TW201343860A - Adhesive tape - Google Patents

Abstract

The purpose of the present invention is to provide an adhesive tape capable of obtaining stable adhesion and detachment properties in a variety of environments. An adhesive tape in which a pressure-sensitive-adhesive layer is formed on one surface of a thermoplastic-resin film, wherein the thermoplastic-resin film and/or the pressure-sensitive-adhesive layer contain(s) an alkylene-bis saturated fatty acid amide containing a C1-4 alkylene group and a C12-18 saturated fatty acid residue.

Description

Adhesive tape

The present invention relates to an adhesive tape.

From the prior art, a PVC (PolyVinyl Chloride) film or the like is used as a base material layer of a re-peelable adhesive tape in a semiconductor manufacturing process or the like. The adhesive tape is formed by coating an adhesive layer on one surface of a base material layer containing such a PVC film, and is added to a substrate or an adhesive by a fatty acid guanamine (Japanese Patent Laid-Open Publication No. SHO 57-139163) And the fatty acid guanamine is appropriately exuded to the adhesive surface to control the rewindability and the adhesion to the adherend.

Further, it has been revealed that a urea compound and hydrotalcite can be added to a vinyl chloride resin to obtain good peelability and stain resistance (Japanese Patent Laid-Open Publication No. Hei 07-276516).

However, in the present state, the adhesive property is unstable, and the roll peeling force is unstable when the adhesive tape is stored as a wound body, or the semiconductor wafer or the like is peeled off when the adhesive tape is peeled off. The pollution of the body is large. In particular, depending on the state of storage in the wound body of the adhesive tape, the state of storage after bonding of the adherend, and the like, there is a case where the adhesive tape is wound from the wound body or the adhesive tape is peeled off from the adherend. It is difficult to peel off or the adhesive or the like remains on the adherend or the like.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an adhesive tape which can be used for preservation of an adhesive tape and adhesion to an adherend in various environments. The balance is preserved, and a peeling property such as a stable roll peeling force is obtained.

The inventors of the present invention conducted intensive studies on the adhesive properties and peeling characteristics of the current re-peelable adhesive tape, and as a result, found that the alkyl di fatty acid contained as an additive in the base layer or the adhesive layer of the adhesive tape Among the guanamines, there are various impurities due to the difference in raw materials during synthesis, etc. However, various alkylene difatty acid decylamines are commercially available, and depending on the type thereof, unexpectedly, in particular, the roll peeling force can be lowered. As a result, by selecting an appropriate alkylenediamine fatty acid amide, especially a compound which is saturated as an additive, it is possible to balance the storage of the adhesive tape and the adhesion of the adherend in various environments. The peeling property such as a stable roll peeling force is obtained, thereby obtaining the adhesive tape of the present invention.

In other words, the adhesive tape of the present invention is characterized in that it is formed of a pressure-sensitive adhesive layer formed on one surface of a thermoplastic resin film, and is contained in at least one of a thermoplastic resin film and a pressure-sensitive adhesive layer. The alkylenedi-saturated fatty acid decylamine containing a C 1~4 alkylene group and a C12-12 fatty acid residue.

Such an adhesive tape preferably has one or more of the following.

The alkylene di-saturated fatty acid amide is added in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin film includes a film of a soft polyvinyl chloride containing a plasticizer.

The pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer.

A release liner is disposed on the pressure-sensitive adhesive layer side of the adhesive tape.

According to the adhesive tape of the present invention, it is possible to balance the storage of the adhesive tape and the adhesion to the adherend in various environments, and to obtain a peeling property such as a stable roll peeling force.

[adhesive tape]

The adhesive tape of the present invention is mainly formed of a thermoplastic resin film as a base material layer and a pressure-sensitive adhesive layer laminated on one surface of the thermoplastic resin film. The alkylene di-saturated fatty acid decylamine is contained in one of the thermoplastic resin film and the pressure-sensitive adhesive layer. The alkylene di-saturated fatty acid decylamine may be contained only in the pressure-sensitive adhesive layer or only in the thermoplastic resin film, or may be contained in both the pressure-sensitive adhesive layer and the thermoplastic resin film. As described below, in the case where the thermoplastic resin film and/or the pressure-sensitive adhesive layer is a laminated structure, it may be contained in one of the layers, preferably at least the thermoplastic resin film and the pressure-sensitive adhesive layer are in contact with each other. Contained in the layer.

The adhesive tape of the present invention is preferably provided with a release liner in contact with the pressure-sensitive adhesive layer as needed.

[Alkyl di-saturated fatty acid decylamine]

The alkylene di-saturated fatty acid decylamine of the present invention contains an alkylene group having 1 to 4 carbon atoms and a saturated fatty acid residue having 12 to 18 carbon atoms. Here, the alkylene group may also be one of a straight chain or a branched chain. Further, the term "saturated fatty acid residue" means a group from which a hydroxyl group is removed from a saturated aliphatic monocarboxylic acid.

Such alkylene di-saturated fatty acid guanamine can be represented, for example, by the formula (II).

(In the formula, R represents an alkylene group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a saturated hydrocarbon group having 11 to 17 carbon atoms.)

