive resins may be used depending on the application of the adhesive tape or sheet to be obtained.

The pressure-sensitive adhesive layer (II) in the present invention can be appropriately crosslinked if necessary. However, in this case, it is important to consider so as not to lose the balance between the flexibility and the tensile elongation of the pressure-sensitive adhesive layer and the balance between the adhesive force and the cohesive force.

As the above-mentioned method of cross-linking, the polyunsaturated group monomer (diallyl phthalate, divinylbenzene, 1) exemplified as the polymerizable monomer (B) of the resin layer (I) at the time of producing the adhesive resin is used. , 6-hexanediacrylate, etc.) and internally cross-linking; for example, unsaturated carboxylic acid such as acrylic acid during production of adhesive resin, hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate, glycidyl methacrylate. Epoxy group-containing monomer such as N-methylolacrylamide, substituted amide group-containing monomer such as N-methylolacrylamide, functional silicon-containing monomer such as vinyltriethoxysilane, etc. After introducing a functional group into, polyisocyanate compound, silane compound, organometallic compound, polyepoxy compound, aziridine compound,
A method of adding and reacting a cross-linking agent such as an amino compound; for example, after adding and dispersing the polyunsaturated group monomer and the UV initiator to the adhesive resin as necessary, radiation such as ultraviolet rays and electron beams And the like; and other methods can be adopted as necessary.

Among the above-mentioned cross-linking agents, the polyisocyanate compound is an aromatic diisocyanate compound, an aliphatic or alicyclic diisocyanate compound used in the acrylate prepolymer (A) in the resin layer (I), or these diisocyanates. And a dimer of these diisocyanates and an adduct of a divalent or trivalent polyol can be used.

Blocked isocyanate compounds can also be used. Examples of the polyisocyanate compound such as trimethylolpropane tritolylene diisocyanate methyl ethyl ketoxime adduct include methyl alcohol, ethyl alcohol, n-butyl alcohol, cyclohexyl alcohol, and the like. Aliphatic, alicyclic or aromatic alcohols such as benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, phenol; hydroxy tertiary amines such as dimethylaminoethanol, diethylaminoethanol; acetoxime, methylethylketoxime, etc. Ketoxime; for example, active methylene compounds such as acetylacetone, acetoacetic acid ester, malonic acid ester, etc. ; .Epsilon. lactams such as caprolactam; may include those obtained by adding the volatile low molecular weight active hydrogen compounds such as.

Examples of silane compounds include 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-lcapto. Propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, etc .;

Examples of the organometallic compound include i-propyl (tri-i-stearoyl) titanate, i-propyl (trioctanoyl) titanate, i-propyltris (dioctylpyrophosphate) titanate, titanium di-i- Stearate oxyacetate, titanium tetra-i-propylate, titanium tetra-2-ethylhexylate, tetraoctylene glycol titanate, triethanolamine titanium di-i-propylate, ammonium salt of titanium lactate, polyalkyl titanate, polytitanium Acylate (polymer of titanium tetrabutyrate, polymer of titanium oleate), aluminum tri-i-propionate, aluminum tri-s-
Butyrate, mono-s-butoxy aluminum di-i-propionate, ethyl acetoacetate aluminum di-i-
Propionate, ethyl acetoacetate aluminum di-i-propylate, aluminum tris (ethyl acetoacetate), aluminum tris acetylacetonate, antimony butyrate, zirconium-s-butyrate, zirconium diethoxy-t-butyrate, hafnium-t-butyrate, etc. ,

Examples of the epoxy compound include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like;
As the aziridine compound, a reaction product of the polyisocyanate compound and ethyleneimine, for example, a reaction product of MDI and ethyleneimine, and the like; as the amino resin, for example, melamine resin, guanamine resin, urea resin, melamine-urea Examples thereof include resins and melamine-phenol co-condensation resins.

The amount of these cross-linking agents used is the same as the above-mentioned adhesive resin.
The amount is 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight. Further, various catalysts may be used in combination as a crosslinking accelerator, if necessary.

The thickness of one layer of the pressure-sensitive adhesive layer (II) in the present invention is generally 10 to 500 μm, preferably 10 to 100 μm.

