TW201534680A - An adhesive tape - Google Patents

Abstract

An adhesive tape provided by the present invention has an adhesive layer formed on one side of a substrate, and after being heated at 135DEG C for 25 minutes, its adhesive force ratio (after being heated/ before being heated) is lower than 10 when being measured according to JIS Z 0237 (2000). Accordingly, an adhesive tape which is thermal resistant with good conformability is provided by the present invention, which can be applied to an adherend having an irregular surface and provides protection for objects that must go through heating steps. Even if the adherend has an irregular surface, the adhesive tape can satisfy the adhesive requirements (conformability) before and after being heated. It also provides good workability after being heated without breaking easily or having residual adhesives.

Description

Adhesive tape

The present invention relates to an adhesive tape.

Adhesive tapes are used in many areas. For example, Patent Document 1 discloses an adhesive tape which can maintain the balance between the adhesion of the adhesive tape and the adhesion of the adherend in various environments, and obtains a peeling property such as a stable roll peeling force, and can be used as a surface protection for an electronic component or the like. Or improve processability or provide protection during the dicing step.

Further, as disclosed in Patent Document 2, an adhesive tape which can be used for semiconductor processing or LED dicing is disclosed, and when the wafer is fixed on the susceptor for dicing, etc., it is possible to effectively suppress excessive adhesion due to susceptor heating, and prevent The wafer is broken.

Others such as painting work, etc., also use adhesive tape. For example, an adhesive tape of a specific shape is adhered to a non-painting portion of a painted surface as a protective film, and after being sprayed, the coating is dried by heat treatment, and the adhesive tape is peeled off to form a coating pattern having a specific shape.

Prior technical literature Patent literature

Patent Document 1: International Publication No. 2013/129463

Patent Document 2: International Publication No. 2013/129080

When the conventional adhesive tape is used for the painting work of the surface having the unevenness, due to the stickiness The adhesion between the belt and the uneven surface and the heat resistance are insufficient, and not only the coating may penetrate into the protective portion, but also the appearance of the pattern is poor, and the stability is poor when heated and dried, and there is a problem that the residual glue may not be peeled off after heating. Further, when the adhesive tape is peeled off from the adherend after coating and drying, there is also a problem that the coating adhered to the back surface of the adhesive tape is scattered and becomes a source of contamination. The present invention has been made in view of the above-described problems, and an object of the invention is to provide an adhesive tape having excellent heat resistance and unevenness and conformability, and is applicable to the surface of an adherend having irregularities and the protection of articles including a heating step. Even if the surface of the adherend has irregularities, it is sufficient to satisfy the requirements of adhesion (concavity and conformability) before and after heating, and it has good processability after heating, and it is less likely to cause cracking or residual glue.

The adhesive tape of the present invention is an adhesive layer which is formed on one surface of a substrate and which is measured according to JIS-Z-0237 (2000) before and after heating at 135 ° C for 25 minutes (after heating/heating) The front) is 10 or less.

In a preferred embodiment, at least one of the substrate or the adhesive contains an alkylene di-saturated fatty acid decylamine.

In a preferred embodiment, the adhesive tape of the present invention further comprises a non-adhesive layer, and the mixing ratio of the polyoxymethylene to the (meth)acrylic polymer in the non-adhesive layer is polyoxylium by weight: (methyl) Acrylic polymer = 1:1~1:5.

In a preferred embodiment, the resin material in the substrate comprises polyvinyl chloride.

In a preferred embodiment, the adhesive layer contains an acrylic polymer.

In a preferred embodiment, the content of the plasticizer in the adhesive is 38% by weight or more.

In a preferred embodiment, the substrate has a thickness of 20 to 200 μm.

In a preferred embodiment, the thickness of the adhesive layer is 5 to 30 μm.

In a preferred embodiment, the adhesive tape of the present invention is used for a protective tape having an uneven adherend.

According to the present invention, it is possible to provide an adhesive tape which can be suitably used as a protective film in a painting operation, and which has a good adhesion to an adherend (convex conformability), even if the adhesive body has a complicated shape. Fully sealed, the coating will not penetrate into the protective part, and has good heat resistance. In the harsh environment of high temperature drying in the coating process, it can also play a protective function, is not easy to crack, and can effectively inhibit the generation of residual glue. , maintain good peelability. Moreover, the present invention can also provide an adhesive tape which has good bonding property with a coating material. When the coating material is adhered to the back surface, the coating adhered on the back side of the adhesive tape does not scatter after being dried at a high temperature, so that no peeling is caused when the coating is removed. In addition, lines such as alignment adjustment marks can be printed on the adhesive tape.

The adhesive tape of the present invention has an adhesive layer on at least one side of the substrate. Further, a non-adhesive layer may be further included on the surface of the substrate opposite to the side of the adhesive layer, or a release liner may be further provided on the surface of the adhesive layer. Further, at least one of the substrate and the adhesive layer may further contain an alkylene di-saturated fatty acid decylamine. The details are as follows.

The adhesive strength of the adhesive tape of the present invention measured at 135 ° C for 25 minutes before and after heating according to JIS-Z-0237 (2000) (adhesive force after heating at 135 ° C / adhesion before heating) is 10 or less, preferably 9 or less, more preferably 8 or less. By setting the variation of the adhesive property to the above range, the adhesiveness of the adhesive tape to the surface of the adherend having irregularities and the heat resistance (residual property and peeling property) after the heat treatment can be improved. In particular, when the adhesive tape is used as a protective tape used for an article coating operation, the tape can be prevented from being broken when the adhesive tape is peeled off after coating. The method of measuring the adhesion before heating and the adhesion after heating at 135 ° C will be described in detail later.