Examples of the alkylene group of R include a methylene group, an ethyl group, an ethyl group, and an isopropyl group. Base, n-butylene, and the like.

The saturated hydrocarbon group of R ¹ and R ² also includes one of a straight chain, a branched chain, a cyclic group, and a combination thereof. For example, a chain alkyl group such as undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl or heptadecyl, and the branched alkane thereof may be mentioned. Base.

Further, the compound represented by the formula (II) is more preferably a compound represented by the formula (IV).

CH ₃ -(CH ₂ ) _n -CO-NH-(CH ₂ ) _t -NH-CO-(CH ₂ ) _m -CH ₃ (IV)

(wherein n and m each independently represent an integer from 10 to 16, and t represents 1 or 2.)

The alkylene di-saturated fatty acid decylamine may be contained singly or in combination of two or more. More specifically, the compound represented by the formula (II) may be one type or a mixture of two or more types. R ¹ and R ² may also be different from each other, and are preferably the same.

In the formula (II), the R system preferably has a carbon number of 1 to 3, more preferably a carbon number of 1 or 2.

R ¹ and R ^{2 are} preferably a linear or branched saturated hydrocarbon group, preferably one or more selected from the group consisting of 11, 13, 15 and 17 carbon atoms, more preferably 15 to 17 carbon atoms, or More preferably, it is undecyl, heptadecyl, and the like.

In the formula (IV), n and m are preferably selected from one or more of the group consisting of 10, 12, 14 and 16 carbon atoms, more preferably 14 to 16 carbon atoms, or more preferably 10 or more. 16.

As a specific compound of the formula (II), N,N'-methylenebisguanyl laurate, N,N'-methylenebis myristate, N,N'-methylenebispalmitine Indoleamine, N,N'-methylenebisstearate decylamine, N,N'-ethylenebisguanyl laurate decylamine, N,N'-ethylenebisbis myristate amide, N,N '-Ethylene dipalmitate decylamine, N,N'-ethylidene bis-stearate, N,N'-propylene bismuth laurate, N,N'-propylene bis-myristate, N,N'-butylene dipalmitate Indoleamine, N,N'-butylidene bis-stearate, of which N,N'-methylenebisstearate decylamine, N,N'-methylenebislaurate decylamine , N,N'-methylenebispalmitine decylamine and combinations thereof, more preferably N,N'-methylenebisstearate decylamine and N,N'-methylenebispalmitic acid a mixture of guanamine. Further, the content of N,N'-methylenebisstearate decylamine and N,N'-methylenebispalmitine decylamine may be exemplified by methylene bis-stearate decylamine: methylene Bismuth palmitate =0~10:10~0, preferably about 5~8:2~5.

In general, an alkyl di-saturated fatty acid amide is produced by the reaction of a saturated fatty acid decylamine with an aldehyde as shown below. Further, the saturated fatty acid guanamine is industrially produced by the reaction of a saturated fatty acid with ammonia.

2R ^a -CO-NH ₂ +R ^b CHO→R ^a -CO-NH-CH ₂ -NH-CO-R ^a

R ^a -CO-NH ₂ +R ^b CHO→R ^a -CO-NH-R ^b' OH

(wherein R ^a , R ^b and R ^{b '} represent a saturated or unsaturated hydrocarbon group)

Further, in the above production method, not only the di-fatty acid decylamine but also the mono-fatty acid decylamine (including the remaining material as a raw material) is contained, and the purity of the alkyl-saturated fatty acid decylamine changes depending on the production conditions and the like. And in industrial processes, it seems that the accuracy cannot be strictly controlled. At the present time, when the purity of the alkylenedi-saturated fatty acid guanamine as a commercial product is analyzed, it is confirmed that the impurity component is contained in a large amount as described below, and the difference per manufacturing lot is also large.

A total of about 70% of methylene bis-stearate decylamine / methylene dipalmitate decylamine, 1 to 4% of decylamine stearate, 0.5 to 1.5% of decyl palmitate, Stearic acid 1~5%, palmitic acid 0.5~1.5% and triterpenoids about 20%.

Thus, in theory, there may be an alkylene di-saturated fatty acid decylamine which is obtained by the reaction of a saturated fatty acid decylamine with formaldehyde and which is purified by its purity, but in fact, as an industrial product, there is no substance. An alkyl di-saturated fatty acid decylamine which does not contain impurities.

In the adhesive tape of the present invention, by containing a specific alkyl di-saturated fatty acid guanamine, the balance of the storage of the adhesive tape and the adhesion to the adherend can be achieved, and in particular, the roll peeling force can be effectively suppressed. With the rise of time, stable adhesive properties are obtained without residual adhesive.

Therefore, the alkyl di-saturated fatty acid amide compound used in the adhesive tape of the present invention is preferably purified by applying an extraction (including cleaning, etc.) using a specific solvent.