In providing the pressure-sensitive adhesive layer (II), a resin layer (I) and a pressure-sensitive adhesive layer (II) are prepared by using an undercoating agent or by subjecting the surface of the resin layer (I) to corona discharge treatment. And can be more firmly adhered.

For the production of the pressure-sensitive adhesive tape or sheet of the present invention, any conventionally known method is adopted. That is, for example, a prepared liquid of the acrylate-based prepolymer (A) and the polymerizable monomer (B) is applied to a release paper at an appropriate thickness using a doctor blade coater or the like, and irradiated with radiation. The resin layer (I) is formed by curing and further laminating as necessary. Separately from this, the organic solvent liquid of the adhesive resin is used as it is, or a cross-linking agent is added if necessary, and similarly coated on release paper, dried, and cured and laminated as necessary to form an adhesive. Form layer (II). Resin layer (I) obtained earlier
The pressure-sensitive adhesive layer (II) is laminated on one side or both sides to obtain the pressure-sensitive adhesive tape or sheet of the present invention.

When the pressure-sensitive adhesive layer (II) is laminated on both sides of the resin layer (I), the pressure-sensitive adhesive resin forming each pressure-sensitive adhesive layer may be the same type or the same type depending on the use of the obtained pressure-sensitive adhesive tape or sheet. Different kinds of adhesive resins may be used, or adhesive resins of different systems may be used.

The resin layer obtained as described above
A method in which an adhesive resin solution for forming the pressure-sensitive adhesive layer (II) is applied to one side or both sides of (I), dried, and cured and laminated if necessary can also be adopted.

The adherend on which the pressure-sensitive adhesive tape or sheet of the present invention can be preferably used is, for example, paper,
Textile products such as woven fabrics, knitted fabrics, non-woven fabrics; various metal materials such as iron, steel, stainless steel, zinc, galvanized iron, tin plate, copper, brass, aluminum and duralumin; polyvinyl chloride,
Thermoplastic resins such as thermoplastic polyester, polyamide, polystyrene, polycarbonate resin, acrylonitrile-butadiene-styrene resin, thermoplastic polyurethane;
Examples thereof include thermosetting resins such as phenolic resins, melamine resins, urea resins and unsaturated polyester resins; inorganic materials such as glass, ceramics, slate, mortar and concrete; natural materials such as wood and stone materials;

Specifically, the adhesive tape or sheet is formed of the adherend such as a nameplate, rock wool board, gypsum board, signboard, characters for display, home electric appliance parts, side moldings of vehicles such as automobiles. It can be used by pasting it on the surface of the molded article by a conventionally known method, for example, a roll crimping method or the like, and further sticking it to another adherend.

[0074]

The pressure-sensitive adhesive tape or sheet of the present invention comprises:
On one or both sides of the resin layer (I) substantially free of bubbles,
Since the adhesive layer (II) is provided, its physical properties are not affected by the strong pressure when using it, and the adhesive strength, creep characteristics, and curved surface adaptability that cannot be separated by conventional technology are used. A structure having excellent adhesive properties in all of the above was obtained.

Conventional pressure-sensitive adhesive tapes or sheets containing bubbles, glass balloons, etc. are
The pressure-sensitive adhesive tape or sheet or sheet of the present invention has stable and excellent pressure-sensitive adhesive property, although the pressure-sensitive adhesive property changes depending on external conditions such as breakage of bubbles or glass balloons during production or use and is unstable. Have.

[0076]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The methods for measuring the physical properties are as follows.

(1) 200% modulus of resin layer (I), elongation at break
Degree and breaking strength The resin layer (I) is cut out into 15 mm x 75 mm to make a test piece, and after leaving it for 24 hours in the standard condition (23 ° C, 65% RH), the gripping interval is 25 mm and the peeling speed is 100 mm in the standard condition. The tensile test is performed under the condition of / min, and the 200% modulus, the elongation at break and the breaking strength are measured.