The adhesive tape of the present invention has a pre-heating adhesive force at a temperature of 23 ° C and a humidity of 50%, preferably 70 gf / 25 mm or more, more preferably 80 gf / 25 mm or more, and still more preferably 90 gf / 25 Mm or more. The upper limit of the adhesive force before the adhesion of the adhesive tape is preferably 300 gf / 25 mm or less, more preferably 200 gf / 25 mm or less, and still more preferably 150 gf / 25 mm or less. By setting it as the above range, the adhesiveness of the adhesive tape to the surface of the adherend having irregularities can be improved.

When the adhesive tape of the present invention is heated at 135 ° C and has a bonding strength of 23 ° C and a humidity of 50%, it is preferably 1300 gf / 25 mm or less, more preferably 1000 gf / 25 mm or less, and still more preferably 850 gf / 25 mm or less. The lower limit of the adhesive force after heating at 135 ° C of the adhesive tape is preferably 120 gf / 25 mm or more, more preferably 150 gf / 25 mm or more, and still more preferably 300 gf / 25 mm or more. By setting it as the said range, the heat resistance (resistibility, peeling property) after heat processing can be improved.

The 50% modulus of the adhesive tape of the present invention at 23 ° C is preferably 7 kgf / 20 mm or less, more preferably 5 kgf / 20 mm or less, and still more preferably 3 kgf / 20 mm or less. The lower limit of the 50% modulus of the adhesive tape at 23 ° C is not particularly limited, and is preferably 1 kgf / 20 mm or more, more preferably 2 kgf / 20 mm or more. The method of measuring the 50% modulus at 23 ° C will be described in detail later.

The elongation of the adhesive tape of the present invention at a temperature of 23 ° C and a humidity of 50% is preferably 100% or more, more preferably 150% or more, and still more preferably 200% or more. The upper limit of the elongation is preferably 500% or less, more preferably 400% or less, and still more preferably 300% or less. The method of measuring the elongation will be described in detail later.

The elongation of the adhesive tape of the present invention after coating and heating at 135 ° C for 25 minutes is preferably 50% or more, more preferably 70% or more, and still more preferably 100% or more. The upper limit of the elongation after coating and heating at 135 ° C for 25 minutes is preferably 400% or less, more preferably 350% or less, still more preferably 300% or less. By setting it in the said range, the heat resistance (resistibility, peeling property) after heat processing can be improved. In particular, when the adhesive tape is used as a protective tape used for an article coating operation, the tape can be prevented from being broken when the adhesive tape is peeled off after coating.

The so-called coating and elongation at 135 ° C for 25 minutes means that the sample is attached to the SUS430BA plate, and after spraying the coating, it is dried at 135 ° C for 25 minutes, and the sample is removed from the SUS plate according to JIS-K- 7127 (1999) was subjected to a tensile test, and the value at the time of the fracture was measured. on The coating material is not particularly limited as long as it is liquid and can be hardened/adhered by volatilization/drying of a solvent (organic solvent or water), and a coating film is formed on the surface, and is preferably an acrylic resin diluted with an organic solvent. coating.

The coating of the adhesive tape of the present invention and the ratio of elongation (pre-heating/heating) measured according to JIS-K-7127 (1999) before and after heating at 135 ° C for 25 minutes are preferably 4 or less, more preferably 3 Hereinafter, it is more preferably 2.5 or less. By setting it in the above range, after the heat treatment, the adhesiveness of the adhesive tape to the surface of the adherend having irregularities and the heat resistance (residual property and peeling property) after the heat treatment can be improved. In particular, when the adhesive tape is used as a protective tape used for an article coating operation, the tape can be prevented from being broken when the adhesive tape is peeled off after coating.

"1. Substrate"

The substrate is not particularly limited and may include any suitable resin material. The resin material is preferably, for example, polyvinyl chloride, polyolefin, polyester, polyimine or polyamine. More preferably, it is polyvinyl chloride or polyolefin, and more preferably List polyvinyl chloride. Polyvinyl chloride is excellent in stress relaxation, and in particular, it is possible to improve the adhesion of the adhesive tape to the adherend having irregularities.

The content ratio of the above-mentioned resin material in the substrate can be set to any appropriate content ratio depending on the purpose and use. The content ratio is, for example, preferably 100% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less. The lower limit of the content ratio of the above-mentioned resin material in the substrate is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more.

A plasticizer may also be included in the substrate. The content of the plasticizer in the substrate is preferably from 0.5% by weight to 50% by weight, more preferably from 1.0% by weight to 40% by weight, based on the above-mentioned resin material in the substrate. By including the plasticizer in the above-mentioned content ratio in the substrate, flexibility can be imparted to the substrate, and the adhesion property when the adhesive tape is adhered to the adherend having irregularities can be improved.

Examples of the plasticizer include phthalic acid esters and trimellitic acid. Ester system (W-700 manufactured by Dainippon Ink Co., Ltd., trioctyl trimellitate, etc.), adipate ester (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate) Ester, diisodecyl adipate, etc.), phosphate (such as tricresyl phosphate), adipic acid ester, citric acid ester (such as tributyl citrate), sebacate, bismuth Acid esters, maleic acid esters, benzoic acid esters, polyether polyesters, epoxy polyesters (epoxidized soybean oil, epoxidized linseed oil, etc.), polyesters (including carboxylic acids and glycols) Low molecular weight polyester, etc.). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more.

The substrate may also contain any suitable other components insofar as it does not impair the effects of the present invention.

The elongation of the substrate measured according to JIS-K-7127 (1999) is preferably 100% or more, more preferably 200% to 1000%. By using the substrate exhibiting the above elongation, it is possible to impart appropriate elongation characteristics to the adhesive tape of the present invention and to improve the conformability to the adherend.

The thickness of the substrate is preferably 20 μm or more, more preferably 40 μm or more, and still more preferably 50 μm or more. The upper limit of the thickness of the substrate is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less. When the thickness of the substrate is less than 20 μm, there is a problem that the workability is deteriorated, and it is particularly difficult to carry out the bonding work when the adhesive tape is formed. If the thickness of the substrate is more than 200 μm, the conformability to the adherend may be deteriorated.