As the solvent here, a solvent which dissolves the saturated fatty acid guanamine used as a raw material but does not dissolve the alkyl di-saturated fatty acid decylamine is suitable. Further, in order to further increase the purity of the alkylenedi-saturated fatty acid decylamine obtained by the reaction of the saturated fatty acid decylamine with formaldehyde, it is preferred to further use a solvent which dissolves the fatty acid used as a raw material of the fatty acid guanamine. Here, the term "dissolving" means that the amount of the solvent required to dissolve 1 g of the solute is 10 g or less, and the term "insoluble" means that the amount of the solvent required to dissolve 1 g of the solute is 100 g or more.

Specific examples of the solvent include chloroform, ethanol, methanol, and the like. Among them, chloroform, ethanol is heated, methanol is heated, and the like.

As the extraction, any one of known methods can also be used. For example, a method of immersing an alkylenedi-saturated fatty acid decylamine obtained by a reaction of a saturated fatty acid monodecylamine with formaldehyde in a solvent, and using a solvent in the obtained alkyl di-saturated fatty acid decylamine may be mentioned. Soxhlet extraction method, etc. The conditions at this time are not particularly limited, for example, adding The solvent of 30 to 100 times the capacity or weight of the alkyl di-saturated fatty acid decylamine is impregnated, infiltrated, washed or extracted for about 30 minutes to several hours. The solvent can also be heated at room temperature to about 100 ° C depending on the type of solvent used. Again, such operations may be repeated as many times as needed. The obtained insoluble matter is separated by a known method such as filtration.

It is preferred to dry the insoluble matter after the extraction. Drying can also utilize any of the methods conventionally performed in the art. The drying conditions and temperature are not particularly limited, and it is preferred to adjust them as appropriate.

Specifically, in the case of extracting chloroform, for example, 40 ml of chloroform is added to about 1 g of a commercially available alkylenedi-saturated fatty acid decylamine, and permeabilized by a permeator for 1 hour, after which it is filtered by suction. It is separated into an insoluble portion and a soluble portion. The obtained chloroform-insoluble portion is arbitrarily subjected to the same operation twice, whereby a purified alkylenedi-saturated fatty acid decylamine composition can be obtained.

Further, in the case of extracting ethanol, for example, 40 ml of ethanol is added to about 1 g of a commercially available alkylenedi-saturated fatty acid decylamine, and the mixture is heated and extracted at 80 ° C (hot plate temperature) for 1 hour. Thereafter, the supernatant is separated into a supernatant (soluble portion) and a sediment (insoluble portion), and the obtained ethanol-insoluble portion is optionally subjected to the same operation twice to obtain a purified alkyl-saturated fatty acid decylamine. combination.

Thus, by solvent extraction of the alkylene di-saturated fatty acid decylamine, the fatty acid monodecylamine (preferably, the fatty acid removed) which is formed/remained when the alkylene di-saturated fatty acid decylamine is formed can be removed. A higher purity alkylene di-saturated fatty acid decylamine.

The alkylenedi-saturated fatty acid decylamine used in the present invention is suitable for removing fatty acid monoamines and/or fatty acids without substantially containing them. In the normal analysis equipment (liquid chromatography apparatus, high-speed liquid chromatography apparatus, etc.), the fatty acid monoamine and/or fatty acid are contained in a single type, and the measurement is not performed. 0.5% by weight, preferably less than 0.4% by weight, less than 0.25% by weight, less than 0.2% by weight, less than 0.1% by weight, 0.05% by weight, or less than the detection limit; or, in a plurality of types, the total content thereof Less than 2% by weight, preferably less than 1.6% by weight, less than 1% by weight, less than 0.8% by weight, less than 0.5% by weight, less than 0.4% by weight, less than 0.3% by weight, 0.05% by weight, tested Below the limit.

That is, the alkylenedi-saturated fatty acid guanamine used in the present invention preferably does not substantially contain a fatty acid monoamine which is produced by a raw material, a production method, or the like, and a fatty acid of the same or different kind, such as monoamine or lauric acid. Acid monodecylamine, monodecyl oleate, monodecyl erucic acid, monodecyl citrate, monodecyl palmitate, monodecylamine myristate, monodecyl behenate, and the like.

Further, the alkylenedi-saturated fatty acid guanamine used in the present invention preferably does not contain a fatty acid produced by a raw material or the like and a fatty acid of the same or different kind, such as citric acid, stearic acid, oleic acid, erucic acid, lauric acid. , palmitic acid, myristic acid, behenic acid, etc., especially stearic acid, oleic acid, palmitic acid and the like.

In the adhesive tape of the present invention, the content of the alkyl bis-saturated fatty acid phthalamide in the thermoplastic resin film is, for example, about 0.1 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic resin in the thermoplastic resin film. More preferably, it is about 0.1 to 3.0 parts by weight.

Further, the content of the pressure-sensitive adhesive layer of the alkyl bis-saturated fatty acid guanamine is, for example, preferably in the range of about 0.1 to 5.0 parts by weight, more preferably 0.1 to 100 parts by weight of the base polymer described below. 3.0 parts by weight or so.

In the case where the alkylene di-saturated fatty acid decylamine is contained in both the thermoplastic resin film and/or the pressure-sensitive adhesive layer, the total amount thereof is preferably from 0.1 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic resin. Appropriate adjustment within the range of the left and right, preferably about 0.1 to 3.0 parts by weight.

