JP2008045000A - Adhesive tape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive tape which is excellent in an end peeling-preventing property and can exhibit a proper rewinding force. <P>SOLUTION: This adhesive tape having a construction produced by forming an adhesive layer on at least one side of a substrate, wherein the substrate is formed from an olefinic resin composition comprising a polyolefin-based resin and a metal hydroxide, and the adhesive layer is formed from an emulsion type acrylic adhesive composition comprising an acrylic emulsion having an average emulsion particle diameter of ≤0.2 μm. The emulsion type acrylic adhesive composition preferably comprises 100 pts.wt. of (A) an emulsion type acrylic polymer, 1 to 50 pts.wt. of (B) a petroleum resin, and 1 to 50 pts.wt. of (C) of a rosin-based resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive tape, and more particularly, to a pressure-sensitive adhesive tape that is excellent in pressure-sensitive adhesiveness and terminal peeling prevention and can exhibit an appropriate rewinding force even when the substrate is a polyolefin-based substrate. .

  Conventionally, as an adhesive tape (bundling adhesive tape) used when bundling various electric wires and cables, etc., from the viewpoint of workability and flame retardancy, it is called vinyl chloride resin ("PVC"). Adhesive tapes based on the base material have been widely used. However, since adhesive tapes using PVC generate toxic gases when incinerated, in recent years, adhesive tapes based on plastics that do not contain halogen atoms such as chlorine ("non-halogen adhesive tape") In particular, pressure-sensitive adhesive tapes based on a polyolefin resin composition mainly composed of a polyolefin resin have begun to be used.

  However, it has been very difficult to give the polyolefin resin composition a balance between strength suitable for binding applications, flexibility, and stress relaxation as in the case of PVC. Therefore, various studies have been made on, for example, the balance between the strength and flexibility of the polyolefin resin composition so that it can be suitably used as a base material in a pressure-sensitive adhesive tape for bundling (Patent Documents 1 to 3). (See Patent Document 2)

  On the other hand, non-halogen adhesive tapes that ensure tackiness and adhesiveness have been proposed (see Patent Documents 3 to 4).

  Moreover, the water-dispersed adhesive composition containing the acryl-type polymer in which the silane monomer was used as a monomer component is also proposed (refer patent document 5-patent document 6).

JP 2001-192629 A JP 2001-311061 A JP 2001-131509 A JP 2001-164215 A JP 2001-131511 A JP 2003-176469 A

  However, the stress relaxation property has not yet been sufficiently solved, and therefore, in the adhesive tape based on the polyolefin resin composition, the reliability problem that the terminal peels off after binding, The rewinding force of the adhesive tape is too heavy, and the adhesive is taken on the back side, or conversely, the unwinding force of the adhesive tape is too light and cannot be firmly bound. Workability issues remain.

  In addition, non-halogen adhesive tapes that ensure tackiness and adhesiveness as described above are still sufficient in terms of terminal peeling prevention and workability (rewinding properties) to prevent peeling from the terminal after binding. I can't say that.

  It has been proposed that rewinding properties that affect workability can be solved by adding a plasticizer to the pressure-sensitive adhesive.

  As for terminal peeling prevention, generally, a method of improving tackiness and tackiness by adding a plasticizer to the base polymer, transferring it from the base material, or adding a tackifier is known. It has been. However, there is no disclosure or suggestion about the effect of a specific combination of these plasticizers and tackifiers.

  Therefore, in order to solve the problems relating to terminal peeling prevention and workability at the time of rewinding, the present inventors have adopted a pressure-sensitive adhesive tape based on a polyolefin-based substrate using a polyolefin-based resin composition. A rosin ester-based tackifier is added to the adhesive to improve the terminal peeling prevention, and an adhesive composition in which the unwinding force is controlled to an appropriate size by the effect of the plasticizer and petroleum resin has been provided. It was.

  However, a pressure-sensitive adhesive tape that further improves the adhesiveness and terminal peeling prevention and has an appropriate rewinding force is desired.

  In particular, in a system using a cross-linking agent, the dispersion state of the cross-linking agent in the pressure-sensitive adhesive composition is not good (uniform or almost non-uniform), and the drying conditions for forming the pressure-sensitive adhesive layer fluctuate. If the tape is scattered (constant or almost non-constant), problems such as excessive rewinding force when rewinding the adhesive tape or excessive sound during rewinding occur. There was a case.

