JP6837879B2 - Adhesive tape - Google Patents

Description

The present invention relates to an adhesive tape.

Generally, for LED packages (electronic components in which LED chips and phosphors are sealed with a sealing resin on lead frames, stems, boards, cases, etc.), the LED chips mounted on the shipping adhesive tape are collected (picked up). Manufactured. The pickup abuts a stick called a pin or needle from the side of the adhesive tape on which the LED chip is not mounted (so-called "needle push-up"), and then uses a suction jig called a collet on the adhesive tape. It is a method of adsorbing and separating the LED chip from the above. Generally, the LED chip is shipped from the LED chip manufacturer to the LED package manufacturer in a state of being mounted on the shipping adhesive tape. Therefore, the LED chip is stored on the adhesive tape for shipping for a predetermined period (several weeks to several months) until the LED chip is used in the manufacturing process of the LED package, and the manufacturing process of the LED package. Then it will be picked up from the adhesive tape for shipping.

As illustrated in the adhesive tape for shipping the LED chip, when the adherend is picked up after being attached to the adhesive tape for a long period of time, adhesive residue is likely to occur on the adherend. There is a problem that the adhesive residue contaminates the adherend.

Japanese Unexamined Patent Publication No. 2005-019607

Conventionally, as a pressure-sensitive adhesive having excellent cohesive power, a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composed of a carboxyl group-containing polymer has been widely used. Further, usually, the pressure-sensitive adhesive layer or the base material constituting the pressure-sensitive adhesive tape contains a plasticizer. In the conventional adhesive tape, the inventors of the present invention have altered the polymer and / or the plasticizer due to the reaction between the carboxyl group of the carboxyl group-containing polymer and the plasticizer, and as a result, the altered plasticizer itself. It was found that the plasticizer, which easily exudes from the pressure-sensitive adhesive layer and whose dispersibility is reduced due to alteration, exudes from the pressure-sensitive adhesive layer. The plasticizer exuded from the pressure-sensitive adhesive layer becomes adhesive residue when the adherend is peeled off, and causes contamination of the adherend.

The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to have sufficient adhesive strength (having a pressure-sensitive adhesive layer having sufficient cohesiveness) and plasticizer. It is an object of the present invention to provide an adhesive tape which contains an agent but suppresses exudation of the plasticizer from the adhesive layer and does not easily contaminate the adherend.

The adhesive tape of the present invention is an adhesive tape provided with a base material and a pressure-sensitive adhesive layer arranged on at least one surface of the base material and composed of an acrylic-based pressure-sensitive adhesive. The constituent base polymer contains a structural unit having a hydrogen-binding functional group containing no free hydrogen, the pressure-sensitive adhesive layer contains a plasticizer, and the adhesive force of the pressure-sensitive adhesive tape to a SUS plate after 23 ° C. × 30 minutes. However, it is 2.1 N / 20 mm or less.
In one embodiment, the content ratio of the structural unit having a hydrogen-bonding functional group containing no free hydrogen is 9 parts by weight to 23 parts by weight with respect to 100 parts by weight of the base polymer.
In one embodiment, the base polymer further contains a structural unit derived from a carboxyl group-containing monomer, and the content ratio of the structural unit derived from the carboxyl group-containing monomer is 0.2 weight by weight with respect to 100 parts by weight of the base polymer. It is less than a part.
In one embodiment, the base polymer does not contain structural units derived from carboxyl group-containing monomers.
In one embodiment, the free hydrogen-free hydrogen-bonding functional groups are N-vinyl-2-pyrrolidone, N, N-diethylacrylamide, acryloylmorpholin and 2- (2-methylimidazolyl). It is a structural unit derived from at least one monomer selected from the group consisting of ethyl (meth) acrylate.

According to the present invention, the plasticizer has sufficient adhesive strength (has a pressure-sensitive adhesive layer having sufficient cohesiveness), and while containing a plasticizer, the exudation of the plasticizer from the pressure-sensitive adhesive layer is suppressed. It is possible to provide an adhesive tape that does not easily contaminate the adherend.

It is the schematic sectional drawing of one Embodiment of the adhesive tape of this invention. It is the schematic sectional drawing of another embodiment of the adhesive tape of this invention.

A. Overall Configuration of Adhesive Tape FIG. 1 is a schematic cross-sectional view of the adhesive tape according to one embodiment of the present invention. The adhesive tape 100 includes a base material 10 and an adhesive layer 20 arranged on at least one surface (one side in the illustrated example) of the base material 10. The pressure-sensitive adhesive layer 20 is composed of an acrylic pressure-sensitive adhesive. Further, the pressure-sensitive adhesive layer 20 contains a plasticizer. The plasticizer in the pressure-sensitive adhesive layer is a plasticizer contained in a material for forming the pressure-sensitive adhesive layer (specifically, a pressure-sensitive adhesive), and a plasticizer contained in the material for forming the base material and transferred from the base material to the pressure-sensitive adhesive layer. Means a plasticizer. Although not shown, the pressure-sensitive adhesive sheet of the present invention may be provided with a release liner on the outside of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface until it is used.

The acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 20 contains a base polymer, and the base polymer contains a structural unit having a hydrogen-bonding functional group containing no free hydrogen (details will be described later). In the present invention, by using a base polymer containing a structural unit having a hydrogen-bonding functional group containing no free hydrogen (hereinafter, also referred to as structural unit A), a decrease in the cohesiveness of the polymer in the pressure-sensitive adhesive layer is suppressed. While doing so (that is, without impairing the adhesive strength of the pressure-sensitive adhesive layer), the content of carboxyl groups in the base polymer constituting the pressure-sensitive adhesive can be reduced or reduced to zero. Deterioration of the plasticizer in the pressure-sensitive adhesive layer can be prevented by reducing the content ratio of the carboxyl group in the polymer constituting the pressure-sensitive adhesive. As a result, the exudation of the plasticizer from the adhesive layer is suppressed, and even when the adherend that has been adhered for a long period of time is peeled off from the adhesive tape, the adhesive residue on the adherend (substantially, the plasticizer). Adhesion) is prevented.

FIG. 2 is a schematic cross-sectional view of an adhesive tape according to another embodiment of the present invention. The adhesive tape 200 includes a base material 10, a pressure-sensitive adhesive layer 20 arranged on one surface of the base material 10, and a non-adhesive layer 30 arranged on the surface of the base material 10 opposite to the pressure-sensitive adhesive layer 20. To be equipped.

The thickness of the adhesive tape of the present invention is preferably 20 μm to 120 μm, more preferably 30 μm to 120 μm, and further preferably 40 μm to 120 μm. Within such a range, the effect of the present invention becomes more remarkable. If the thickness of the adhesive tape of the present invention is too thin, the handleability may be deteriorated. If the thickness of the adhesive tape of the present invention is too thick, the followability to deformation such as stretching may be deteriorated, and the pick-up property due to the needle pushing up may be deteriorated.