(thermoplastic resin film)

The thermoplastic resin film of the present invention is not particularly limited, and examples thereof include films of low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, and random copolymerization. Polyolefin, block copolymerized polypropylene, homopolypropylene, polybutene, polymethylpentene, etc.; ethylene-vinyl acetate copolymer, ion a polyolefin resin such as a polymer resin, an ethylene-(meth)acrylic acid copolymer, an ethylene-(meth)acrylate (random, alternating) copolymer, an ethylene-butene copolymer, or an ethylene-hexene copolymer; Polyester resin such as polyurethane, polyethylene terephthalate or polyethylene naphthalate; (meth)acrylic polymer, polystyrene, polycarbonate, polyimine , polyamine, polyamidimide, polyether phthalimide, polyfluorene, polyether oxime, polyvinyl chloride, polyvinylidene chloride, fluororesin, cellulose resin, and the like, etc. Thermoplastic resin. These thermoplastic resins may also be blended with a plurality of types as needed. Among them, a vinyl chloride resin film is preferred.

The vinyl chloride resin includes a mixture of polyvinyl chloride, a vinyl chloride copolymer, a graft copolymer of polyvinyl chloride, and other resins.

Examples of the comonomer in the vinyl chloride copolymer include vinyl esters such as vinyl acetate, vinyl ethers such as ethylene vinyl ether, α-olefins such as ethylene, propylene, and 1-butene, and methyl acrylate. And (meth) acrylates such as ethyl acrylate, methyl methacrylate and butyl methacrylate, and vinylidene chloride.

In particular, in the case of using a vinyl chloride resin, a soft vinyl chloride resin to which a plasticizer described below is added is preferred.

The thermoplastic resin film preferably contains a plasticizer so that the adhesive tape obtained thereby exhibits moderate flexibility, and further contains a stabilizer, a filler lubricant, a colorant, an ultraviolet absorber, an antioxidant, etc. as needed. additive.

The plasticizer is not particularly limited, and examples thereof include a phthalic acid ester type, a trimellitic acid ester type (manufactured by Dainippon Ink Co., Ltd., W-700, trioctyl trimellitate, etc.), and Acid ester (manufactured by J-plus, D620, dioctyl adipate, diisononyl adipate, etc.), phosphate ester (tricresyl phosphate, etc.), adipic acid ester, citric acid ester (Ethyl tributyl citrate, etc.), sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (epoxy soybean oil, Epoxidized linseed oil, etc., polyester (including low molecular weight polyesters of carboxylic acid and ethylene glycol, etc.). Among them, an ester-based plasticizer is preferably used. These also They may be used singly or in combination of two or more.

The plasticizer is suitably used in an amount of, for example, 10 to 60 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of the thermoplastic resin.

The stabilizer is not particularly limited, and examples thereof include a composite stabilizer such as a cerium-zinc system, a tin system, a calcium-zinc system, and a cadmium-antimony system.

Examples of the filler include inorganic fillers such as carbonic acid, alumina, and mica; and metal fillers such as iron and lead.

Examples of the colorant include a pigment, a dye, and the like.

Other additives may also be used in any of those well known in the art.

The thermoplastic resin film may be a single layer film or a laminate (multilayer film) of a film having different materials or compositions and exhibiting the advantages of each resin.

The thickness of the thermoplastic resin film can be adjusted depending on the physical properties of the adhesive tape to be obtained, and examples thereof include 30 to 1000 μm, preferably 40 to 800 μm, more preferably 50 to 500 μm, and particularly preferably 60 to 200. Mm.

In order to improve the adhesion to the adhesive on the front side of the thermoplastic resin film, particularly the upper surface, that is, the side on which the adhesive layer is provided, a conventional surface treatment such as corona treatment, chromic acid treatment, or ozone may be performed. Oxidation of chemical or physical methods such as exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, etc.

As described above, the adhesive tape of the present invention can particularly reduce the peeling force of the roll, and therefore it is not necessary to carry out the backside treatment on the back side of the thermoplastic resin film, that is, only on the side of the face where the adhesive layer is in contact with the wound body, for example, lowering The treatment such as the unevenness of the contact area with the adhesive layer, the release treatment, and the like can maintain an appropriate roll peeling force.

(pressure-sensitive adhesive layer)

The pressure-sensitive adhesive (hereinafter sometimes simply referred to as "adhesive") layer is formed by a pressure-sensitive adhesive. The pressure-sensitive adhesive is not particularly limited, and examples thereof include a rubber-based adhesive and an acrylic adhesive, depending on the type of the base polymer constituting the adhesive. A polyamide-based adhesive, an anthrone-based adhesive, a polyester-based adhesive, a urethane-based adhesive, or the like can be appropriately selected from these known adhesives. Among them, the acrylic pressure-sensitive adhesive is excellent in various properties such as heat resistance and weather resistance, and can be preferably used because it can exhibit desired characteristics by selecting the type of the monomer component constituting the acrylic polymer.