  Furthermore, when a plastic film used as a base material contains a polyvalent metal salt such as a metal hydroxide used as a flame retardant, a phenomenon in which the adhesive strength is significantly reduced over time is observed. There is. In addition, it has been found that this phenomenon facilitates peeling of the terminal and hinders practicality. Thus, when a polyvalent metal salt is contained in the substrate, this polyvalent metal salt undergoes a crosslinking reaction with a reactive functional group (mainly a carboxyl group) in the base polymer of the pressure-sensitive adhesive. It is thought that the pressure-sensitive adhesive is cured and leads to a decrease in the adhesive strength. However, in some cases, the emulsifier is deposited on the surface of the pressure-sensitive adhesive layer, and thus the pressure-sensitive adhesive force is further decreased.

Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive tape that is excellent in adhesiveness and terminal peeling prevention property and can exhibit an appropriate rewinding force even when the substrate is a polyolefin-based substrate. .
Another object of the present invention is to provide an adhesive tape useful as a binding adhesive tape.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have determined that the pressure-sensitive adhesive layer in the pressure-sensitive adhesive tape based on polyolefin resin contains acrylic particles containing emulsion particles having a specific average particle diameter. When formed with a pressure-sensitive adhesive composition containing an emulsion, even if the base material is a polyolefin base material, it is possible to obtain a pressure-sensitive adhesive tape that has excellent adhesiveness and terminal peeling prevention and can be rewound with an appropriate rewinding force. I found out that I can. The present invention has been completed based on these findings.

  That is, the present invention is an adhesive tape or sheet having a configuration in which an adhesive layer is formed on at least one surface of a base material, and the base material contains an polyolefin resin and a metal hydroxide. It is formed of a resin composition, and the pressure-sensitive adhesive layer is formed of an emulsion-type acrylic pressure-sensitive adhesive composition containing an acrylic emulsion having an average particle diameter of emulsion particles of 0.2 μm or less. It is an adhesive tape.

The emulsion-type acrylic pressure-sensitive adhesive composition includes the following components (A), (B) and (C): (A) component: 100 parts by weight, and (B) component 1 to 50 parts by weight Part and component (C) are preferably contained in a proportion of 1 to 50 parts by weight.
(A): Emulsion type acrylic polymer (B): Petroleum resin (C): Rosin resin

  In such an emulsion-type acrylic pressure-sensitive adhesive composition, the emulsion-type acrylic polymer (A) includes (meth) acrylic acid ester, an ethylenically unsaturated monomer having a hydrolyzable silicon atom-containing group, An acrylic polymer obtained by copolymerization of a monomer mixture containing at least is preferable. The emulsion type acrylic polymer (A) is obtained by emulsion polymerization of monomer components in the presence of a reactive emulsifier having a group capable of copolymerization with (meth) acrylic acid ester. The emulsion type acrylic polymer that can be used can be suitably used.

  In the present invention, the total amount of the component (B) and the component (C) is preferably 10 to 60 parts by weight with respect to the component (A): 100 parts by weight.

  In this specification, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and “(meth)” is used in this sense. .

  According to the pressure-sensitive adhesive tape of the present invention, since it has the above-described configuration, even if the base material is a polyolefin base material, it is excellent in adhesiveness and terminal peeling prevention and exhibits an appropriate rewinding force. Can do. Therefore, the adhesive tape of the present invention is useful as a binding adhesive tape. Moreover, since the base material is a polyolefin-type base material, the adhesive tape also has a feature that it is possible to prevent generation of toxic gas during incineration.

[Adhesive layer]
The pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer formed of an emulsion-type acrylic pressure-sensitive adhesive composition containing an acrylic emulsion having an average particle size of emulsion particles of 0.2 μm or less. Thus, since the acrylic emulsion in the emulsion type acrylic pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer has an average particle size of the emulsion particles of 0.2 μm or less, the polymer component in the emulsion particles The molecular weight (particularly the weight average molecular weight) is large (therefore, the proportion of low molecular weight components is small), and an excellent cohesive force can be exhibited. This is because the smaller the particle system of emulsion particles, the greater the number of particles in the emulsion, thereby reducing the amount of polymerization initiator incorporated into one emulsion particle, resulting in a polymer in the emulsion particle. This is because the molecular weight (particularly the weight average molecular weight) of the component is increased. Moreover, since the average particle diameter of the emulsion particles is extremely small, the surface of the pressure-sensitive adhesive layer has a smooth surface with little unevenness, and it is possible to ensure an effective contact area (adhesion area). . Therefore, even if the base material is an olefin base material, the pressure-sensitive adhesive tape of the present invention can exhibit excellent adhesiveness and terminal peeling prevention properties and can exhibit an appropriate rewinding force.