"2. Adhesive layer"

The adhesive tape of the present invention is one in which an adhesive layer is formed on one side of the substrate.

The thickness of the adhesive layer is not particularly limited, but is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit of the thickness of the adhesive layer is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. By setting it in the above range, the wettability to the adherend can be improved, and the adhesion to the adherend having irregularities can be improved.

As the material of the above adhesive layer, any suitable adhesive can be employed without departing from the effects of the present invention.

Examples of the material of the adhesive layer include a (meth)acrylic polymer; However, rubber; special natural rubber obtained by grafting monomers such as methyl methacrylate; synthetic rubber such as SBS, SBR, SEPS, SIS, SEBS, polybutene, polyisobutylene, polyisobutylene, butyl rubber, etc. Among these, a (meth)acrylic polymer is preferred because it has less residual residue of the adherend after peeling, has high cohesiveness, and is excellent in transparency.

In the case where the adhesive layer contains a (meth)acrylic polymer, the content ratio of the (meth)acrylic polymer in the adhesive layer can be appropriately set depending on the purpose.

The (meth)acrylic polymer is a resin containing a monomer component containing a (meth)acrylic monomer as a main monomer. The content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight. The above is particularly preferably 95% by weight or more. The upper limit of the content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 100% by weight or less, and more preferably 97% by weight or less. The monomer in the above monomer component may be one type or two or more types.

The (meth)acrylic monomer is preferably (meth)acrylate or (meth)acrylic acid.

Examples of the (meth) acrylate include an alkyl (meth)acrylate having a carbon number of 1 to 30 (including a cycloalkyl group), a (meth)acrylate containing a hydroxyl group, and the like. The (meth) acrylate may be used alone or in combination of two or more.

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)acrylate, ethyl (meth)acrylate, and (methyl). ) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate , amyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (methyl) Isodecyl acrylate, undecyl (meth)acrylate Base ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (methyl) Octadecyl acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate, lauryl (meth) acrylate, etc., having a carbon number of 1 to 30 (also included A cycloalkylalkyl (meth) acrylate or the like. Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of an alkyl group (also containing a cycloalkyl group).

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

In order to sufficiently exhibit the effect as an adhesive, the monomer component constituting the (meth)acrylic polymer preferably contains at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer. More preferably, it is a monomer having a carboxyl group. Further, the monomer component constituting the (meth)acrylic polymer may contain acrylonitrile in order to sufficiently exhibit the effect as an adhesive.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and allyl alcohol. The monomer having a hydroxyl group may be one type or two or more types.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, maleic acid, and fumaric acid. , methylene succinic acid, and the like. The monomer having a carboxyl group may be one type or two or more types.

When the monomer component constituting the (meth)acrylic polymer contains a monomer having a hydroxyl group, the content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer is higher. It is preferably 0.1% by weight or more, more preferably 0.8% by weight or more, still more preferably 1% by weight or more. The upper limit of the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer is preferably 20% by weight or less, more preferably 10% by weight or less. The monomer component constituting the above (meth)acrylic polymer contains In the case of a monomer having a carboxyl group, the content of the monomer having a carboxyl group in the monomer component constituting the (meth)acrylic polymer is preferably 0.1% by weight or more, more preferably 0.8% by weight or more, and further More preferably, it is 1% by weight or more. The upper limit of the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer is preferably 20% by weight or less, more preferably 10% by weight or less. In this way, the monomer component constituting the (meth)acrylic polymer contains at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer, and when a crosslinking agent is used, the monomer component can be efficiently used. A crosslinking reaction with the crosslinking agent is generated to sufficiently exhibit the effect as an adhesive. Further, the content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer or the carboxyl group in the monomer component constituting the (meth)acrylic polymer is adjusted. The content ratio of the monomer is maintained within the above range, and the breakage of the adherend at the time of the peeling operation can be effectively prevented. The content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer or the content of the monomer having a carboxyl group in the monomer component constituting the (meth)acrylic polymer When the ratio exceeds the above range, the adhesion is too large, and it is liable to cause breakage of the adherend during the peeling operation.

The adhesive layer preferably contains a crosslinking agent. In the case where the adhesive layer contains a crosslinking agent, the content ratio of the crosslinking agent in the adhesive layer can be appropriately set depending on the purpose, but is preferably relative to the main resin component (preferably (meth)acrylic acid) The polymer) is from 0.1% by weight to 20% by weight, more preferably from 2% by weight to 10% by weight, still more preferably from 3% by weight to 7% by weight. By setting the content ratio of the crosslinking agent in the adhesive layer to the above range, a moderate crosslinking reaction can be produced, and the breakage of the adherend at the time of the peeling operation can be effectively prevented.

Examples of the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a metal alkoxide crosslinking agent, and a metal chelate crosslinking. A crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, An oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, and the like. Among these crosslinking agents, an epoxy crosslinking agent, an isocyanate crosslinking agent, and a melamine crosslinking agent are preferable in that the effect of the present invention is sufficiently exhibited. Further, the crosslinking agent may be appropriately selected as needed, and may be one type or a mixture of two or more types.

The adhesive layer may also contain a plasticizer. In the case where the adhesive layer contains a plasticizer, the content ratio of the plasticizer in the adhesive layer can be appropriately set according to the purpose, but is preferably 0.1% by weight or more, more preferably 10% by weight or more, and still more preferably It is 38% by weight or more. The upper limit of the content ratio of the plasticizer in the adhesive layer is preferably 50% by weight or less, more preferably 48% by weight or less, still more preferably 44% by weight or less. The effect of the present invention is further effectively exhibited by maintaining the content ratio of the plasticizer in the adhesive layer within the above range. If the content of the plasticizer in the adhesive layer is more than 50% by weight, the adhesive layer is too soft, and it is liable to cause residual glue or contamination of the adherend.