The acrylic adhesive is usually formed of a base polymer composed mainly of an acrylic polymer such as an alkyl (meth)acrylate.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. ) butyl acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (A) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isophthalic acid (meth) acrylate Ester, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate Ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, (methyl) An alkyl ester of a C1 to C20 (meth)acrylic acid such as an amyl acrylate (preferably an alkyl ester of a C1 to C12 (meth) acrylate. Further preferably a C1 to C8 alkyl (meth) acrylate. Base ester) and the like. The alkyl (meth)acrylate may be used singly or in combination of two or more.

The acrylic polymer is intended to be modified by cohesive force, heat resistance, crosslinkability, etc., and may optionally contain units corresponding to other monomer components copolymerizable with the alkyl (meth)acrylate.

Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. a monomer of a carboxyl group; (meth)hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxy octyl acrylate, (meth) hydroxy decyl acrylate, (methyl) hydroxy ten a monomer having a hydroxyl group such as a dialkyl acrylate or a methyl (4-hydroxymethylcyclohexyl)methyl acrylate; a styrenesulfonic acid, an allylsulfonic acid, or a 2-(methyl)acrylamidoamine-2 a monomer containing a sulfonic acid group such as methyl propanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate or (meth) propylene decyl naphthalene sulfonic acid; - a phosphate group-containing monomer such as a hydroxyethyl propylene fluorenyl group, a (meth) acrylamide group, an N,N-dimethyl(meth) acrylamide group, or an N-butyl (meth) propylene group (N-substituted) guanamine monomer such as guanamine, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.; Ester, N,N-dimethylamine (meth)acrylate (meth)acrylic acid amine alkyl monomer such as ester, tert-butylaminoethyl (meth)acrylate; (meth)acrylic alkoxyalkyl monomer; N-cyclohexylmaleimide , N-isopropylmaleimide, N-lauric maleimide, N-phenylmaleimide, and the like, maleic imine monomer; N-methyl itaconimine, N-ethyl itaconium imine, N-butyl itaconimine, N-octyl ketimine, N-2-ethylhexyl ketamine, N-cyclohexyl amide N-(methyl) propylene oxymethylene succinimide, N-(methyl) propylene fluorenyl - N-(methyl) propylene oxymethylene succinimide a butadieneimine monomer such as 6-oxyhexamethylene succinimide, N-(methyl)propenyl-8-oxyoctamethylene succinimide; vinyl acetate, C Vinyl acetate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, Vinyl A vinyl monomer such as azole, vinylmorpholine, N-vinylcarboxylic acid decylamine, styrene, α-methylstyrene or N-vinyl caprolactam; cyanide such as acrylonitrile or methacrylonitrile Acrylate-based monomer; epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; (meth)acrylic acid polypropylene glycol, (meth)acrylic acid methoxyethylene glycol, (methyl) a glycol-based acrylate monomer such as methoxypolypropylene glycol; a tetrahydrofurfuryl (meth)acrylate, a fluorine (meth) acrylate, or a polyoxyalkylene (meth) acrylate having a hetero ring; Acrylate monomer such as halogen atom or germanium atom; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentane Diol (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , epoxy acrylate, polyester acrylate, urethane acrylate, divinyl benzene, butyl di (meth) acrylate Polyfunctional monomers hexyl di (meth) acrylate and the like; isoprene, di-butadiene, isobutylene and other olefin-based monomers; vinyl ether, vinyl ether-based monomers. These monomer components may be used alone or in combination of two or more.

The acrylic copolymer can be produced by subjecting the above (meth)acrylic acid alkyl ester and other monomers to polymerization by a known and appropriate method as needed.

The molecular weight and the like of the acrylic copolymer are not particularly limited, and for example, a weight average molecular weight of from 100,000 to 2,000,000, preferably from 150,000 to 1,000,000, and more preferably from 300,000 to 1,000,000 can be used. The weight average molecular weight is, for example, a molecular weight standard material, and can be, for example, a value measured by gel permeation chromatography (GPC, Gel Permeation Chromatography) using polystyrene.

The adhesive can be an energy ray-curable adhesive by adding an energy ray polymerizable compound or introducing an energy ray polymerizable double bond to a base polymer or the like. The adhesive layer using the energy ray-curable adhesive exhibits a sufficient adhesive force before the energy ray irradiation, but the force is remarkably lowered after the energy ray irradiation, and can be easily peeled off without applying stress to the adherend. Further, examples of the energy line include ultraviolet rays, electron beams, and the like.

As an energy ray polymerizable compound, it can be used for two or more kinds of energy in a molecule. A compound of a linear polymerizable carbon-carbon double bond. As such a compound, a polyfunctional acrylate type compound is mentioned, for example.

Examples of the polyfunctional acrylate-based compound include 1,4-butylbutyl di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, and 1,6-hexanediol. Linear aliphatic polymorphisms such as (meth) acrylate, 1,9-nonanediol di(meth)acrylate or polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate a (meth) acrylate of an aliphatic monomer having an alicyclic group, such as an alcohol (meth) acrylate; cyclohexane dimethanol di(meth) acrylate; tricyclodecane dimethanol diacrylate; a (meth) acrylate of a branched aliphatic polyol such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate or the like (di-trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, etc.). These may be used alone or in combination of two or more.