The upper limit of the adhesive force of the adhesive tape of the present invention on the SUS plate after 23 ° C. × 30 minutes is preferably 2.1 N / 20 mm, more preferably 1 N / 20 mm, and further preferably 0.5 N / 20 mm. Yes, particularly preferably 0.2 N / 20 mm, and most preferably 0.1 N / 20 mm. In one embodiment, the adhesive strength can be controlled by the content ratio of carboxyl groups contained in the polymer in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. In other words, it is preferable to adjust the content ratio of the carboxyl group contained in the polymer in the pressure-sensitive adhesive so that the adhesive strength is 2.1 N / 20 mm or less. The lower limit of the adhesive force of the adhesive tape of the present invention on the SUS plate after 23 ° C. × 30 minutes is preferably 0.01 N / 20 mm, more preferably 0.05 N / 20 mm, and further preferably 0.07 N / 20 mm. It is 20 mm, particularly preferably 0.08 N / 20 mm, and most preferably 0.09 N / 20 mm. In the present specification, the "adhesive force to the SUS plate after x ° C. x y minutes" is the adhesive force measured by a method according to JIS Z 0237: 2000, and is pressure-bonded with one reciprocating 2 kg roller to provide an adhesive tape. And SUS plates are laminated, and the obtained laminate is stored in an environment of x ° C. for y minutes, and then the adhesive tape is peeled off at a tensile speed of 300 mm / min and a peeling angle of 180 ° in an environment of 23 ° C. , Refers to the measured adhesive strength.

The adhesive strength of the adhesive tape of the present invention to the SUS plate after 50 ° C. × 2 days is 0.05 N / 20 mm to 0.85 N / 20 mm, preferably 0.1 N / 20 mm to 0.8 N / 20 mm, and more. It is preferably 0.12N / 20mm to 0.7N / 20mm, and particularly preferably 0.15N / 20mm to 0.5N / 20mm.

The adhesive strength after 50 ° C. × 2 days is a long-term storage, that is, a long period from when the adherend is attached to the adhesive tape until it is peeled off (for example, about 60 days at room temperature). Adhesive strength under accelerated test conditions assuming a case. The accelerated test conditions (50 ° C. x 2 days) assuming long-term storage were determined as follows. A heating acceleration test is used as a method for estimating the behavior of the adhesive after storage for a certain period of time. It predicts long-term changes in a short time by heating, and it is assumed that the rate of change is accelerated according to Arrhenius's law. The Arrhenius equation is represented by K = A × exp (-Ea / RT). Here, K is the reaction rate coefficient, A is the frequency factor, Ea is the activation energy, R is the gas constant, and T is the absolute temperature (K). Ea (activation energy) is available from "Nitto Giho" Vol. 27, No. As described in 2 (Nov. 1989), 21000 [cal / mol] calculated on the assumption that the shift factor obtained from the measured mechanical properties of the acrylic pressure-sensitive adhesive using the time-temperature conversion law is the Arrhenius type. ] Was used. As a result, the reaction rate constants at 20 ° C and 50 ° C are
K (20 ° C) = A × exp (-21000 / 293R)
K (50 ° C) = A × exp (-21000 / 323R)
Will be. Using this formula, the reaction rate coefficient ratio at both temperatures is
K (50 ° C) / K (20 ° C) = 28.5
Will be. Here, it is assumed that the adherend is stored in an environment of an average temperature of 20 ° C. in a state of being attached to the adhesive tape. When the temperature of the accelerated test is set to 50 ° C. and the storage period at 20 ° C. according to the Arrhenius equation is estimated and calculated, it is 50 ° C. × 2 days ≈ 20 ° C. × 57 days.

B. Adhesive layer B-1. Acrylic adhesive As described above, the adhesive layer is composed of an acrylic adhesive.

B-1-1. Base Polymer The acrylic pressure-sensitive adhesive contains a (meth) acrylic polymer as a base polymer. In one embodiment, the (meth) acrylic polymer is a monomer containing a (meth) acrylic acid ester as a main monomer and having a hydrogen-bonding functional group containing no free hydrogen (hereinafter, also referred to as monomer a). ) Can be produced from the monomer component.

In the (meth) acrylic polymer, the content ratio of the constituent unit derived from the main monomer is preferably 60 parts by weight or more, more preferably 60 parts by weight to 95 parts by weight, based on 100 parts by weight of the base polymer. More preferably, it is 65 parts by weight to 85 parts by weight.

In the (meth) acrylic polymer, the content ratio of the structural unit having a hydrogen-binding functional group containing no free hydrogen is preferably 5 parts by weight to 40 parts by weight, more preferably, with respect to 100 parts by weight of the base polymer. Is 8 parts by weight to 35 parts by weight, more preferably 9 parts by weight to 30 parts by weight, and particularly preferably 9 parts by weight to 23 parts by weight. Within such a range, it is possible to form a pressure-sensitive adhesive layer having excellent cohesiveness and little adhesive residue.

In the (meth) acrylic polymer, the content ratio of the structural unit having a hydrogen-bonding functional group is preferably 10 parts by weight to 50 parts by weight, and more preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the base polymer. It is 40 parts by weight, more preferably 10 parts by weight to 32 parts by weight. Within such a range, a pressure-sensitive adhesive layer having excellent cohesiveness can be formed.

(Monomer having a hydrogen-bonding functional group containing no free hydrogen (monomer a))
Monomer a has a hydrogen-bonding functional group. Here, hydrogen bonds are hydrogen atoms (hydrogen bond donors) that are covalently bonded to atoms with high electronegativity such as nitrogen, oxygen, and sulfur, and nitrogen, oxygen, sulfur, etc. that exist in the vicinity of the hydrogen atoms. It means a non-covalent chemical bond formed by electrical interaction with a solitary electron pair of an atom (hydrogen bond acceptor) having a large electronegativity.

A hydrogen-bonding functional group containing no free hydrogen is a functional group that can be a hydrogen-bonding acceptor in a hydrogen bond, and is, for example, a highly electronegative atom (for example, nitrogen, oxygen, etc.) to which hydrogen is not directly bonded. Functional groups containing hydrogen) can be mentioned. Specific examples of the hydrogen-bonding functional group containing no free hydrogen include an amino group (however, a hydrogen atom is not bonded to the amino group nitrogen atom), a carbonyl group, and a thioamide group (however, the thioamide group sulfur atom has a hydrogen atom). , A thioether group, an N-alkylamide group (however, a hydrogen atom is not bonded to the amide group nitrogen atom), an N-alkylimide group and the like. Of these, an amino group (however, a hydrogen atom is not bonded to the amino group nitrogen atom), a thioamide group, a thioether group, an N-alkylamide group or an N-alkylimide group is preferable. Since these functional groups have atoms with high electronegativity (nitrogen atom, sulfur atom), they have strong hydrogen bonding properties, and if a base polymer having the functional groups is used, they have high cohesiveness and plasticity. A pressure-sensitive adhesive that can disperse the agent well can be obtained.

Specific examples of the monomer a include N-vinyl-2-pyrrolidone, N, N-diethylacrylamide, acryloylmorpholine, 2- (2-methylimidazolyl) ethyl (meth) acrylate and the like. As the monomer a, only one type may be used alone, or two or more types may be used in combination.

The glass transition temperature of the homopolymer formed from the monomer a is preferably 50 ° C. to 150 ° C., more preferably 60 ° C. to 150 ° C., and further preferably 70 ° C. to 145 ° C. When the glass transition temperature of a homopolymer is in the above range, it means that the intermolecular force between the polymer chains of the homopolymer is strong, and the hydrogen bond of the hydrogen-bonding functional group of the monomer constituting the homopolymer. It means that the ability is excellent.

(Main monomer)
As the (meth) acrylic acid ester, it is preferable to use a monomer having no hydrogen bonding property. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having an alkyl group (including a cycloalkyl group) having 1 to 30 carbon atoms. As the (meth) acrylic acid ester, only one type may be used alone, or two or more types may be used in combination.

Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and propyl (meth) acrylic acid. Isobutyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Amil acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, Isononyl (meth) acrylate, Decyl (meth) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Tridecyl (meth) acrylate, (meth) acrylic Alkyl groups having 1 to 30 carbon atoms such as tetradecyl acid acid, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, eikosyl (meth) acrylate, and lauryl (meth) acrylate. Examples thereof include (meth) acrylic acid alkyl esters (including cycloalkyl groups). Among these (meth) acrylic acid esters, a (meth) acrylic acid alkyl ester having an alkyl group (including a cycloalkyl group) having 2 to 20 carbon atoms is preferable, and a (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms is more preferable. It is a (meth) acrylic acid alkyl ester of an alkyl group (including a cycloalkyl group).

(Other monomers)
The (meth) acrylic polymer may contain structural units derived from the (meth) acrylic acid ester (main monomer) and other monomers other than the monomer a, as long as the effects of the present invention can be obtained.

Examples of the other monomers include carboxyl group-containing monomers such as acrylate, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and carboxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, (meth). Hydroxyl group-containing monomers such as hydroxypropyl acrylate and hydroxybutyl (meth) acrylate; sulfonic acid group-containing monomers such as styrene sulfonic acid and allyl sulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate and the like. Be done. In one embodiment, carboxyl group-containing monomers and / or hydroxyl group-containing monomers are used as other monomers.

As the other monomer, a monomer having a hydrogen-bonding functional group containing free hydrogen (for example, a carboxyl group-containing monomer and / or a hydroxyl group-containing monomer) may be used. In the (meth) acrylic polymer, the content ratio of the structural unit having a hydrogen-bonding functional group containing free hydrogen is preferably 20 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer. Is 15 parts by weight or less, more preferably 10 parts by weight or less. In one embodiment, a carboxyl group-containing monomer is used as the other monomer, and in the (meth) acrylic polymer, the content ratio of the structural unit derived from the carboxyl group-containing monomer is the base polymer ((meth) acrylic polymer). ) 0.2 parts by weight or less with respect to 100 parts by weight. In another embodiment, the (meth) acrylic polymer does not contain building blocks derived from carboxyl group-containing monomers.

B-1-2. Additives The acrylic pressure-sensitive adhesive may contain any suitable additive.

In one embodiment, the acrylic pressure-sensitive adhesive comprises a plasticizer. If an acrylic pressure-sensitive adhesive containing a plasticizer is used, it is possible to prevent the plasticizer in the base material from migrating to the pressure-sensitive adhesive layer and suppress the influence of the transferred plasticizer, and the change with time is small. Adhesive tape can be obtained. Examples of the plasticizer include terephthalic acid ester-based plasticizers, isophthalic acid ester-based plasticizers, phthalic acid ester-based plasticizers, trimellitic acid ester-based plasticizers (trioctyl trimellitic acid, etc.), and adipic acid ester-based plasticizers. (Dioctyl adipate, diisononyl adipate, etc.), phosphate ester plasticizer (tricrecil phosphate, etc.), adipic acid ester plasticizer, citrate ester plasticizer (tributyl acetylcitrate, etc.), sebacic acid ester type Plasticizers, acerainic acid ester plasticizers, maleic acid ester plasticizers, benzoic acid ester plasticizers, polyether polyester plasticizers, epoxy polyester plasticizers (epoxidized soybean oil, epoxidized flaxseed oil, etc.) , Polyester composed of polyvalent carboxylic acid and polyvalent glycol and the like. The plasticizer may be only one kind or two or more kinds.

In one embodiment, a terephthalic acid ester-based plasticizer is used as the plasticizer. If a terephthalic acid ester-based plasticizer is used, even when a relatively large adherend (for example, an LED chip) is attached, the adherend can be picked up satisfactorily without deteriorating the pick-up property. You can get an adhesive tape that can be used. Further, even when the adherend is stored for a long period of time with the adherend attached, the deterioration of the pick-up property is suppressed. An adhesive tape having excellent pick-up properties is preferably used as a shipping adhesive tape. As the terephthalic acid ester-based plasticizer, for example, a diester of terephthalic acid and an alkyl alcohol having 4 to 16 carbon atoms (preferably 6 to 14, more preferably 8 to 13) can be used. Examples of the terephthalic acid ester-based plasticizer include dibutyl terephthalate (DBTP), diisobutyl terephthalate (DIBTP), dinormal hexyl terephthalate (DHTP), bis (2-ethylhexyl) terephthalate (DOTP), and dinormal terephthalate. Examples thereof include octyl (DnOTP), diisononyl terephthalate (DINTP), dinonyl terephthalate (DNTP), diisodecyl terephthalate (DIDTP), and bisbutylbenzyl terephthalate (BBTP). Of these, DOTP is preferable.

As the phthalate ester-based plasticizer, for example, a diester of phthalic acid and an alkyl alcohol having 4 to 16 carbon atoms (preferably 6 to 14, more preferably 8 to 13) can be used. Examples of the phthalate ester-based plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, and diisodecyl phthalate.

As the trimellitic acid ester-based plasticizer, for example, a trimellitic acid and an alkyl alcohol having 6 to 14 carbon atoms (preferably 8 to 12) can be used. Examples of the trimellitic acid ester-based plasticizer include trin-octyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, triisononyl trimellitic acid, tri-n-decyl trimellitic acid, and triisodecyl trimellitic acid. Can be mentioned.

As the pyromellitic acid ester-based plasticizer, for example, a tetraester of pyromellitic acid and an alkyl alcohol having 6 to 14 carbon atoms (preferably 8 to 12) can be used. Examples of the pyromellitic acid ester-based plasticizer include tetra-n-octyl pyromellitic acid, tetra-2-ethylhexyl pyromellitic acid, and tri-n-decyl pyromellitic acid.

As the adipate-based plasticizer, for example, a diester of adipic acid and an alkyl alcohol having 4 to 16 carbon atoms (preferably 6 to 14, more preferably 8 to 13) can be used. Examples of the adipic acid ester-based plasticizer include di-n-octyl adipate, di-2-ethylhexyl adipate, and diisononyl adipate.

Examples of the polyester composed of the polyvalent carboxylic acid and the polyhydric glycol include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and the like. Terephthalic acid and (poly) ethylene glycol (here, "(poly) ethylene glycol" means to comprehensively refer to ethylene glycol and polyethylene glycol; the same shall apply hereinafter), (poly) propylene glycol, (poly). ) Polyester compounds obtained from polyvalent alcohols such as butylene glycol, (poly) hexanediol, (poly) neopentyl glycol, and polyvinyl alcohol can be used. The polyvalent carboxylic acid is preferably an aliphatic dicarboxylic acid having 4 to 12 (preferably 6 to 10) carbon atoms, and examples thereof include adipic acid and sebatic acid. The polyhydric alcohol is preferably an aliphatic diol having 2 to 10 carbon atoms, and examples thereof include ethylene glycol, 1,3-butanediol, and 1,4-butanediol.

When the acrylic pressure-sensitive adhesive contains a plasticizer, the content ratio of the plasticizer is preferably 10 parts by weight to 90 parts by weight, more preferably 20 parts by weight, based on 100 parts by weight of the base polymer in the acrylic pressure-sensitive adhesive. It is from 7 parts by weight to 80 parts by weight, more preferably 30 parts by weight to 70 parts by weight, and particularly preferably 40 parts by weight to 60 parts by weight.