Examples of the plasticizer include a phthalic acid ester type, a trimellitic acid ester type (W-700 manufactured by Dainippon Ink Co., Ltd., trioctyl trimellitate, etc.), and Diacid ester system (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate, diisononyl adipate, etc.), phosphate ester (such as tricresyl phosphate), adipic acid ester , citrate (acetyl tributyl citrate, etc.), sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (ring Oxidized soybean oil, epoxidized linseed oil, etc.), polyester (low molecular weight polyester containing carboxylic acid and diol, etc.). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more.

The adhesive layer may contain any appropriate catalyst in order to promote a crosslinking reaction or the like. In the case where the adhesive layer contains a catalyst, the content ratio of the catalyst in the adhesive layer can be appropriately set depending on the purpose, but is preferably 0.01% by weight to 10% by weight. By setting the content ratio of the catalyst in the adhesive layer within the above range, the effects of the present invention can be more effectively exhibited. If the amount of the catalyst added is too small, the adhesive residue is likely to be generated when the adhesive tape is peeled off by the adhesive body. On the other hand, when the amount of the catalyst added is too large, the cohesive force of the adhesive itself is too strong, so that the adhesive is adhered to the adhesive body. The fit is degraded.

Examples of such a catalyst include tetraisopropyl titanate, tetra-n-butyl titanate, stannous octoate, lead octoate, cobalt octoate, zinc octoate, calcium octylate, lead naphthenate, and cobalt naphthenate. Organometallic compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate; butylamine, dibutylamine, hexylamine, third Basic compounds such as butylamine, ethylenediamine, isophorone diamine, imidazole, lithium hydroxide, potassium hydroxide, sodium methoxide; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphate, phosphoric acid An acidic compound such as an alkyl ester, a phosphate of β-hydroxyethyl acrylate, a monoalkyl phosphite or a dialkyl phosphite; an amine resin such as an aniline resin, a melamine resin or a urea resin. The catalyst may be one type or two or more types.

Any suitable additive may be contained in the adhesive layer insofar as it does not impair the effects of the present invention. Examples of such an additive include an ultraviolet absorber, a filler, an anti-aging agent, an adhesion-imparting agent, a pigment, a dye, a decane coupling agent, and the like.

"3. Alkyl double saturated fatty acid amide"

At least one of the substrate or the adhesive layer of the adhesive tape of the present invention may further comprise an alkylene di-saturated fatty acid guanamine. The alkylene di-saturated fatty acid decylamine 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 be either 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 a straight chain, a branched chain, a cyclic group, and any 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)

In the adhesive tape of the present invention, the adhesiveness of the adhesive tape to the surface of the adherend having irregularities and the heat resistance after heat treatment (resistance property) can be further improved by containing a specific alkyl bis-saturated fatty acid decylamine. , stripping). In particular, when the adhesive tape is used as a protective tape for use in an article coating operation, the adhesion between the back surface of the adhesive tape on the coated side and the coating film can be improved, and when the adhesive tape is peeled off, the coating film can be prevented from falling off. When the adhesive tape is peeled off after loading, the cracking of the strip can be suppressed. 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 a solvent here, it is suitable to use a saturated fat which can be used as a raw material. The acid amide but does not dissolve the solvent of the alkyl di-saturated fatty acid decylamine. 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 washing the obtained alkyl di-saturated fatty acid decylamine using a solvent may be mentioned. Soxhlet extraction method, etc. The conditions at this time are not particularly limited. For example, a solvent having a capacity of about 30 to 100 times the weight of the alkyl bis-saturated fatty acid decylamine or a weight is added, and immersion, penetration, washing, or extraction is performed 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 chloroform extraction, 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, and thereafter, separated by suction filtration. Insoluble part and soluble part. 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 ethanol extraction, for example, 40 ml of ethanol is added to about 1 g of a commercially available alkyl di-saturated fatty acid decylamine, and heated at 80 ° C (heated plate temperature) for 1 hour. Time. 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 preferably substantially free of fatty acid monoamines and/or fatty acids. In the case of a normal analysis device (liquid chromatography device, high-speed liquid chromatography device, etc.), when the fatty acid monoamine and/or fatty acid are contained in a single type, the measurement is not performed. Up to 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, when contained in plural kinds, The total content is 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 , below the detection limit.

That is, the alkylenedi-saturated fatty acid decylamine 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, for example, monodecyl laurate, Monodecylamine stearate, monodecylamine oleate, monodecylamine erucic acid, monodecylamine citrate, monodecyl palmitate, monodecylamine myristate, monodecyl behenate, and the like.

Further, the alkylenedi-saturated fatty acid decylamine used in the present invention preferably contains no 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 di-saturated fatty acid guanamine in the substrate is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and still more preferably 0.3% by weight. %the above. The upper limit of the content of the alkyl di-saturated fatty acid decylamine in the substrate is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 2% by weight or less.

Further, the content of the alkyl di-saturated fatty acid decylamine in the adhesive layer is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.3% by weight or more. The upper limit of the content of the alkyl di-saturated fatty acid decylamine in the adhesive layer is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 2% by weight or less.

When the alkylene di-saturated fatty acid decylamine is contained in the substrate and/or the adhesive layer, the content thereof is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and still more preferably 0.3% by weight or more. . The upper limit of the content is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 2% by weight or less.

By setting the content of the alkylene-saturated fatty acid decylamine to the above range, the adhesiveness of the adhesive tape to the surface of the adherend having irregularities and the heat resistance (residuality and releasability) after heat treatment can be improved. In particular, when the adhesive tape is used as a protective tape for use in an article coating operation, the adhesion between the back surface of the adhesive tape on the coated side and the coating film can be improved, and when the adhesive tape is peeled off, the coating film can be prevented from falling off. When the adhesive tape is peeled off after loading, the cracking of the strip can be suppressed.