As the energy ray polymerizable compound, for example, a polyfunctional acrylate oligomer such as an urethane acrylate oligomer can be used.

The urethane acrylate oligomer can be obtained, for example, by subjecting an alkyl (meth) acrylate having a hydroxyl group to an amide obtained by reacting a diisocyanate compound with a polyol compound. The ester oligomer is reacted.

Examples of the diisocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, phenyl diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, and tetramethyl benzene dimethyl group. Diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, and the like.

Examples of the polyol compound include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, and polypropylene glycol. a polyhydric alcohol such as pentaerythritol, dipentaerythritol or glycerin; or an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, sebacic acid or maleic acid or terephthalic acid or isophthalic acid a polyester-based polyol compound obtained by a condensation reaction of an aromatic dicarboxylic acid such as formic acid; Polyether polyol compounds such as diethyl ether glycol, poly(propylene ether glycol), polytetramethylene ether glycol, and polyhexamethylene ether glycol; polycaprolactone ethylene glycol, polypropylene glycol, a lactone-based polyol compound such as polyethylene glycol valerolactone; a polyol such as ethylene glycol, propylene glycol, butanediol, pentanediol, octanediol or decanediol, and diethyl carbonate, carbonic acid A polycarbonate-based polyol compound obtained by a dealcoholization reaction such as propylene glycol. Examples of the hydroxyl group-containing (meth)acrylic acid alkyl ester compound include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylic acid. Ester, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl methacrylate, 12-lauryl hydroxy methacrylate, (4-hydroxymethylcyclohexyl) Methyl methacrylate and the like.

The energy ray polymerizable compound can be used, for example, in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 10 to 45 parts by weight, per 100 parts by weight of the base polymer.

As a method of introducing an energy ray-polymerizable double bond to a base polymer, for example, when preparing an acrylic polymer as a base polymer, copolymerization of a reactive functional group such as a carboxyl group, a hydroxyl group or an amine group is used. Sexual monomer copolymerization. Thereby, a functional group which becomes a base point of the reaction can be introduced into the base polymer, and a polyfunctional monomer having an energy ray-polymerizable carbon-carbon double bond or oligomerization can be obtained via a functional group which becomes a base point of the above reaction. The substance is bonded to obtain a base polymer having an energy ray polymerizable carbon-carbon double bond on the branch.

The energy ray-curable adhesive may also contain a photopolymerization initiator as needed. The photopolymerization initiator is excited and activated by irradiation of an energy ray to generate a radical, and promotes an effective polymerization hardening reaction of the adhesive layer.

Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Benzoin alkyl ether initiator; benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene benzophenone, etc. Starting agent; α-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethyl An aromatic ketone initiator such as acetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone; benzene An aromatic ketal-based initiator such as decyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthiophene Tons of ketone, 2-dodecylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di a thioxanthone initiator such as isopropyl thioxanthone; a benzyl initiator such as benzyl; a benzoin-based initiator such as benzoin; and an α-keto alcohol compound (2-methyl-2-hydroxypropiophenone) Etc.), aromatic sulfonium chloride-based compound (2-naphthylsulfonium chloride, etc.), photoactive ruthenium compound (1-benzophenone-1, 1-propanedione-2-(o-ethoxycarbonyl) hydrazine, etc.) , camphorquinone, halogenated ketone, mercaptophosphine oxide, sulfhydryl phosphate Acid esters, etc. These may be used alone or in combination of two or more.

The adhesive can also be used to form a hydrophilic hydrophilic adhesive by using a polymer having an acidic group such as a carboxyl group as a base polymer and adding a neutralizing agent to neutralize all or a part of the acidic groups in the base polymer. . The hydrophilic adhesive is usually less in the paste residue of the adherend, and can be easily removed by washing with pure water even in the case where the residue of the paste is generated.

The polymer having an acidic group can be obtained by copolymerizing a monomer having an acidic group having a carboxyl group-containing monomer or the like in the preparation of the base polymer.

Examples of the neutralizing agent include primary amines such as monoethylamine and monoethanolamine; secondary amines such as diethylamine and diethanolamine; triethylamine, triethanolamine, N,N,N'-trimethylethylene A basic amine compound such as an amine, a N-methyldiethanolamine or a tertiary amine such as N,N-diethylhydroxylamine.

The adhesive may also contain a crosslinking agent as needed.

As the crosslinking agent, for example, an epoxy crosslinking agent, an isocyanate crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent can be used. , a metal salt crosslinking agent, a carbon bismuth imide crosslinking agent, As the crosslinking agent such as an oxazoline crosslinking agent, an aziridine crosslinking agent, or an amine crosslinking agent, an epoxy crosslinking agent, an isocyanate crosslinking agent, or the like can be preferably used. These may be used alone or in combination of two or more.

Examples of the epoxy-based crosslinking agent include N,N,N',N'-tetraglycidyl meta-xylylenediamine, diglycidylaniline, and 1,3-bis(N,N-glycidol). Amine methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol glycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol glycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane Polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl-tris(2-hydroxyethyl)isocyanurate, resorcinol diglycidyl Ether, bisphenol-S-diglycidyl ether, epoxy resin having two or more epoxy groups in the molecule, and the like.

Examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethanediisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; Aliphatic polyisocyanates such as diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene An aromatic polyisocyanate such as isocyanate, 4,4'-diphenylmethane diisocyanate or benzene dimethylene diisocyanate.

The adhesive layer preferably contains a plasticizer. The plasticizer is the same as the above. Preferably, the amount of the plasticizer added in this case is suitably 100 parts by weight based on the thermoplastic resin constituting the adhesive, and is used, for example, in a ratio of 10 to 100 parts by weight, preferably 10 to 80 parts by weight. More preferably, it is 10 to 60 parts by weight.

The adhesive layer may further contain a stabilizer, a filler lubricant, and a coloring as needed. Additives such as agents, UV absorbers, antioxidants, and colorants. The additives mentioned above may be the same as described above.

The adhesive layer can be formed by applying the above adhesive to a base by a suitable method such as a knife coater, a roll coater, a gravure coater, a die coater, a reverse coater or the like. On the material. Further, for example, the pressure-sensitive adhesive layer may be formed on a suitable casting step sheet such as a film having a release treatment on the surface, and the pressure-sensitive adhesive layer may be transferred onto the thermoplastic resin film.

The thickness of the adhesive layer is not particularly limited, and is preferably 5 to 100 μm, more preferably 5 to 60 μm, and particularly preferably 5 to 30 μm. When the thickness of the adhesive layer is within the above range, the stress of the thermoplastic resin film can be alleviated, and the stress relaxation rate of the adhesive tape can be improved.

The adhesive tape of the present invention is preferably such that, for example, regardless of the state of storage, the silicon wafer can be suppressed to a variation value within ±0.5 N/20 mm before and after storage. Further, from the other viewpoints, it is preferably suppressed within ±70% of the initial value, preferably within 65%, and more preferably within ±63%. By changing the range, it is possible to prevent the adhesion of the adhesive tape from being lowered regardless of the state of storage, and the peeling from the adherend can be easily performed. Here, the pre-storage and initial values refer to the production of the adhesive tape (after forming the wound body) or after the adhesive tape is formed and the release liner is brought into contact with the adhesive layer side. After the storage, it is usually referred to as a time point from the time of manufacture (when the wound body is formed) or when the release liner contacts the adhesive layer side for about one week or more.

The adhesive tape can be used for various purposes. For example, it can be used for fixing various members such as optical devices, films, resins, glass, metals, and the like having a plate shape or a curved surface, wafers in a semiconductor process, etc.; semiconductor back surface polishing; semiconductor cutting; semiconductor packaging, glass For cutting such as ceramics or the like; for the protection of the circuit surface or the like during the processes, it is used as an adhesive tape for bonding (and further peeling). Therefore, the adhesive tape of the present invention can be formed into shapes suitable for such applications, such as various shapes and sizes such as a sheet shape and a short strip shape.

Thus, the adhesive tape of the present invention is adhered to at least a thermoplastic resin film and pressure-sensitive adhesive One of the agent layers contains a specific alkyl di-saturated fatty acid guanamine, which can further balance the preservation of the adhesive tape and the adhesion to the adherend, and in particular, can effectively suppress the elapse of the roll peeling force. Rise. Further, regardless of the state of storage (that is, even under storage or processing conditions at a high temperature), sufficient adhesion can often be obtained. Or, even in the storage condition of the wound body and the storage condition of about 60 ° C in the state of being attached to the adherend such as the tantalum wafer (that is, the storage in the wound body and the bonded body) In the state of the wound body, it is possible to effectively prevent the adhesive from remaining on the adherend or the like when the film is wound from the wound body and is again peeled off from the adherend.

(release liner)

The adhesive tape of the present invention may be provided with a release liner in contact with the adhesive layer on the side of the adhesive layer to protect the adhesive layer and the like.

The release liner can be used without particular limitation as long as it is a general user in the field. For example, the following may be used as a substrate: various metal foils such as paper, rubber, aluminum foil, copper foil, stainless steel foil, iron foil, Dura aluminum foil, tin foil, titanium foil, gold foil, etc.; polyethylene, polypropylene, polychlorinated a film made of various resins such as ethylene, polyester, and polyamide; a foam such as a polyurethane foam, a vinyl foam, a polyethylene foam, or a styrene foam, or a non-woven fabric, A woven fabric, a felt, and a film obtained by laminating these materials with a polymer material. The thickness of the substrate is not particularly limited, and is, for example, 5 μm to 5 mm, preferably about 30 μm to 100 μm.

The oxime-based resin, the long-chain alkyl resin, the fluorine-based resin, the low-molecular-weight polyethylene, the polypropylene, and the rubber-based polymer are applied in a layer form on the surface on the side in contact with the adhesive layer in the substrate. Examples of the release agent such as a phosphate ester surfactant include a release treatment which is well known in the art.

The release liner may also be provided with one or a plurality of straight, wavy, serrated, zigzag strips (so-called engagement) to improve the attaching operability when the adhesive tape is attached to the adherend.