  In the emulsion type acrylic pressure-sensitive adhesive composition, the average particle diameter of the emulsion particles is not particularly limited as long as it is 0.2 μm or less, but is preferably 0.01 to 0.18 μm (more preferably 0.08 to 0.00). 15 μm). The average particle diameter of the emulsion particles in the emulsion-type acrylic pressure-sensitive adhesive composition is measured using a laser scattering diffraction particle size distribution analyzer “LS 13 320” manufactured by BECKMAN COULTER (Beckman Coulter, Inc.). Value.

  Such an emulsion-type acrylic pressure-sensitive adhesive composition is not particularly limited as long as it contains an acrylic emulsion having an average particle size of 0.2 μm or less, and the emulsion-type acrylic polymer (A) and petroleum resin (B) and the rosin resin (C) at least, and the ratio of the petroleum resin (B) is 1 to 50 parts by weight with respect to 100 parts by weight of the emulsion type acrylic polymer (A). In addition, it is preferable that the ratio of the rosin resin (C) is 1 to 50 parts by weight with respect to 100 parts by weight of the emulsion type acrylic polymer (A). Of course, the emulsion type acrylic polymer (A) needs to be an acrylic polymer in an acrylic emulsion in which the average particle diameter of the emulsion particles is 0.2 μm or less.

  Thus, when the petroleum resin (B) and the rosin resin (C) are used in an appropriate ratio with respect to the emulsion type acrylic polymer (A) as the base polymer of the pressure-sensitive adhesive, Excellent adhesiveness and terminal peeling prevention properties can be exhibited, and an appropriate unwinding force can be expressed. Specifically, by containing the rosin-based resin (C) in an appropriate ratio, when the adhesive tape is used (for example, when bound), the terminal peeling preventing property (this is prevented) The terminal peeling prevention property can be greatly improved as a practically important characteristic as an adhesive tape for binding. Moreover, by using petroleum resin (B) in an appropriate ratio, the rewinding property when rewinding the pressure-sensitive adhesive tape is greatly improved with little or no reduction in terminal peeling prevention property, and an appropriate rewinding force is achieved. Can be expressed.

[Emulsion type acrylic polymer (A)]
As the acrylic polymer (sometimes referred to as “acrylic polymer (A)”) in the emulsion type acrylic polymer (A), (meth) acrylic acid ester (acrylic acid ester, methacrylic acid ester) is the main monomer. A (meth) acrylic acid ester polymer used as a component (monomer main component) can be used. Examples of such (meth) acrylic acid esters include (meth) acrylic acid alkyl esters shown below, (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid cyclohexyl, and (meth) acrylic acid phenyl compounds. And (meth) acrylic acid aryl esters.

  As the acrylic polymer (A), in particular, a (meth) acrylic acid alkyl ester polymer mainly composed of a (meth) acrylic acid alkyl ester can be suitably used. The (meth) acrylic acid alkyl ester polymer may be a polymer (homopolymer) of only one kind of (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl ester, and (meth) acrylic. Copolymerization with other (meth) acrylic acid esters such as acid cycloalkyl esters and (meth) acrylic acid aryl esters, and monomers that can be copolymerized with (meth) acrylic acid alkyl esters (copolymerizable monomers) It may be a coalescence. That is, in the (meth) acrylic acid alkyl ester-based polymer, monomer components (monomer components) such as (meth) acrylic acid alkyl ester may be used alone or in combination of two or more. It may be.

Examples of the (meth) acrylic acid alkyl ester in the acrylic polymer (A) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate, ( T) Decyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, (meta ) (Meth) acrylic acid C _1-20 alkyl ester such as eicosyl acrylate [preferably (meth) acrylic acid C _2-14 alkyl ester, more preferably (meth) acrylic acid C _2-10 alkyl ester] and the like. It is done. As the (meth) acrylic acid alkyl ester, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly suitable.

  The (meth) acrylic acid ester is used as a monomer main component, and the ratio of (meth) acrylic acid ester [particularly, (meth) acrylic acid alkyl ester] is 50 with respect to the total amount of monomer components. It is important that the amount is not less than wt%, preferably not less than 80 wt%, more preferably not less than 90 wt%. When the proportion of the (meth) acrylic acid ester is less than 50% by weight with respect to the total amount of the monomer components, the adhesiveness and cohesiveness (or adhesive strength and cohesive strength) of the pressure-sensitive adhesive composition are lowered.