"4. Non-adhesive layer"

The adhesive tape of the present invention may further comprise a non-adhesive layer (backside treatment) on the side of the substrate opposite to the side of the adhesive layer. The non-adhesive layer is a mixed layer of a polyfluorene oxide and a (meth)acrylic polymer. By using a mixed layer of polyoxymethylene and a (meth)acrylic polymer as a non-adhesive layer, the adhesion between the non-adhesive layer and the substrate is improved, so that the adhesive tape of the present invention can be prevented from being deformed by stretching or the like. The non-adhesive layer falls off.

The (meth)acrylic polymer in the non-adhesive layer has a calculated Tg of 10 ° C or more, preferably 20 ° C or more, more preferably 30 ° C or more, and still more preferably 45 ° C or more. The upper limit of the calculated Tg of the (meth)acrylic polymer in the non-adhesive layer is not particularly limited, but is preferably 200 ° C or lower, more preferably 150 ° C or lower, and still more preferably 100 ° C or lower. By making non The calculated Tg of the (meth)acrylic polymer in the adhesive layer is maintained within the above range, and the heat resistance of the non-adhesive layer can be improved.

The "calculated Tg" of the copolymer of the present invention (the (meth)acrylic polymer in the non-adhesive layer, etc.) means the Tg derived from the structural unit of the monomer constituting the copolymer, and the calculation formula by Fox And find the calculated glass transition temperature. The formula of Fox refers to the relationship between the glass transition temperature Tg (° C.) of the copolymer shown below and the glass transition temperature Tg _i (° C.) of the homopolymer obtained by separately polymerizing each of the monomers constituting the copolymer. . Further, in the following Fox formula, Tg (°C) represents the glass transition temperature of the copolymer, W _i represents the weight fraction of the monomer i, and Tg _i (° C) represents the glass transition temperature of the homopolymer of the monomer i. .

1/(273+Tg)=Σ(W _i /(273+Tg _i ))

Further, as the glass transition temperature Tg _i (°C) of the homopolymer, specifically, the values described in "Polymer Handbook 3rd Edition" (A WILEY-INTERSCIENCE PUBLICATION, 1989) can be used.

The arithmetic mean surface roughness Ra of the non-adhesive layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and still more preferably 0.5 μm or more. The upper limit of the arithmetic mean surface roughness Ra of the non-adhesive layer is preferably 3.0 μm or less, more preferably 2.0 μm or less.

Regarding the (meth)acrylic polymer in the non-adhesive layer, the SP value 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. ~11.5 (cal/cm ³ ) ^0.5 , further preferably 9.5 (cal/cm ³ ) ^0.5 to 11.0 (cal/cm ³ ) ^0.5 . The SP value is a solubility parameter calculated by the formula of Small. The calculation of the SP value can be carried out by a method described in a well-known literature (for example, Journal of Applied Chemistry, 3, 71, 1953., etc.).

The non-adhesive layer preferably has a phase separation structure. By providing the non-adhesive layer with a phase-separated structure, a minute uneven structure can be efficiently formed on the surface of the non-adhesive layer. It is presumed that the unevenness is generated by the difference in the mobility of the material of the polyoxymethylene or the (meth)acrylic polymer when the phase separation structure is formed.

The non-adhesive layer preferably comprises: a polyfluorene-rich polyphase containing more polyoxymethylene than the (meth)acrylic polymer, and more (meth)acrylic polymerization than polyfluorene. The (meth)acrylic polymer is enriched in the phase. More specifically, the non-adhesive layer is preferably contained in a phase-separated structure in which the polyfluorene-rich phase and the (meth)acryl-based polymer-rich phase are independent of each other, more preferably the above-mentioned polyfluorene-enriched The phase exists on the air interface side (opposite side of the substrate), and the above (meth)acrylic polymer-rich phase exists on the substrate side. By having such a phase separation structure, adhesion can be effectively suppressed by the polyfluorene-rich phase existing on the air interface side, and the (meth)acrylic polymer-rich phase existing on the substrate side can be obtained. The adaptability of the non-adhesive layer to the substrate is improved to make the deformation conformability good. Such a phase separation structure can be formed by adjusting the mixing ratio of the polyfluorene oxide 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, contains a polyfluorene-rich polyphase containing more polyoxymethylene than the (meth)acrylic polymer, and contains more than polyfluorene. The case of enriching the phase of the (meth)acrylic polymer of the poly(meth)acrylic polymer can be observed by any appropriate method. Examples of such an observation method include a transmission electron microscope (TEM), a scanning electron microscope (SEM), and an electron emission scanning electron microscope (FE-SEM). Electron microscope) A method of morphological observation of a non-adhesive layer profile by an electron microscope. The two-layer separation structure can be interpreted by observing the faintness of the morphological image. Further, a method of observing the change in the content of ruthenium and carbon contained in the composition by changing the depth of the probe light from the side of the non-adhesive layer air to the inside by using the infrared absorption spectrum of the total reflection method may be mentioned. Take this observation. Further, a method of observation by an X-ray microanalyzer or X-ray photoelectron spectroscopy may be cited. Further, these methods can be combined as appropriate to observe.

Mix ratio of polyoxymethylene to (meth)acrylic polymer in non-adhesive layer by weight ratio Preferably, it is a polyoxymethylene: (meth)acrylic polymer = 1:1 to 1:5, more preferably polyoxyn: (meth)acrylic polymer = 1:2 to 1:3. By setting the mixing ratio of the polyfluorene oxide and the (meth)acrylic polymer in the non-adhesive layer, the adhesion of the adhesive tape to the surface of the adherend having irregularities and the heat resistance after heat treatment can be further improved ( Residual, peeling). Further, when the adhesive tape is used as a protective tape for use in an article coating operation, the surface of the non-adhesive layer on the coated side is improved in suitability with the paint, and the adhesion between the surface of the non-adhesive layer and the paint can be improved, and peeling can be improved. When the tape is adhered, the coating film can be prevented from falling off, and the tape can be prevented from being broken when the adhesive tape is peeled off after coating. It is presumed that the (meth)acrylic polymer-rich polymer phase has a higher content of (meth)acrylic polymer than the poly(n-oxygen) (meth)acrylic polymer-rich phase, thereby improving the adhesion to the coating.