[Method of making adhesive tape]

The adhesive tape of the present invention can be produced by adding a specific alkyl bis-saturated fatty acid decylamine to a resin to form a thermoplastic resin film or a pressure-sensitive adhesive layer.

The thermoplastic resin film and the pressure-sensitive adhesive layer are laminated.

A method of adding an alkylene di-saturated fatty acid decylamine as an additive to a resin or the like to form a thermoplastic resin film or a pressure-sensitive adhesive layer can be carried out by a method known in the art.

Further, the formation and lamination of the thermoplastic resin film or the pressure-sensitive adhesive layer may be sequentially performed. That is, the thermoplastic resin film and the pressure-sensitive adhesive layer may be separately formed by a method known in the art. Therefore, for example, a melt extrusion molding method (expansion method, T-die method, etc.), a melt casting method, a calendering method, or the like can be used. Further, the adhesive layer may be separately formed by the above method. As described above, in the case where the thermoplastic resin film and the pressure-sensitive adhesive layer are separately formed, both of them can be laminated by a method known in the art.

The formation and lamination of the thermoplastic resin film or the pressure-sensitive adhesive layer can also be carried out simultaneously. In other words, the thermoplastic resin film can be formed by a co-extrusion method, a lamination method (extrusion lamination method, a lamination method using an adhesive), a heat sealing method (external heating method, internal heat generation method, etc.). The pressure-sensitive adhesive layer is formed in a multilayer structure.

The release liner is usually attached to the side of the adhesive layer after forming the adhesive tape, whereby an adhesive tape with a release liner can be obtained.

[Examples] (production of adhesive tape)

The following raw materials were prepared, blended in advance using a Henschel mixer, and the plasticizer was allowed to permeate into the resin to be dried. A polyvinyl chloride mixture obtained by kneading with a Banbury mixer was used, and a thermoplastic resin film having a thickness of 110 μm was obtained by a calender film forming machine.

As the lubricant, an alkylene difatty acid decylamine shown in the following table was used. lubricating The agent is added during the mixing of the Banbury mixer.

The obtained adhesive was diluted to 20% with toluene, and applied to the thermoplastic resin film so as to have a thickness of 10 μm after drying, and wound into a roll shape by a drying step at 150 ° C for 1 minute.

The following evaluation was carried out using the obtained adhesive tape.

The rolled adhesive tape was cut to a width of 20 mm to prepare a sample.

The sample was rewinded using an Instron type tensile tester at a tensile speed of 0.3 m/min, and the peeling force from the roll was measured.

The peeling force was less than 1.0 N/20 mm, and the peeling force was 1.0 N/20 mm or more and less than 3.6 N/20 mm was set to Δ, and the peeling force was set to 3.6 N/20 mm or more to X.

Further, the measurement of the peeling force was carried out by measuring the following: one after winding in a roll, one week after storage at room temperature, and one week after drying in a dryer at 60 ° C and at room temperature. Place it for 1 hour.

The results of these are shown in the table below.

The components in Table 1 are as follows.

Methylene bis-stearate amide of Example 1: bis- decylamine LA (manufactured by Nippon Kasei Co., Ltd.), ethylene bis-stearate amide of Example 2: SLIPACKS E (manufactured by Nippon Kasei Co., Ltd.) Ethylene dilaurate decylamine of Example 3: SLIPACKS L (manufactured by Nippon Kasei Co., Ltd.), bismuth bismuthate amide of Comparative Example 1 : SLIPACKS B (manufactured by Nippon Kasei Co., Ltd.), Comparative Example 2 Hexamethylene bis-stearate amide: SLIPACKS ZHS (manufactured by Nippon Kasei Co., Ltd.), Ethylene bis-oleic acid decylamine of Comparative Example 3: SLIPACKS O (manufactured by Nippon Kasei Co., Ltd.), ethylene erucic acid decylamine of Comparative Example 4: SLIPACKS R (manufactured by Nippon Kasei Co., Ltd.), Comparative Example 5, hexa Ammonium methyl oleate: SLIPACKS ZHO (manufactured by Nippon Kasei Co., Ltd.).

[Industrial availability]

The adhesive tape of the present invention can be widely used as a surface protective tape or sheet for various kinds of adherends such as electronic parts, a processing tape or a sheet for cutting, or a protective tape or the like.

Claims (5)

An adhesive tape comprising a pressure-sensitive adhesive layer formed on one surface of a thermoplastic resin film, and containing at least one of a thermoplastic resin film and a pressure-sensitive adhesive layer The alkyl di-saturated fatty acid decylamine is an alkylene group having 1 to 4 alkyl groups and a saturated fatty acid residue having 12 to 18 carbon atoms. The adhesive tape of claim 1, wherein the alkyl bis-saturated fatty acid amide is added in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic resin. The adhesive tape of claim 1 or 2, wherein the thermoplastic resin film comprises a film of a soft polyvinyl chloride containing a plasticizer. The adhesive tape according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer. The adhesive tape according to any one of claims 1 to 4, wherein a release liner is disposed on the pressure-sensitive adhesive layer side of the adhesive tape.