In one embodiment, the acrylic pressure-sensitive adhesive comprises a cross-linking agent. The content ratio of the cross-linking agent is preferably 0.1 parts by weight to 30 parts by weight, more preferably 0.3 parts by weight to 25 parts by weight, and further preferably 0. It is 5 parts by weight to 25 parts by weight, more preferably 1 part by weight to 25 parts by weight, further preferably 3 parts by weight to 20 parts by weight, and particularly preferably 5 parts by weight to 15 parts by weight. Within such a range, an increase in adhesive strength can be further suppressed even after the fragmented adherend (for example, LED chip) is stored on the adhesive tape for a long period of time, and an adhesive tape that can be easily picked up can be obtained. be able to. In addition, an appropriate cross-linking reaction can be generated, and adhesive residue on the adherend can be effectively prevented.

Examples of the cross-linking agent include epoxy-based cross-linking agents, isocyanate-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, and carbodiimide-based cross-linking agents. Examples thereof include agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents. The cross-linking agent may be only one kind or two or more kinds.

The acrylic pressure-sensitive adhesive may further contain any suitable other additives as long as the effects of the present invention are not impaired. Examples of the additive include a catalyst, an ultraviolet absorber, a filler, an antioxidant, a tackifier, a pigment, a dye, a silane coupling agent and the like.

B-2. Characteristics of the pressure-sensitive adhesive layer, etc. The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 30 μm, more preferably 1 μm to 20 μm, and further preferably 3 μm to 15 μm. If the thickness of the pressure-sensitive adhesive layer is less than 1 μm, sufficient adhesive strength may not be exhibited. If the thickness of the pressure-sensitive adhesive layer is larger than 30 μm, it may be embedded in the pressure-sensitive adhesive layer of a fragmented adherend (for example, LED chip), and the accuracy of the needle pushing position at the time of pickup may be lowered.

The elastic modulus of the pressure-sensitive adhesive layer by the nanoindentation method at 25 ° C. (hereinafter, also simply referred to as nanoindentation elastic modulus) is 4.0 MPa to 30 MPa, preferably 4.5 MPa to 27 MPa, and more preferably 6. It is 0.0 MPa to 25 MPa, and particularly preferably 7.0 MPa to 22 MPa. The elastic modulus by the nanoindentation method can be measured under the following conditions.
(Measuring equipment and measurement conditions)
Equipment: Hysiron Inc. Made by Tribo Indicator
Indenter used: Berkovic (triangular pyramid type)
Measurement method: Single push measurement Measurement temperature: 25 ° C
Pushing depth setting: Approximately 300 nm
Pushing speed: Approximately 10 nm / sec
Measurement atmosphere: Sample size in air: Approximately 1 cm x Approximately 1 cm
(Measuring method)
Using the above device, a Berkovich diamond indenter was pushed vertically from the surface of the pressure-sensitive adhesive layer to a depth of 300 nm. Using the analysis software "Triboscan Ver. 9.2.12.0", the elastic modulus of the surface is obtained from the displacement and load obtained after removing the indenter and the theoretically calculated indentation area.

As described above, the pressure-sensitive adhesive layer contains a plasticizer (plasticizer derived from the pressure-sensitive adhesive and / or plasticizer derived from the substrate). The content ratio of the plasticizer in the pressure-sensitive adhesive layer is preferably 10 parts by weight to 100 parts by weight, and more preferably 20 parts by weight to 90 parts by weight with respect to 100 parts by weight of the base polymer constituting the pressure-sensitive adhesive. It is more preferably 30 parts by weight to 80 parts by weight, and particularly preferably 30 parts by weight to 70 parts by weight. Within such a range, it is possible to obtain an adhesive tape having high flexibility and excellent followability to the adherend, and the plasticizer does not easily exude from the adhesive layer.

Any suitable means can be adopted as a method of providing the pressure-sensitive adhesive layer on the substrate. For example, the pressure-sensitive adhesive layer can be formed by applying a coating liquid for forming the pressure-sensitive adhesive layer onto the base material.

As the coating method, any appropriate coating method can be adopted. Examples of the coating method include a reverse method, a direct method, and various methods combining a metering roll.

The adhesive tape of the present invention may be provided with a release liner on the surface of the adhesive layer.

Any suitable separator may be used as the release liner. Examples of such a release liner include a base material having a release layer such as a plastic film or paper surface-treated with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide; polytetrafluoroethylene, Low adhesive substrate composed of fluoropolymers such as polychlorotrifluoroethylene, polyvinylfluorovinyl, vinylidene polyvinylfluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer; olefin-based Low adhesive base material made of non-polar polymer such as resin (for example, polyethylene, polypropylene, etc.); and the like.

When a release liner is used, the pressure-sensitive adhesive layer may be provided on the base material by applying a coating liquid on the release liner and bonding the coating liquid onto the base material to transfer the pressure-sensitive adhesive layer.

C. Base material The thickness of the base material is preferably 20 μm to 120 μm, more preferably 30 μm to 120 μm, and further preferably 40 μm to 120 μm. If the thickness of the base material is too thin, the handleability may deteriorate. If the thickness of the base material is too thick, the followability to deformation such as stretching is deteriorated, and the pick-up property due to the needle pushing up may be deteriorated.

The base material has a maximum elongation of preferably 100% or more, more preferably 200% to 1000%, as measured according to JIS-K-7127 (1999). By using a base material exhibiting such maximum elongation, it is possible to impart appropriate extensibility to the adhesive tape of the present invention, and for example, the followability to an adherend can be improved. Maximum elongation can be measured in an environment of 23 ° C.

Any suitable material can be used as the material constituting the base material. Preferably, a plastic film is used as the base material.

The plastic film may include any suitable resin material. Examples of such a resin material include polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer, polyester, polyimide, polyamide and the like. Of these, polyvinyl chloride, polyolefin or ethylene-vinyl acetate copolymer is preferable, and polyvinyl chloride is more preferable. Since polyvinyl chloride is excellent in stress relaxation property, it can appropriately relax the impact when the needle is pushed up, and can suppress the displacement and dropout of the fragmented adherend (for example, LED chip). By using such a polyvinyl chloride, it is possible to obtain an adhesive tape suitable as an adhesive tape for shipping a fragmented adherend (for example, an LED chip).

The content ratio of the resin material in the plastic film is, for example, 50 parts by weight to 100 parts by weight, preferably 60 parts by weight to 100 parts by weight, and more preferably 70 parts by weight with respect to 100 parts by weight of the plastic film. It is a part by weight to 100 parts by weight.

In one embodiment, the plastic film used for the substrate comprises a plasticizer. Examples of the plasticizer contained in the plastic film include the plasticizer described in Section B-1-2 above. The content ratio of the plasticizer in the plastic film is preferably 0.5 parts by weight to 50 parts by weight, more preferably 1.0 parts by weight to 40 parts by weight, based on 100 parts by weight of the resin material in the plastic film. It is a part by weight. By including the plasticizer in the plastic film at the above content ratio, it is possible to obtain an adhesive tape having excellent followability to deformation such as stretching and good pick-up property.

The plastic film may contain any suitable other components as long as the effects of the present invention are not impaired.

The substrate can be produced by any suitable production method. For example, a base material can be obtained by a molding method such as injection molding, extrusion molding, inflation molding, calender molding, or blow molding.