As the polyoxane, any suitable polyoxane can be used. Examples of such a polyfluorene oxide include addition-formed polyfluorene oxide which uses a platinum-based compound as a catalyst, and an alkenyl group-containing polydialkyloxirane and polydioxane by an addition reaction. The hydrogen hydride is cured to form a detachable film; the condensed polyoxyxene is a polydialkyl oxirane containing a hydroxymethyl group and a polydialkyl hydrogen condensed by a tin-based catalyst. The oxirane is reacted to obtain an equivalent. Examples of the addition polyoxyl oxide include "KS-776A" and "KS-839L" manufactured by Shin-Etsu Silicones. Examples of the condensed polyfluorene oxide include "KS723A/B" manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Further, in the production of polyfluorene oxide, other crosslinking agents, crosslinking accelerators, and the like may be suitably used in addition to the platinum-based catalyst or the tin-based catalyst. Further, the properties of polyfluorene oxide can be classified into a type in which an organic solvent such as toluene is dissolved, a milky type obtained by emulsifying them, and the like, and a solvent-free type containing only polyfluorene oxide. Further, in addition to the addition of polyfluorene oxide and condensed polyfluorene oxide, a polyfluorene/acrylic graft polymer, a polyoxyn/acrylic block polymer or the like can be used. Examples of the polyoxymethylene/acrylic acid graft polymer include Symac GS-30, GS101, US-270, US-350, and US-380 (the above is manufactured by Toagosei Co., Ltd.). Examples of the polyoxyn/acrylic block polymer include MODIPER FS700 and FS710. FS720, FS730, FS770 (above is manufactured by Nippon Oil Co., Ltd.).

As the (meth)acrylic polymer, any suitable (meth)acrylic polymer can be used as long as the Tg is 10 ° C or more. In the present invention, "(meth)acrylic" means "acrylic acid and/or methacrylic acid".

The (meth)acrylic polymer is a polymer containing a monomer component containing a (meth)acrylic monomer as a main monomer. The content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight. More preferably, it is 95% by weight or more. The upper limit of the content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 100% by weight or less, and more preferably 97% by weight or less. The monomer in the above monomer component may be one type or two or more types.

The (meth)acrylic monomer is preferably (meth)acrylate or (meth)acrylic acid.

Examples of the (meth) acrylate include an alkyl (meth)acrylate having a carbon number of 1 to 30 (including a cycloalkyl group), a (meth)acrylate containing a hydroxyl group, and the like. The (meth) acrylate may be used alone or in combination of two or more.

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)acrylate, ethyl (meth)acrylate, and (methyl). ) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate , amyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (methyl) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, ( Pentadecyl (meth)acrylate, octadecyl (meth)acrylate a group of alkyl esters having a carbon number of from 1 to 30 (including a cycloalkyl group) such as a group of esters, a 19-alkyl (meth)acrylate, an amyl (meth)acrylate or a lauryl (meth)acrylate. Alkyl (meth)acrylate or the like. Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of an alkyl group (also containing a cycloalkyl group).

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

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

Examples of the carboxyl group-containing monomer include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, maleic acid, fumaric acid, and methylene butadiene. Acid, etc. The monomer having a carboxyl group may be one type or two or more types.

When the (meth)acrylic polymer in the non-adhesive layer contains a monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer, the single (meth)acrylic polymer is formed. The content ratio of the hydroxyl group-containing monomer in the body component is preferably 2% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more. The upper limit of the content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less. . By maintaining the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer in the non-adhesive layer in the above range, minute irregularities can be formed more effectively on the surface of the non-adhesive layer. structure.

The (meth)acrylic polymer in the non-adhesive layer preferably contains (meth)acrylic acid and/or (methyl) in a monomer component other than the monomer having a hydroxyl group in the monomer component constituting the monomer. )Acrylate. In this case, the content ratio of (meth)acrylic acid to (meth)acrylic acid ester is preferably a weight ratio of (meth)acrylic acid:(meth)acrylic acid ester. 0:100~20:80, more preferably 0:100~10:90, and further preferably 0:100~5:95.

When the content ratio of (meth)acrylic acid and (meth)acrylic acid ester is set within the above range, a minute uneven structure is more effectively formed on the surface of the non-adhesive layer.

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

In the non-adhesive layer, any suitable additive may be included in the range which does not impair the effects of the present invention. Examples of such an additive include a catalyst, an ultraviolet absorber, a filler, an anti-aging agent, an adhesion-imparting agent, a pigment, a dye, and a decane coupling agent.

The thickness of the non-adhesive layer is preferably 0.01 μm or more, and more preferably 0.1 μm or more. The upper limit of the thickness of the non-adhesive layer is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 2 μm or less. By setting it within the above range, the adhesive tape of the present invention can prevent the non-adhesive layer from falling off due to deformation such as stretching.

As a method of forming a non-adhesive layer on one surface of a substrate, for example, a method in which a non-adhesive layer is formed by applying a material of a non-adhesive layer on one side of a substrate and drying it is exemplified. Examples of the coating method include a bar coater, a gravure coater, a spin coater, a roll coater, a knife coater, and an applicator.

"5. Stripping liner"

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

As the release liner, any suitable separator can be used. Examples of the release liner include a substrate having a release layer such as a substrate treated with a release agent such as a polyfluorene-based, a long-chain alkyl group, a fluorine-based or a molybdenum sulfide, and a release layer such as paper; Low-adhesion groups of fluorine-based polymers such as tetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer A low-adhesive substrate containing a nonpolar polymer such as an olefin resin (for example, polyethylene or polypropylene).

Example

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not Limited to these embodiments. "Parts" means parts by weight. Moreover, the amount of the reagent supplied in the solution is represented by the amount of the solid content (the amount of solid content converted) remaining to volatilize the solution.