  Examples of the copolymerizable monomer that can be copolymerized with the (meth) acrylic acid alkyl ester in the acrylic polymer (A) include (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid. , Fumaric acid, crotonic acid and other carboxyl group-containing monomers; maleic anhydride, itaconic anhydride and other acid anhydride group-containing monomers; acrylonitrile, methacrylonitrile and other cyanoacrylate monomers; (meth) (Meth) acrylic acid aminoalkyl monomers such as aminoethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; (meth) acrylamide, N, N -Dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxy (meth) a (N-substituted) amide monomers such as rilamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide; vinyl ester monomers such as vinyl acetate and vinyl propionate; styrene , Styrene monomers such as α-methylstyrene and vinyltoluene; hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Monomer; Epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate; (meth) acrylic acid alkoxyalkyl monomer such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; Acrylic acid lactone monomers such as acrylic acid ε-caprolactone; Olefin monomers such as ethylene, propylene, isoprene and butadiene; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; morpholine (meth) acrylate; N-vinyl-2-pyrrolidone, N-vinyl pyridine, N- And heterocyclic ring-containing vinyl monomers such as vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole and N-vinyloxazole.

  In the acrylic polymer (A), as copolymerizable monomers, hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene Polyfunctional monomers such as butyl di (meth) acrylate and hexyl di (meth) acrylate can also be used.

  As such a copolymerizable monomer, a functional group-containing monomer can be suitably used. Among them, an acidic functional group-containing monomer [particularly, a carboxyl group-containing monomer such as (meth) acrylic acid] Can be suitably used. A copolymerizable monomer can be used individually or in combination of 2 or more types.

  In addition, since functional group containing monomers, such as an acidic functional group containing monomer, have the effect of improving cohesive force and adhesive force, it is important to use according to the objective. However, excessive addition hardens the pressure-sensitive adhesive and greatly affects the adhesive properties. Therefore, the amount of the functional group-containing monomer used is (meth) as the main monomer component of the acrylic polymer (A). Acrylic acid ester [particularly (meth) acrylic acid alkyl ester]: preferably 30 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less with respect to 100 parts by weight. Is preferred.

  In the present invention, an acrylic polymer (A) having a functional group-containing monomer as a monomer component is applied to a polyolefin-based substrate containing a polyvalent metal salt (for example, magnesium hydroxide, aluminum hydroxide, etc.). In some cases, the ionized metal salt and the functional group in the acrylic polymer (A) may react with each other to promote the crosslinking of the pressure-sensitive adhesive, so care must be taken. Therefore, although depending on the type of the substrate, when a polyolefin-based substrate containing a polyvalent metal salt is used as the support, the amount of the functional group-containing monomer added is simply the acrylic polymer (A). (Meth) acrylic acid ester as a main component of the monomer [particularly, (meth) acrylic acid alkyl ester]: preferably 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight, In particular, the amount is preferably 1.5 parts by weight or less.

  In the present invention, the acrylic polymer (A) is an ethylenically unsaturated monomer having a hydrolyzable silicon atom-containing group as a copolymerizable monomer (sometimes referred to as “silane monomer”). May be used. That is, the acrylic polymer (A) may have a structural unit of a silane monomer as a monomer component. Such an acrylic polymer (A) has at least one hydrolyzable silicon atom-containing group in the molecule. Thus, by using a silane monomer, it is possible to easily and stably prepare an acrylic polymer having hydrolyzable silicon atom-containing groups introduced uniformly or almost uniformly in the molecule. Therefore, by using a silane monomer as the copolymerizable monomer, the hydrolyzability introduced into the acrylic polymer (A) can be obtained without adding a crosslinking agent when forming the pressure-sensitive adhesive layer. It can be cross-linked by the condensation reaction of silicon atom-containing groups, is not affected by the dispersibility of the cross-linking agent, and is hardly affected by variations in drying conditions during drying. It can be produced with productivity.

  In such a silane monomer, examples of the hydrolyzable silicon atom-containing group include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a triisopropoxysilyl group, a tributoxysilyl group, and a triisopropylene group. Trialkoxysilyl groups such as butoxysilyl group; dimethoxymethylsilyl group, dimethoxyethylsilyl group, dimethoxypropylsilyl group, dimethoxyisopropylsilyl group, dimethoxybutylsilyl group, diethoxymethylsilyl group, diethoxyethylsilyl group, diethoxypropyl Dialkoxyalkylsilyl groups such as silyl group, diethoxyisopropylsilyl group, diethoxybutylsilyl group; methoxydimethylsilyl group, methoxydiethylsilyl group, methoxydipropylsilyl group, methoxydiisopropylsilyl group, A silyl group having 1 to 3 alkoxy groups such as an alkoxydialkylsilyl group such as a toxidibutylsilyl group, an ethoxydimethylsilyl group, an ethoxydiethylsilyl group, an ethoxydipropylsilyl group, an ethoxydiisopropylsilyl group, and an ethoxydibutylsilyl group Can be mentioned.