D. Non-Adhesive Layer In one embodiment, the pressure-sensitive adhesive tape of the present invention comprises a pressure-sensitive adhesive layer on one side of the substrate and a non-adhesive layer on the surface of the substrate opposite to the pressure-sensitive adhesive layer. The non-adhesive layer is a layer that cannot maintain a close contact state even when pressure-bonded to a SUS plate at 23 ° C., and easily shifts in position or spontaneously peels off.

The composition of such a non-adhesive layer is not particularly limited, and examples thereof include a silicone layer, a (meth) acrylic polymer layer, a mixed layer of a silicone layer and a (meth) acrylic polymer layer, and (meth). ) Examples thereof include a silicone layer in which an acrylic polymer is graft-polymerized. Among these, a mixed layer of silicone and a (meth) acrylic polymer is preferable. By using a mixed layer of silicone and a (meth) acrylic polymer as the non-adhesive layer, the non-adhesive layer and the base material (particularly, a plastic film) become more compatible, and the adhesive tape of the present invention is deformed by stretching or the like. The followability to is good.

The surface of the non-adhesive layer preferably has an uneven structure. Since the surface of the non-adhesive layer has an uneven structure, an adhesive tape having excellent handleability can be obtained. Specifically, in this uneven structure, the arithmetic average surface roughness Ra of the non-adhesive layer is preferably 0.1 μm or more, more preferably 0.1 μm to 3.0 μm, and further preferably 0.2 μm. It is ~ 2.0 μm, particularly preferably 0.3 μm to 2.0 μm, and most preferably 0.5 μm to 2.0 μm. Within such a range, an adhesive tape in which blocking is suppressed can be obtained. The surface roughness Ra can be measured according to JIS B 0601: 1994.

In the non-adhesive layer, the glass transition temperature Tg by differential scanning calorimetry (DSC measurement) is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 55. It is above ℃. The upper limit of the glass transition temperature Tg by differential scanning calorimetry of the non-adhesive layer is not particularly limited, but is preferably 200 ° C. or lower, more preferably 170 ° C. or lower, still more preferably 150, from the viewpoint of handleability and the like. It is ℃ or less, particularly preferably 130 ℃ or less, and most preferably 100 ℃ or less. Within such a range, the non-adhesive layer has an appropriate hardness, and it is possible to prevent the non-adhesive layer from falling off due to rubbing or the like during the transport process.

When the non-adhesive layer contains a (meth) acrylic polymer, the SP value of the (meth) acrylic polymer in the non-adhesive layer is preferably 9.0 (cal / cm ³ ) ^{0.5 to} 12.0. (Cal / cm ³ ) ^0.5 , more preferably 9.5 (cal / cm ³ ) ^{0.5 to} 11.5 (cal / cm ^{3 ) 0.5} , still more preferably 9.5 (cal / cm 3). cal / cm ³ ) ^{0.5 to} 11.0 (cal / cm ³ ) ^0.5 . The SP value is a solubility parameter calculated by Small's formula. The calculation of the SP value can be performed by the method described in a known document (for example, Journal of Applied Chemistry, 3, 71, 1953.).

The non-adhesive layer preferably has a phase-separated structure. Since the non-adhesive layer has a phase-separated structure, a minute uneven structure can be efficiently formed on the surface of the non-adhesive layer. For example, when the non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer, it is presumed that unevenness is generated due to the difference in mass transfer between silicone and (meth) acrylic polymer when forming a phase-separated structure. Will be done. If the uneven structure is formed in this way, it is possible to obtain an adhesive tape that is excellent in handleability and has suppressed blocking when it is formed into a roll form.

The non-adhesive layer preferably contains a silicone-rich phase containing more silicone than the (meth) acrylic polymer and a (meth) acrylic polymer-rich phase containing more (meth) acrylic polymer than silicone. More specifically, the non-adhesive layer preferably contains the silicone-rich phase and the (meth) acrylic polymer-rich phase in a phase-separated structure independent of each other, and more preferably the silicone-rich phase has an air interface. It exists on the side (opposite side of the substrate), and the (meth) acrylic polymer-rich phase exists on the substrate side. By having such a phase-separated structure, blocking is effectively suppressed by the silicone-rich phase existing on the air interface side, and the non-adhesive layer and the base material are effectively suppressed by the (meth) acrylic polymer-rich phase existing on the substrate side. It becomes more familiar with and has better deformation followability. For example, such a phase-separated structure can be formed by adjusting the mixing ratio of the silicone and the (meth) acrylic polymer in the non-adhesive layer as follows.

The non-adhesive layer has a phase-separated structure, and as described above, the silicone-rich phase containing more silicone than the (meth) acrylic polymer and the (meth) acrylic polymer containing more silicone (meth). ) The inclusion of an acrylic polymer rich phase can be observed by any suitable method. As such an observation method, for example, a cross section of the non-adhesive layer is viewed using an electron microscope such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), or an electrolytic emission scanning electron microscope (FE-SEM). A method of morphological observation can be mentioned. The two-layer separated structure can be read by the shade of the morphological observation image. In addition, observation is performed by observing changes in the content of silicon, carbon, etc. contained in the composition while changing the probe optical depth from the non-adhesive layer air interface side to the inside by infrared absorption spectroscopy by the total reflection method. There is also a method. In addition, a method of observing by an X-ray microanalyzer or X-ray photoelectron spectroscopy can also be mentioned. Moreover, you may observe by combining these methods as appropriate.

When the non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer, the mixing ratio of silicone and (meth) acrylic polymer in the non-adhesive layer is a weight ratio, preferably silicone: (meth) acrylic. The polymer system = 1:50 to 50: 1, more preferably the silicone: (meth) acrylic polymer = 1:30 to 30: 1, and even more preferably the silicone: (meth) acrylic polymer = 1 : 10 to 10: 1, particularly preferably silicone: (meth) acrylic polymer = 1: 5 to 5: 1, and most preferably silicone: (meth) acrylic polymer = 1: 3 to 5 It is 1. If the content of silicone in the non-adhesive layer is too large, the chemical affinity with the back surface of the base material (particularly the plastic film) becomes low, and it may be difficult to fit the back surface of the base material (particularly the plastic film). Further, if the content ratio of silicone in the non-adhesive layer is too large, the adhesive tape may have poor followability to deformation such as stretching. If the content ratio of the (meth) acrylic polymer in the non-adhesive layer is too large, the non-adhesive layer may act as an acrylic pressure-sensitive adhesive, and blocking may easily occur.

As the silicone, any suitable silicone may be adopted. Examples of such silicones include addition-type silicones and tin-based silicones obtained by curing an alkenyl group-containing polydialkylsiloxane and polydialkylhydrogenpolysiloxane by an addition reaction using a platinum-based compound as a catalyst to form a peelable film. Examples thereof include condensed silicone obtained by reacting a methylol group-containing polydialkylsiloxane with a polydialkylhydrogenpolysiloxane using a catalyst. Examples of the addition type silicone include "KS-776A" and "KS-839L" manufactured by Shinetsu Silicone. Examples of the condensation type silicone include "KS723A / B" manufactured by Shinetsu Silicone. When producing silicone, in addition to the platinum-based catalyst and the tin-based catalyst, other cross-linking agents, cross-linking accelerators and the like may be used as appropriate. Further, the properties of silicone are classified into a type dissolved in an organic solvent such as toluene, an emulsion type obtained by emulsifying these, and a solvent-free type consisting only of silicone. Further, in addition to the addition type silicone and the condensation type silicone, a silicone / acrylic graft polymer, a silicone / acrylic block polymer and the like can be used. Examples of the silicone / acrylic graft polymer include Cymac GS-30, GS101, US-270, US-350, and US-380 (all manufactured by Toagosei Co., Ltd.). Examples of the silicone / acrylic block polymer include Modiper FS700, FS710, FS720, FS730, and FS770 (all manufactured by NOF CORPORATION).