[Evaluation items and measurement methods and conditions] <adhesion>

(adhesion before heating)

The pre-heating adhesion was measured using JIS-Z-0237 (2000) as a criterion. Specifically, the SUS430BA plate was used as an adherend, and the surface of the SUS430BA plate was washed with toluene, and the sample for evaluation was pressed back and forth with a 2 kg roller. After 30 minutes, the Instron tensile tester (Shimadzu Corporation) was used. Manufactured, autostereographer) The adhesion of 180° peeling when the tensile speed was 300 mm/min. At this time, the measurement environment was carried out under the conditions of a temperature of 23 ° C / a humidity of 50%.

(adhesion rate after heating at 135 °C)

The adhesion after heating was measured using JIS-Z-0237 (2000) as a criterion. Specifically, the surface of the SUS430BA plate was washed with toluene using a SUS430BA plate as an adherend, and then the sample for evaluation was pressed back and forth with a 2 kg roller, and after 30 minutes, it was allowed to stand at 135 ° C for 25 minutes. Then, after the evaluation sample was returned to 23 ° C, the adhesion force at 180° peeling when the tensile speed was 300 mm/min was measured by an Instron tensile tester (manufactured by Shimadzu Corporation). At this time, the measurement environment was carried out under the conditions of a temperature of 23 ° C / a humidity of 50%.

<50% modulus>

The sample for evaluation was cut into a width of 20 mm × a length of 150 mm, and "Autograph ASG-50D type" (manufactured by Shimadzu Corporation) was used as an Instron tensile tester at a tensile speed of 300 mm/min, a distance between chucks of 50 mm, and a temperature of 23 A tensile test was carried out under the conditions of ° C / humidity of 50%, and a stress-strain curve was obtained. The average stress per unit area at 50% elongation of the adhesive sheet was taken as a 50% modulus at 23 °C.

<elongation rate>

The elongation was measured in accordance with JIS-K-7127 (1999) by an Instron tensile tester (manufactured by Shimadzu Corporation, an autostereograph). Specifically, a rectangular sample (1) having a width of 19 mm (first direction) × a length of 150 mm (second direction) and a rectangular sample having a width of 19 mm and a length of 150 mm perpendicular to the second direction are respectively cut out from the sample for evaluation (2). ), and use them as measurement samples. For example, the traveling direction of the sample (MD, typically the longitudinal direction of the sample) can be set to the second direction, and the direction perpendicular thereto can be set to the first direction. The sample (1) and (2) were placed at a distance of 50 mm between the chucks, and then stretched at a tensile speed of 300 mm/min to read the value at the time of fracture. Among the values at the time of rupture of each sample, the larger value is used as the elongation of the present invention, and if the values are the same, the value is taken as the elongation of the present invention. At this time, the temperature was 23 ° C / humidity 50% as the measurement environment and the storage environment.

Further, the elongation after coating and heating was carried out by attaching a sample having a width of 19 mm to a length of 150 mm to a SUS430BA plate, spraying an acrylic paint, and drying at 135 ° C for 25 minutes. Thereafter, the sample was taken out from the SUS plate, and the elongation was measured in the same manner as above.

<Adhesive test of adhesive tape>

A rectangular sample having a width of 20 mm and a length of 150 mm was cut out from the sample for evaluation, and this was used as a measurement sample. The above sample was attached to a SUS430BA plate, sprayed with an acrylic paint, and dried at 135 ° C for 25 minutes. Thereafter, the sample was allowed to stand at 5 ° C for 30 minutes, and then the sample was peeled off at a stretching speed of 3 m/min and a peeling angle of 180 degrees in an environment of 5 ° C to carry out a crack test of the adhesive tape. The above test was carried out using 10 samples according to the following evaluation criteria.

When all the samples were peeled off without cracking, it was ○, and if there was one crack, it was judged as ×.

<矽 content>

The cerium content was measured by X-ray fluorescence analysis (XRF) according to the following measurement conditions.

X-ray fluorescence analyzer: "Supermini" manufactured by Rigaku

X-ray source: vertical Rh tube

Analysis range: within a circle of 30mm diameter

Spectroscopic crystallization: Si-Kα

Output: 50kV, 70mA

<Floating after heating>

A rectangular sample having a width of 20 mm and a length of 150 mm was cut out from the sample for evaluation, and this was used as a measurement sample. It is prepared to provide a bump having a height of 250 μm and a width of 5 mm at an interval of 5 mm by an adherend, and attach the sample to the concave portion in an environment of 23 ° C. The area of the close portion of the sample and the concave portion was measured as an initial state. Thereafter, the acrylic coating was sprayed and dried at 135 ° C for 25 minutes. After the sample was returned to 23 ° C, the float after heating was evaluated. The above test was carried out by measuring the area of the adhesion portion between the sample and the concave portion. When the area was unchanged from the initial state, it was judged as ○, and when the area was decreased, it was judged as ×.

<Residual glue after heating>

Using a SUS430BA plate as an adherend, the surface of the SUS430BA plate was washed with toluene, and then a 2 kg roller was pressed back and forth with a sample having a width of 25 mm and a length of 150 mm, and after 30 minutes, it was allowed to stand at 135 ° C for 30 minutes. Then, the sample to be evaluated was returned to 23 ° C, and the sample for evaluation was peeled off under the conditions of a tensile speed of 300 mm/min and 180° peeling using an Instron tensile tester (manufactured by Shimadzu Corporation, autostereograph). Then, the surface of the adherend SUS430BA plate was visually observed, and the case where the adhesive residue or only the slight residue (identified as a dot shape) was not confirmed was ○, and the case where the adhesive residue was confirmed was ×.

[Manufacturing Example 1]

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 film (1) having a thickness of 70 μm was obtained by a calender film forming machine using a polyvinyl chloride mixture obtained by kneading it with a Banbury mixer.

The alkylene difatty acid decylamine shown in the table below was used as a lubricant. The lubricant is added during the mixing of the Banbury mixer.