(2) Shear strength of adhesive sheet Two aluminum plates (thickness 0.8 mm, width 25.4 mm, length 100)
mm) with a 25 mm x 25 mm double-sided adhesive sheet, and
After applying a load of kg to the adhesive surface for about 10 minutes and then leaving it for 72 hours in the standard condition (23 ℃, 65% RH), 50 mm / mi in the standard condition
Tensile at a speed of n, shear strength was measured and used as a guide for creep properties.

(3) Adhesive Strength of Adhesive Sheet A thickness obtained by vapor-depositing aluminum on one surface of the double-sided adhesive sheet.
Width of 50 μm polyester terephthalate (PET) film so that the aluminum vapor deposition surface is in contact
It was cut into 25 mm to make a test piece, and this was pressure-bonded to a SUS 304 stainless steel plate polished with # 280 water-resistant abrasive paper specified in JIS R-6253 according to the method of JIS Z-0237, and then the standard condition for 24 hours (23 After leaving it at 65 ° C and 65% RH), measure its 180 ° peel strength (kg / 25 mm) under a standard condition with a peel rate of 100 mm / min.

Reference Example 1 Method for Producing Acrylate Prepolymer In a separable flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping device, 110 parts by weight of ethyl acetate (EAc) as an organic solvent and a polyol compound were used. 150 parts by weight of PPG (molecular weight 3000) which is a polyether polyol and "Coronate 437" as a polyisocyanate compound.
0 ”[MDI polytetramethylene glycol adduct,
Isocyanate content 15% by weight; Nippon Polyurethane Co., Ltd.
30.8 parts by weight was mixed, and 0.308 parts by weight of dibutyltin dilaurate was added as a catalyst to this mixture, and the mixture was reacted at 75 ° C. for 3 hours. Next, 2.2 parts by weight of 2-hydroxyethyl acrylate (HEA) as a hydroxyl group-containing (meth) acrylate was added to this reaction mixture, and the reaction was continued until infrared absorption (IR) analysis stopped absorption of isocyanate. The resulting urethane acrylate prepolymer solution had a solid content of about 62.5% by weight,
w was about 100,000.

Reference Example 2 In Reference Example 1, instead of using 30.8 parts by weight of "Coronate 4370", 33.4 parts by weight was used and reacted for 2 hours instead of reacting at 75 ° C for 3 hours, and then 2.2 parts by weight of HEA was added. A urethane acrylate prepolymer was prepared in the same manner as in Reference Example 1 except that 3.1 parts by weight was added instead. The resulting urethane acrylate prepolymer solution had a solid content of about 62.9% by weight, and the Mw of the prepolymer was about 50,000.

Reference Example 3 In a separable flask similar to that used in Reference Example 1, 1000 parts by weight of EAc as an organic solvent, 1550 parts by weight of PPG (molecular weight 3000) as a polyether polyol, and polyvalent carboxylic acid alkyl ester were used. As dimethyl adipate 8
7.0 parts by weight were mixed, and 8.2 parts by weight of dibutyltin dilaurylate was added to this mixture as a catalyst and reacted at 130 ° C. for 5 hours. Next, 0.04 parts by weight of acrylic acid (AA) as a (meth) acrylic acid compound was added to this reaction mixture, and the reaction was continued. The obtained polyester acrylate prepolymer solution had a solid content of about 62% by weight, and the Mw of the prepolymer was about 100,000.

Method for Producing Acrylic Adhesive Resin Solution Reference Example 4 In the same separable flask as used in Reference Example 1, 90 parts by weight of butyl acrylate (BA) and 10 parts of acrylic acid (AA) were added.
A mixture was prepared by mixing 100 parts by weight of azobis-i-butyronitrile (AIBN) with 100 parts by weight of ethyl acetate (EAc). Then, as an initial charge, 25% by weight of this mixture was placed in a separable flask, heated while stirring, and polymerized for 40 minutes under reflux at an internal temperature of 80 to 85 ° C. Next, while maintaining the internal temperature at 80 to 85 ° C, the remaining amount of the mixture of 75% by weight was successively added dropwise over about 60 minutes. After maintaining the reflux temperature for another 120 minutes, 50 parts by weight of toluene was added to dilute the mixture to a solid content of about 35% by weight and a viscosity of 9000 cps (B-type rotational viscometer, 25 ° C, 10r
pm) to obtain an acrylic adhesive resin solution. This adhesive resin had an Mw of 650,000 and a Tg of -46 ° C.