The (meth) acrylic polymer contained in the non-adhesive layer is a polymer composed of a monomer component containing a (meth) acrylic monomer as a main monomer. Further, the monomer component constituting the (meth) acrylic polymer may contain other monomers such as a hydroxyl group-containing monomer and a carboxyl group-containing monomer.

In the (meth) acrylic polymer contained in the non-adhesive layer, the content ratio of the structural unit derived from the (meth) acrylic monomer is preferably 50 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic polymer. , More preferably 70 parts by weight to 100 parts by weight, further preferably 90 parts by weight to 100 parts by weight, and particularly preferably 95 parts by weight to 100 parts by weight. The monomer in the above-mentioned monomer component may be only one kind or two or more kinds.

Preferred examples of the (meth) acrylic monomer include (meth) acrylic acid ester and (meth) acrylic acid.

Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having an alkyl group (including a cycloalkyl group) having 1 to 30 carbon atoms, a hydroxyl group-containing (meth) acrylic acid ester, and the like. The (meth) acrylic acid ester may be only one kind or two or more kinds.

Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and propyl (meth) acrylic acid. Isobutyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Amil acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, Isononyl (meth) acrylate, Decyl (meth) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Tridecyl (meth) acrylate, (meth) acrylic Alkyl groups having 1 to 30 carbon atoms such as tetradecyl acid acid, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, eikosyl (meth) acrylate, and lauryl (meth) acrylate. Examples thereof include (meth) acrylic acid alkyl esters (including cycloalkyl groups). Among these (meth) acrylic acid esters, a (meth) acrylic acid alkyl ester having an alkyl group (including a cycloalkyl group) having 2 to 20 carbon atoms is preferable, and a (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms is more preferable. It is a (meth) acrylic acid alkyl ester of an alkyl group (including a cycloalkyl group).

Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

The monomer component constituting the (meth) acrylic polymer may contain at least one selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer in order to fully exhibit the effects of the present invention.

Examples of the hydroxyl group-containing monomer include allyl alcohol. The hydroxyl group-containing monomer may be only one type or two or more types.

Examples of the carboxyl group-containing monomer include carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, and itaconic acid. The carboxyl group-containing monomer may be only one type or two or more types.

When the non-adhesive layer contains a (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer preferably contains a hydroxyl group-containing (meth) acrylic acid ester in the monomer components constituting the non-adhesive layer. , It is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25% by weight, and particularly preferably 5% by weight, based on the total amount of the monomer components other than the hydroxyl group-containing (meth) acrylic acid ester. % To 20% by weight. When the non-adhesive layer contains a (meth) acrylic polymer, the content ratio of the hydroxyl group-containing (meth) acrylic acid ester in the monomer component constituting the (meth) acrylic polymer in the non-adhesive layer is the hydroxyl group-containing (meth) acrylic acid ester. ) If the total amount of the monomer components other than the acrylic acid ester is within the above range, a minute uneven structure is more efficiently formed on the surface of the non-adhesive layer, and the formation of this uneven structure causes the adhesion of the present invention. In the tape, blocking in the roll form can be more effectively suppressed, and tearing or tearing when rewinding from the roll form can be further suppressed.

When the non-adhesive layer contains a (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer is preferably contained in a monomer component other than the hydroxyl group-containing (meth) acrylic acid ester in the monomer component constituting the non-adhesive layer. Can include (meth) acrylic acid and / or (meth) acrylic acid ester. In this case, the content ratio of (meth) acrylic acid and (meth) acrylic acid ester is, in terms of weight ratio, (meth) acrylic acid: (meth) acrylic acid ester, preferably 0: 100 to 20:80. , More preferably 0: 100 to 10:90, and even more preferably 0: 100 to 5:95.

If the content ratio of (meth) acrylic acid and (meth) acrylic acid ester is within the above range, a minute uneven structure is more efficiently formed on the surface of the non-adhesive layer, and the formation of this uneven structure results in the invention. In the adhesive tape of the present invention, blocking in the roll-shaped form can be more effectively suppressed, and tearing or tearing when rewinding from the roll-shaped form can be further suppressed.

The (meth) acrylic polymer can be produced by any suitable polymerization method.

The non-adhesive layer may contain any suitable additive as long as the effects of the present invention are not impaired. Examples of such additives include catalysts, UV absorbers, fillers, anti-aging agents, tackifiers, pigments, dyes, silane coupling agents and the like.

The thickness of the non-adhesive layer is preferably 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm, and even more preferably 0.1 μm to 2 μm. If the thickness of the non-adhesive layer is less than 0.01 μm, blocking is likely to occur. If the thickness of the non-adhesive layer is larger than 10 μm, the followability to deformation such as stretching may deteriorate.

Examples of the method of forming the non-adhesive layer on one surface of the base material include a method of forming the non-adhesive layer by applying the material of the non-adhesive layer to one surface of the base material and drying it. Examples of the coating method include a method using a bar coater, a gravure coater, a spin coater, a roll coater, a knife coater, an applicator and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, parts mean parts by weight and% means% by weight. The amount of the reagent supplied as a solution is represented by the amount of solids remaining after volatilizing the solution (solid content equivalent amount).

[Production Example 1] Production of soft polyvinyl chloride film (1) DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA Corporation, trade name " Adeka sizer D-810 ") A soft polyvinyl chloride film (1) containing 30 parts by weight was produced by a calendar method. The thickness of this soft polyvinyl chloride film (1) is 70 μm, the elastic modulus (MD) measured according to JIS-K-7127 is 250 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 is 400%. Met. The surface roughness (arithmetic mean surface roughness Ra) immediately after production was 0.1 μm.

[Production Example 2] Production of soft polyvinyl chloride film (2) 30 parts by weight of DINP plasticizer (bis (isononyl phthalate), manufactured by J-PLUS) is included with respect to 100 parts by weight of polyvinyl chloride having a degree of polymerization of P = 1050. However, a soft polyvinyl chloride film (2) was produced by the calendar method. The thickness of this soft polyvinyl chloride film (2) is 70 μm, the elastic modulus (MD) measured according to JIS-K-7127 is 250 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 is 400%. Met. The surface roughness (arithmetic mean surface roughness Ra) immediately after production was 0.1 μm.

[Production Example 3] Production of soft polyvinyl chloride film (3) Adipic acid-based low-molecular-weight polyester plasticizer (manufactured by ADEKA Corporation, trade name "ADEKA Sizer PN-" with respect to 100 parts by weight of polyvinyl chloride having a degree of polymerization of P = 1050. 7160 ") A soft polyvinyl chloride film (3) containing 30 parts by weight was produced by a calendar method. The thickness of this soft polyvinyl chloride film (3) is 70 μm, the elastic modulus (MD) measured according to JIS-K-7127 is 250 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 is 400%. Met. The surface roughness (arithmetic mean surface roughness Ra) immediately after production was 0.1 μm.

[Production Example 4] Production of soft polyvinyl chloride film (4) 30 parts by weight of DOP plasticizer (bis (2-ethylhexyl phthalate), manufactured by J-PLUS) with respect to 100 parts by weight of polyvinyl chloride having a degree of polymerization of P = 1050. A soft polyvinyl chloride film (4) containing the above was produced by a calendar method. The thickness of this soft polyvinyl chloride film (4) is 70 μm, the elastic modulus (MD) measured according to JIS-K-7127 is 250 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 is 400%. Met. The surface roughness (arithmetic mean surface roughness Ra) immediately after production was 0.1 μm.