100 parts by weight of polyvinyl chloride having a polymerization degree of P=1050

Bis(2-ethylhexyl) phthalate, manufactured by J-PLUS 30 parts by weight

Stabilizer: Ba-Zn mixed stabilizer 3 parts by weight

Lubricant: N, N'-methylenebisstearylamine, BISAMIDE LA (Japan Chemical Industry Co., Ltd.) 0.6 parts by weight

[Manufacturing Example 2]

100 parts by weight of a polyvinyl chloride containing a DOP plasticizer (bis(2-ethylhexyl) phthalate, manufactured by J-PLUS) was produced by calendering in an amount of 27 parts by weight of polyvinyl chloride having a degree of polymerization of P = 0,050. Membrane (2). The thickness of the polyvinyl chloride film was 70 μm.

[Example 1]

Toluene solution containing an adhesive of the following composition: 100 parts by weight of an acrylic copolymer composed of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 85 / 15 / 2.5 (weight ratio), plastic Chemical agent (bis(2-ethylhexyl) phthalate, manufactured by J-PLUS) 80 parts by weight, cross-linking agent (trimethylolpropane/diisocyanate toluene 3-mer adduct, CORONATEL, 2 parts by weight of a crosslinking agent (butylated melamine resin, Super Beckamine J-820-60N, manufactured by DIC Corporation) in an amount of 3 parts by weight.

This adhesive solution was applied to one side of the polyvinyl chloride film (1) produced in Production Example 1, and then dried at 130 ° C for 90 seconds to form an adhesive layer having a thickness of 13 μm to obtain an adhesive tape.

[Embodiment 2]

The following components were mixed in a solution state to obtain a mixed solution (1): 25 parts by weight of polyoxynoxy resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), and 15 parts by weight of polyoxyxylene resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.). Acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 90 / 10/10) 85 parts by weight, and tin-based catalyst (Cat-PS3, Shin-Etsu Manufactured by the chemical industry) 12 parts by weight. The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (1) is polyoxyl Acrylic polymer = 1:2.5.

The mixed solution (1) was applied to one side of the polyvinyl chloride film (2) produced in Production Example 2 to form a non-adhesive layer having a thickness of 1.0 μm to obtain a substrate film.

The same adhesive solution as in Example 1 was applied to the surface of the base film opposite to the non-adhesive layer, and then dried at 130 ° C for 90 seconds on the opposite side of the base film from the non-adhesive layer. An adhesive layer having a thickness of 13 μm was formed to obtain an adhesive tape.

[Comparative Example 1]

The following components were mixed in a solution state to obtain a mixed solution (2): 60 parts by weight of polyoxyxylene resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), and 40 parts by weight of polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.). Acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 90 / 10/10) 50 parts by weight, and tin-based catalyst (Cat-PS3, Shin-Etsu Manufactured by the chemical industry) 10 parts by weight. The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (2) is a polyoxymethylene: (meth)acrylic polymer = 2:1 by weight.

The mixed solution (2) was applied to one side of the polyvinyl chloride film (2) produced in Production Example 2 to form a non-adhesive layer having a thickness of 1.0 μm to obtain a substrate film.

Toluene solution containing an adhesive of the following composition: 100 parts by weight of an acrylic copolymer composed of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 85 / 15 / 2.5 (weight ratio), Co-agent (butylated melamine resin, Super Beckamine J-820-60N, manufactured by DIC Corporation) 10 parts by weight, DOP plasticizer (bis(2-ethylhexyl) phthalate, manufactured by J-PLUS) 60 Parts by weight.

The adhesive solution was applied to the surface of the base film opposite to the non-adhesive layer, and dried at 130 ° C for 90 seconds to form a thickness of 13 μm on the surface of the base film opposite to the non-adhesive layer. Adhesive layer to obtain an adhesive tape.

The various evaluation results are shown in Table 1.

Industrial availability

The adhesive tape of the present invention can be used for any suitable purpose. As described above, even if the surface of the adherend has irregularities, the adhesive tape of the present invention can sufficiently satisfy the requirements of adhesion (concavity and conformability) before and after heating, and has good processability after heating, and is not easily broken or discolored. The situation of glue.

The adhesive tape of the present invention can be suitably used as a protective film in a coating operation, and has good adhesion (convex conformability), and can be sufficiently adhered even if the adhesive body has a complicated shape, and the paint does not penetrate into the protective portion. It has good heat resistance, and it can also play a protective function in the harsh environment of high-temperature drying in the coating process. It is not easy to crack, and it can effectively inhibit the generation of residual glue, and maintain good peelability. The attached coating will not be scattered and cause contamination, so it is very suitable for application with complex structure and multi-layer coating A loaded item, such as a bicycle frame, a motor vehicle body, a hard hat, or other painting process with irregular or complicated shapes.

Claims (9)

An adhesive tape attached to an adhesive layer on one side of a substrate, and an adhesive ratio measured according to JIS-Z-0237 (2000) before and after heating at 135 ° C for 25 minutes (after heating/heating) ) is 10 or less. The adhesive tape of claim 1, wherein at least one of the above-mentioned substrate or adhesive contains an alkylene di-saturated fatty acid decylamine. The adhesive tape of claim 1, which further comprises a non-adhesive layer, wherein the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is polyoxylium by weight: (meth)acrylic polymerization Matter = 1:1~1:5. The adhesive tape according to any one of claims 1 to 3, wherein the resin material in the substrate comprises polyvinyl chloride. The adhesive tape according to any one of claims 1 to 3, wherein the adhesive layer contains an acrylic polymer. The adhesive tape according to any one of claims 1 to 3, wherein the content of the plasticizer in the adhesive is 38% by weight or more. The adhesive tape according to any one of claims 1 to 3, wherein the substrate has a thickness of 20 to 200 μm. The adhesive tape of any one of claims 1 to 3, wherein the thickness of the adhesive layer is 5 to 30 μm. An adhesive tape according to any one of claims 1 to 3, which is used for a protective tape having an uneven adherend.