Example 1 In a separable flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping device and a decompression device, 80 parts by weight of the urethane acrylate prepolymer solution obtained in Reference Example 1 (solid content: about 50) was added. (Part by weight), and the inside of the flask is 100 ° C or less, 10m
EAC was distilled off by heating under reduced pressure to mHg or less, and then while maintaining the inside of the flask at about 100 ° C., 49 parts by weight of butyl acrylate (BA) of the polymerizable monomer (B) was added until uniform. After mixing well, cooled to room temperature and the polymerizable monomer (B) 2-
1 part by weight of hydroxyethyl acrylate (HEA) and UV
Initiator "IRGACURE 500" [Japan Ciba Geigy Co., Ltd.
(Production) (IC-500) (1 part by weight) and uniformly mixed to obtain an ultraviolet curable resin composition. Type, amount and M of the acrylate-based prepolymer (A) used in the obtained composition
Table 1 shows w, the type and amount of the polymerizable monomer (B), the type and amount of the UV initiator, and the viscosity and coatability of the composition.
It was shown to.

The obtained ultraviolet curable resin composition was applied onto a PET sheet (hereinafter sometimes abbreviated as PET Separator) which had been subjected to a release treatment by using a doctor blade, and the upper part of the composition layer and PET. A resin layer with a thickness of about 300 μm that is irradiated with ultraviolet rays (UV) of 2400 mJ / cm ² in total from both sides of the separation surface to cure it.
Got (I). The properties (elongation at break, breaking strength) of the obtained resin layer (I) having good flexibility were measured. Table 1 shows the coatability of the used ultraviolet-curable resin composition, Table 2 shows the type and dose of radiation used for curing the composition, and the properties of the resin layer (I) after the irradiation.

Next, 286 parts by weight of the acrylic adhesive resin solution (solid content: about 100 parts by weight) obtained in Reference Example 4 and an isocyanate compound "Coronate L" as a cross-linking agent [trade name: TD
About 45% ethyl acetate solution of trimethylolpropane adduct of I: manufactured by Nippon Polyurethane Co., Ltd.] 5.6 parts by weight (solid content of about 2.5 parts by weight) was thoroughly mixed to prepare an isocyanate crosslinkable adhesive resin composition. After that, this is applied on a release paper and dried at 100 ° C. for 3 minutes to give an adhesive layer (I
I) was obtained, and this was laminated on both sides of the resin layer (I) and left at room temperature for 7 days to crosslink the adhesive layer (II) almost completely to prepare an adhesive sheet. Various adhesive properties (shearing force, adhesive force) were measured using this adhesive sheet. Adhesive layer (I
Table 3 shows the type and amount of the adhesive resin used to form I), the type and amount of the crosslinking agent, the crosslinking method, and various adhesive properties.

Examples 2 to 3 In Example 1, the mixing ratio of the urethane acrylate prepolymer (A) obtained in Reference Example 1 and the polymerizable monomer (B) (the ratio of BA and HEA used was unchanged). ) Was changed or the polymerizable monomer (B) was not used, and an ultraviolet curable resin composition was obtained in the same manner as in Example 1. Using the obtained ultraviolet curable resin composition, an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3.

Comparative Example 1 In a separable flask similar to that used in Example 1, 160 parts by weight of the urethane acrylate prepolymer solution obtained in Reference Example 1 (solid content: about 100 parts by weight) and UV initiator "IC- Five
1 part by weight of "00" was charged and uniformly mixed at room temperature to obtain an ultraviolet curable resin composition. The obtained composition was applied onto PET sepa using a doctor blade and dried at 40 ° C. for 24 hours to form a film, and then a total of 2400 mJ / cm from above the film and from both sides of the PET sepa surface. The resin layer (I) having a thickness of about 300 μm was obtained by irradiating with ultraviolet rays (UV) ² and curing. Using this resin layer (I), an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), amount of polymerizable monomer (B), type and amount of UV initiator, and ,
The viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and dose of radiation used for curing the composition, and the thickness and properties of the resin layer (I) after irradiation. Table 2
Table 3 shows the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties.