[Production Example 5] Production of soft polyvinyl chloride film (5) DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA Corporation, trade name " Adeka sizer D-810 ") A soft polyvinyl chloride film (5) containing 40 parts by weight was produced by a calendar method. The thickness of this soft polyvinyl chloride film (5) is 70 μm, the elastic modulus (MD) measured according to JIS-K-7127 is 200 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 is 400%. Met. The surface roughness (arithmetic mean surface roughness Ra) immediately after production was 0.1 μm.

[Example 1]
Acrylate composed of butyl acrylate (BA) / N-vinyl-2-pyrrolidone (NVP) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15/10/0.25 (weight ratio) Copolymerized polymer A (weight average molecular weight = 1500,000) 100 parts by weight, isocyanate-based cross-linking agent (manufactured by Toso, trade name "Coronate L") 5 parts by weight, ethylenediamine polyol (manufactured by ADEKA, trade name "ADEKA polyol EDP-300" A ethyl acetate solution of a pressure-sensitive adhesive consisting of 2.5 parts by weight and 60 parts by weight of a DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA, trade name "ADEKA Sizer D-810") was prepared. NVP is a monomer having a hydrogen-bonding functional group that does not contain free hydrogen, and the glass transition temperature of the homopolymer composed of the monomer is 54 ° C.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (1) was obtained.

[Example 2]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / N, N-diethylacrylamide (DEAA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15/10/0. An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 100 parts by weight of the acrylic copolymer B (weight average molecular weight = 1500,000) composed of 25 (weight ratio) was used. DEAA is a monomer having a hydrogen-bonding functional group that does not contain free hydrogen, and the glass transition temperature of the homopolymer composed of the monomer is 81 ° C.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (2) was obtained.

[Example 3]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / acryloylmorpholin (ACMO) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15/10/0.25 (weight ratio) Acrylic copolymer polymer C (weight average molecular weight = 1500,000) composed of 100 parts by weight was used, and an ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1. ACMO is a monomer having a hydrogen-bonding functional group that does not contain free hydrogen, and the glass transition temperature of the homopolymer composed of the monomer is 145 ° C.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (3) was obtained.

[Example 4]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / N-vinyl-2-pyrrolidone (NVP) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 90/10/10/0 An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 100 parts by weight of the acrylic copolymer polymer D (weight average molecular weight = 1500,000) composed of .25 (weight ratio) was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (4) was obtained.

[Example 5]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / N, N-diethylacrylamide (DEAA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 75/25/10/0. An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 100 parts by weight of the acrylic copolymer E (weight average molecular weight = 1500,000) composed of 25 (weight ratio) was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (5) was obtained.

[Example 6]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / acryloylmorpholin (ACMO) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 75/25/10/0.25 (weight ratio) ), An acrylic copolymer polymer F (weight average molecular weight = 1500,000) was used, and an ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (6) was obtained.

[Example 7]
Instead of 100 parts by weight of the acrylic copolymer polymer A, butyl acrylate (BA) / N-vinyl-2-pyrrolidone (NVP) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15 / 2.5 An ethyl acetate solution of the adhesive was prepared in the same manner as in Example 1 except that 100 parts by weight of the acrylic copolymer G (weight average molecular weight = 1500,000) composed of / 0.25 (weight ratio) was used. did.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (7) was obtained.

[Example 8]
Acrylic copolymerization Acrylic copolymer composed of butyl acrylate (BA) / acryloylmorpholin (ACMO) / 2-hydroxyethyl acrylate (HEA) / = 75/25/10 / (weight ratio) instead of 100 parts by weight of the acrylic copolymer polymer A An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 100 parts by weight of Polymer H (weight average molecular weight = 1500,000) was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (8) was obtained.

[Example 9]
An adhesive tape (9) was obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was 5 μm.

[Example 10]
DOTP plasticizer (bis terephthalate (2-ethylhexyl), manufactured by ADEKA, trade name "ADEKA Sizer D-810") 60 parts by weight, DINP plasticizer (bis phthalate (isononyl), manufactured by J-PLUS) 60 An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that parts by weight were used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (2) obtained in Production Example 2 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (10) was obtained.

[Example 11]
DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA, trade name "ADEKA Sizer D-810") Instead of 60 parts by weight, adipic acid-based low molecular weight polyester plasticizer (manufactured by ADEKA, trade name "" An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 60 parts by weight of ADEKA Sizer PN-7160 ”) was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (3) obtained in Production Example 3 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (11) was obtained.

[Example 12]
DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA, trade name "ADEKA Sizer D-810") Instead of 60 parts by weight, adipic acid-based low molecular weight polyester plasticizer (manufactured by ADEKA, trade name "" An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 60 parts by weight of ADEKA Sizer PN-7160 ”) was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (12) was obtained.

[Example 13]
DOTP plasticizer (bis terephthalate (2-ethylhexyl), manufactured by ADEKA, trade name "ADEKA Sizer D-810") Instead of 60 parts by weight, DOP plasticizer (bis phthalate (2-ethylhexyl), manufactured by J-PLUS) ) An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 60 parts by weight was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (4) obtained in Production Example 4 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (13) was obtained.

[Example 14]
DOTP plasticizer (bis terephthalate (2-ethylhexyl), manufactured by ADEKA, trade name "ADEKA Sizer D-810") Instead of 60 parts by weight, DOP plasticizer (bis phthalate (2-ethylhexyl), manufactured by J-PLUS) ) An ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 80 parts by weight was used.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (5) obtained in Production Example 5 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (14) was obtained.

[Example 15]
Instead of 100 parts by weight of acrylic copolymer polymer A, butyl acrylate (BA) / imidazole polymerizable monomer (manufactured by Shikoku Kasei, trade name "1H2MZM" / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15 Using 100 parts by weight of acrylic copolymer polymer I (weight average molecular weight = 15000000) composed of / 10/0.25 (weight ratio), DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA, product. The same as in Example 1 except that 80 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, manufactured by J-Plus) was used instead of 60 parts by weight of the name "Adecasezer D-810"). , An ethyl acetate solution of a pressure-sensitive adhesive was prepared.
This pressure-sensitive adhesive solution was applied to one side of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (15) was obtained.

[Example 16]
Acrylate composed of butyl acrylate (BA) / N-vinyl-2-pyrrolidone (NVP) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AA) = 85/15/5/0.25 (weight ratio) Copolymerized polymer J (weight average molecular weight = 1500,000) 100 parts by weight, isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate HX") 5 parts by weight, ethylenediamine polyol (manufactured by ADEKA Corporation, trade name "ADEKA polyol EDP-300") A solution of ethyl acetate, which is a pressure-sensitive adhesive consisting of 2.5 parts by weight and 60 parts by weight of a DOTP plasticizer (bis (2-ethylhexyl terephthalate), manufactured by ADEKA, trade name "ADEKA Sizer D-810") was prepared.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 7 μm.
In this way, the adhesive tape (16) was obtained.

[Example 17]
The blending amount of the isocyanate-based cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate HX") was 0.5 parts by weight, and ethylenediamine polyol (manufactured by ADEKA, trade name "ADEKA polyol EDP-300") was not added. Except for the above, an ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 16.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 7 μm.
In this way, the adhesive tape (17) was obtained.

[Example 18]
The blending amount of the isocyanate-based cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate HX") was 0.3 parts by weight, and ethylenediamine polyol (manufactured by ADEKA, trade name "ADEKA polyol EDP-300") was not added. Except for the above, an ethyl acetate solution of the pressure-sensitive adhesive was prepared in the same manner as in Example 16.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 7 μm.
In this way, the adhesive tape (18) was obtained.

[Example 19]
Use 0.5 parts by weight of an epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "TETRAD-C") instead of 5 parts by weight of an isocyanate-based cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate HX"). , Ethylenediamine polyol (manufactured by ADEKA Corporation, trade name "ADEKA polyol EDP-300") was not added, and an ethyl acetate solution of the adhesive was prepared in the same manner as in Example 16.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 7 μm.
In this way, the adhesive tape (19) was obtained.

[Comparative Example 1]
100 parts by weight of acrylic copolymer polymer J (weight average molecular weight = 15000000) composed of butyl acrylate (BA) / acrylic acid (AA) = 100 / 3.0 (weight ratio), epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals) , Trade name "TETRAD-C") 0.5 parts by weight, DOTP plasticizer (terephthalic acid (2-ethylhexyl), manufactured by ADEKA, trade name "ADEKA Sizer D-810") 60 parts by weight of adhesive acetic acid An ethyl solution was prepared.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (16) was obtained.

[Comparative Example 2]
Acrylic copolymer composed of 2-ethylhexyl acrylate (2-EHA) / acryloylmorpholin (ACMO) / acrylic acid / 2-hydroxyethyl acrylate (HEA) / = 75/25 / 3.0 / 0.1 (weight ratio) Polymerized polymer K (weight average molecular weight = 1500,000) 100 parts by weight, epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "TETRAD-C") 1.0 part by weight, DOTP plasticizer (terephthalic acid (2-ethylhexyl)), An ethyl acetate solution of a pressure-sensitive adhesive composed of 60 parts by weight (manufactured by ADEKA, trade name "Adecasizer D-810") was prepared.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (17) was obtained.

[Comparative Example 3]
100 parts by weight of acrylic copolymer (weight average molecular weight = 15000000) composed of 2-ethylhexyl acrylate (2-EHA) / acrylic acid (AA) = 95 / 5.0 (weight ratio), epoxy-based cross-linking agent (Mitsubishi) Adhesive consisting of 0.5 parts by weight of Gas Chemicals, trade name "TETRAD-C"), 60 parts by weight of DOTP plasticizer (terephthalic acid (2-ethylhexyl), ADEKA, trade name "Adecasizer D-810") An ethyl acetate solution of the agent was prepared.
This pressure-sensitive adhesive solution was applied to one surface of the soft polyvinyl chloride film (1) obtained in Production Example 1 and then dried at 130 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm.
In this way, the adhesive tape (18) was obtained.

The adhesive tapes obtained in Examples and Comparative Examples were subjected to the following evaluation. The results are shown in Tables 1 and 2.

(1) Adhesive strength An adhesive tape (width 20 mm × length 120 mm) was attached to a SUS430BA plate under the conditions of a linear pressure of 78.5 N / cm and a speed of 0.3 m / min. After laminating, the mixture was allowed to stand in a 23 ° C.50% RH environment for 30 minutes, and then in a 23 ° C.50% RH atmosphere, using AUTOGRAPH AG-IS (manufactured by SHIMADZU), a tensile angle of 180 ° and a tensile speed of 0. The adhesive strength was measured under the condition of .3 m / min.

(2) Evaluation of tape floating A Si wafer cut into 10 mm □ was attached to the center (center in the width direction and length direction) of the adhesive tape (width 20 mm × length 120 mm) with one reciprocating hand roller.
After laminating the Si wafers, they were allowed to stand for 30 minutes in a 23 ° C. 50% RH environment, and then under the conditions of a chuck spacing of 50 mm, a tensile speed of 0.3 m / min, and a stretching distance of 50 mm under a ring atmosphere of 50 ° C. The sticking tape sample was stretched.
The floating level at the end of the tape at this time was visually observed. The adhesive area was determined to be the portion where the color of the appearance of the tape was visually darkened by the adhesion between the adhesive and the adherend.
The contact area is calculated by printing out a floating observation image on A4 paper in color, cutting out only the wafer portion, and measuring the weight thereof. After that, the bonded portion (dark portion) and the floating portion (light colored portion) were separated, the weight of the separated paper was measured, the weight ratio of the bonded portion was calculated, and the evaluation was made according to the following criteria.
◯: Tape adhesion area is 70% or more of the initial application area ×: Tape adhesion area is 70% or less of the initial application area

(3) Evaluation of adhesive residue The adhesive tape (width 20 mm × length 120 mm) was attached to the mirror surface of a Si wafer cut into 10 mm □ at the center (center in the width direction and length direction) with one reciprocating hand roller.
After laminating the Si wafers, they were allowed to stand for 30 minutes in a 23 ° C. 50% RH environment, and then under the conditions of a chuck spacing of 50 mm, a tensile speed of 0.3 m / min, and a stretching distance of 50 mm under a ring atmosphere of 50 ° C. The sticking tape sample was stretched. Then, after releasing the tape sample from the stretching, the tape was peeled off from the Si wafer at an angle of 180 ° and a tensile speed of 10 mm / sec, and the level of adhesive residue on the surface of the Si wafer was visually observed.
The wafer surface was observed with a digital microscope (manufactured by KEYENCE) at a magnification of 500 times, and when a contaminant having a long side length of 10 μm or more was confirmed, it was judged that there was adhesive residue (x in Table 1). When no contaminant having a long side length of 10 μm or more was confirmed, it was judged that there was no adhesive residue (x in Table 1).

10 Base material 20 Adhesive layer 30 Non-adhesive layer 100, 200 Adhesive tape

Claims (5)

With the base material
An adhesive tape that is arranged on at least one surface of the base material and includes an adhesive layer composed of an acrylic adhesive.
Base polymer constituting the該A acrylic pressure-sensitive adhesive comprises a structural unit having a hydrogen bonding functional group containing no free hydrogen,
The pressure-sensitive adhesive layer contains a plasticizer and contains
The adhesive strength of the adhesive tape to the SUS plate after 23 ° C. × 30 minutes is 0.01 N / 20 mm to 2.1 N / 20 mm.
Adhesive tape. The adhesive tape according to claim 1, wherein the content ratio of the structural unit having a hydrogen-bonding functional group containing no free hydrogen is 9 parts by weight to 23 parts by weight with respect to 100 parts by weight of the base polymer. The claim that the base polymer further contains a structural unit derived from a carboxyl group-containing monomer, and the content ratio of the structural unit derived from the carboxyl group-containing monomer is 0.2 parts by weight or less with respect to 100 parts by weight of the base polymer. Item 2. The adhesive tape according to Item 1 or 2. The adhesive tape according to claim 1 or 2, wherein the base polymer does not contain a structural unit derived from a carboxyl group-containing monomer. The structural unit having a hydrogen-bonding functional group containing no free hydrogen consists of N-vinyl-2-pyrrolidone, N, N-diethylacrylamide, acryloylmorpholine and 2- (2-methylimidazolyl) ethyl (meth) acrylate. The adhesive tape according to any one of claims 1 to 4, which is a structural unit derived from at least one monomer selected from the group.

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