Comparative Example 2 49 parts by weight of the polymerizable monomer (B), 1 part by weight of HEA and UV were placed in a separable flask similar to that used in Example 1.
1 part by weight of an initiator "IC-500" was charged and uniformly mixed at room temperature to obtain an ultraviolet curable resin composition. The obtained composition could not be coated on PET Sepa and the resin layer (I) could not be formed.

Examples 4 to 5 In Example 1, 80 parts by weight of the solution of the urethane acrylate prepolymer (A) obtained in Reference Example 1 (solid content: about 50) was used.
Instead of using, the solution of the urethane acrylate prepolymer (A) obtained in Reference Example 2 was used in parts by weight (solid content: about 80 parts by weight) or parts by weight (solid content: about 65 parts by weight). Polymerizable monomer (B) BA and HEA
An ultraviolet-curable resin composition was obtained in the same manner as in Example 1 except that the total amount was changed without changing the usage ratio. Using the obtained ultraviolet curable resin composition, an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate-based prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3.

Example 6 In Example 1, 80 parts by weight of the solution of the urethane acrylate prepolymer (A) obtained in Reference Example 1 (solid content: about 50) was used.
UV-curable resin composition in the same manner as in Example 1 except that the solution of the polyester acrylate prepolymer (A) obtained in Reference Example 3 is used in parts by weight (solid content: about 50 parts by weight) instead of using Got Using the obtained ultraviolet curable resin composition, an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using this adhesive sheet.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3.

Examples 7 to 9 Instead of using 49 parts by weight of BA and 1 part by weight of HEA as the polymerizable monomer (B) in Example 1, 24.5 parts by weight of 2-ethylhexyl acrylate (EHA), BA 24.5 parts by weight and HE
A 1 part by weight; BA 24.5 parts by weight, ethyl acrylate (EA)
24.5 parts by weight and HEA 1 part by weight; or BA 47.5 parts by weight and
An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 2.5 parts by weight of AA was used. Using the obtained ultraviolet curable resin composition, an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3.

Examples 10 to 11 In Example 1, instead of using IC-500 as a photopolymerization initiator, "IRGACURE 184" [Japan Ciba Geigy] was used.
Example 1 except that (IC-184) or “Irgacure 369” (manufactured by Ciba-Geigy Co., Ltd.) (IC-369) is used.
An ultraviolet curable resin composition was obtained in the same manner as in. Using the obtained ultraviolet curable resin composition, an adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3.

Example 12 In Example 1, a UV initiator was not used, and ultraviolet rays (UV) were used as a radiation for curing the resin layer (I) in a total amount of 2400 mJ /
An electron beam curable resin composition was obtained in the same manner as in Example 1 except that the electron beam (EB) was irradiated at a total of 5 Mrad instead of cm ² . Using the obtained electron beam curable resin composition, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 below. Various adhesive properties were measured using these adhesive sheets.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, Table 1 shows the viscosity and coatability of the obtained electron beam curable resin composition, the type and dose of radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. Table 2 shows the properties and properties, Table 3 shows the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties. An adhesive sheet was obtained.
Various adhesive properties were measured using this adhesive sheet.

Example 13 After forming the resin layer (I) in the same manner as in Example 1, 286 parts by weight of the acrylic adhesive resin solution obtained in Reference Example 4 (solid content: about 100 parts by weight) was crosslinked. Trimethylolpropane triacrylate (TMPT), which is a polyunsaturated monomer
A) 4.5 parts by weight and 1.5 parts by weight of the UV initiator "IC-184" were added and mixed to prepare a UV-curable adhesive resin composition,
After applying this on release paper and drying at 100 ° C for 3 minutes, 600 mJ / cm ² of ultraviolet ray (UV) is irradiated from above the formed pressure-sensitive adhesive layer to crosslink it, and a pressure-sensitive adhesive layer with a thickness of about 50 μm ( II) was obtained.
A pressure-sensitive adhesive sheet was prepared by laminating the pressure-sensitive adhesive layer (II) on both sides of the resin layer (I). Various adhesive properties were measured using this adhesive sheet.

Type, amount and Mw of acrylate prepolymer (A) used for forming resin layer (I), type and amount of polymerizable monomer (B), type and amount of UV initiator ,
Also, the viscosity and coatability of the obtained ultraviolet curable resin composition are shown in Table 1, the type and irradiation amount of the radiation used for curing the composition, and the thickness of the resin layer (I) after irradiation. The properties and properties are shown in Table 2, and the type and amount of the adhesive resin used for forming the adhesive layer (II), the type and amount of the crosslinking agent, and various adhesive properties are shown in Table 3. An adhesive sheet was obtained.
Various adhesive properties were measured using this adhesive sheet.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

The pressure-sensitive adhesive tape or sheet of the present invention comprises:
A cured resin layer of a radiation-curable resin composition containing a specific amount of each of an acrylate prepolymer (A) and a polymerizable monomer (B), the resin layer containing substantially no bubbles. The pressure-sensitive adhesive layer (II) is provided on one side or both sides of (I).

Since the pressure-sensitive adhesive tape or sheet of the present invention is excellent in creep characteristics, adhesive strength and adaptability to curved surfaces, it is well adapted to uneven surfaces and surfaces with large curvature and does not break even if shear force is applied, In addition, since it does not substantially contain bubbles in the pressure-sensitive adhesive layer, it does not cause dents even when pressed during use, and hardly absorbs water or moisture, so
Since it also has the excellent performance of being able to maintain stable adhesive properties for a long period of time, it can be used to fix various molded bodies such as automobile side moldings, interior materials for building materials, exterior materials, electrical parts, signs, and displays. In addition to being publicly used as an adhesive tape or sheet, it can be used for a wide range of purposes.

Claims (9)

[Claims] 1. A pressure-sensitive adhesive tape or sheet comprising a pressure-sensitive adhesive layer (II) provided on one side or both sides of a resin layer (I) substantially free of bubbles, wherein the resin layer (I) has the following (A) and
(B) a cured resin layer of a radiation curable resin composition comprising (A) an acrylate-based prepolymer in an amount of 10 to 90% by weight, and (B) a polymerizable monomer in an amount of 90 to 10% by weight. An adhesive tape or sheet characterized by being present. 2. The pressure-sensitive adhesive tape or sheet according to claim 1, wherein the acrylate prepolymer (A) has a weight average molecular weight of 50,000 or more. 3. The polymerizable monomer (B) has the following general formula (1): CH ₂ ═CH—COOR ¹ ... (1) (wherein R ¹ has 2 to 18 carbon atoms). A straight chain or branched alkyl group, a straight chain or branched alkenyl group having 12 to 18 carbon atoms,
The pressure-sensitive adhesive tape or sheet according to claim 1, which comprises an acrylic acid ester monomer represented by a cycloalkyl group having 6 to 8 carbon atoms or an aralkyl group having 7 to 12 carbon atoms as a main component. . 4. The pressure-sensitive adhesive tape or sheet according to claim 3, wherein the homopolymer of acrylic acid ester has a glass transition point of −10 ° C. or lower. 5. The adhesive tape or sheet according to claim 1, wherein the resin layer (I) has a breaking elongation of 300 to 5000%. 6. The tensile strength of the resin layer (I) at an elongation of 200% is 0.
The pressure-sensitive adhesive tape or sheet according to claim 1 or 5, which has a weight of 1 to 6 kg / cm ² . 7. The pressure-sensitive adhesive tape or sheet according to claim 1, wherein the pressure-sensitive adhesive layer (II) is made of an acrylic resin. 8. The pressure-sensitive adhesive tape or sheet according to claim 7, wherein the glass transition point of the acrylic resin is −20 ° C. or lower. 9. The weight average molecular weight of the acrylic resin is 15 to 15.
The pressure-sensitive adhesive tape or sheet according to claim 7 or 8, which is in the range of 0,000.