  In addition, when the silyl group having an alkoxy group has a plurality (two or three) of alkoxy groups, the plurality of alkoxy groups may all be the same or partially the same. Well, all may be different. Moreover, when the silyl group which has an alkoxy group has two other groups (for example, alkyl group etc.) other than an alkoxy group, the other groups may be the same or different.

  In the present invention, as the silane monomer, from the viewpoint of excellent copolymerizability for (meth) acrylic acid ester [especially, (meth) acrylic acid alkyl ester], (meth) acryloyloxyalkylsilane derivatives, Silane compounds containing an ethylenically unsaturated bond site and containing a hydrolyzable silicon atom-containing group, such as vinyl silane derivatives and vinyl alkyl silane derivatives, can be preferably used.

  Examples of the (meth) acryloyloxyalkylsilane derivative include a silyl group having 1 to 3 alkoxy groups and a (meth) acryloyloxy group (acryloyloxy group, methacryloyloxy group) via an alkylene group. Examples thereof include silane-based compounds bonded to each other. Specifically, for example, (meth) acryloyloxyalkyl-trialkoxysilane, (meth) acryloyloxyalkyl-dialkoxy-alkylsilane, (meth) acryloyloxyalkyl- And alkoxy-dialkylsilane. Examples of (meth) acryloyloxyalkyl-trialkoxysilane include (meth) acryloyloxymethyltrimethoxysilane, (meth) acryloyloxymethyltriethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2- ( (Meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) Acryloyloxypropyltriisopropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 4- (meth) acryloyl In addition to oxybutyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexyltriethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 8- (meth) acryloyl Oxyoctyltriethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyltriethoxysilane, 12- (meth) acryloyloxidedecyltrimethoxysilane, 12- (meth) acryloyloxidedecyl Examples include triethoxysilane.

  Examples of the (meth) acryloyloxyalkyl-dialkoxy-alkylsilane include (meth) acryloyloxymethyldimethoxymethylsilane, (meth) acryloyloxymethyldimethoxyethylsilane, (meth) acryloyloxymethyldiethoxymethylsilane, (Meth) acryloyloxymethyldiethoxyethylsilane, 2- (meth) acryloyloxyethyldimethoxymethylsilane, 2- (meth) acryloyloxyethyldimethoxyethylsilane, 2- (meth) acryloyloxyethyldiethoxymethylsilane, 2- (Meth) acryloyloxyethyldiethoxyethylsilane, 3- (meth) acryloyloxypropyldimethoxymethylsilane, 3- (meth) acryloyloxypropyldimethoxyethyl Silane, 3- (meth) acryloyloxy propyl diethoxymethyl silane, such as 3- (meth) acryloyloxy propyl diethoxyethyl silane.

  Further, examples of (meth) acryloyloxyalkyl-alkoxy-dialkylsilane include (meth) acryloyloxymethylmethoxydimethylsilane, (meth) acryloyloxymethylmethoxydiethylsilane, (meth) acryloyloxymethylethoxydimethylsilane, (meth) ) Acryloyloxymethylethoxydiethylsilane, 2- (meth) acryloyloxyethylmethoxydimethylsilane, 2- (meth) acryloyloxyethylmethoxydiethylsilane, 2- (meth) acryloyloxyethylethoxydimethylsilane, 2- (meth) acryloyl Oxyethylethoxydiethylsilane, 3- (meth) acryloyloxypropylmethoxydimethylsilane, 3- (meth) acryloyloxypropylmethoxydie Rushiran, 3- (meth) acryloyloxy propyl ethoxy dimethyl silane, such as 3- (meth) acryloyloxy propyl-ethoxy-diethyl silane.

  Examples of the vinyl silane derivative include a silane compound in which a silyl group having 1 to 3 alkoxy groups and a vinyl group are directly bonded. Specifically, for example, vinyl-trialkoxy Silanes (eg, vinyltrimethoxysilane, vinyltriethoxysilane, etc.), vinyl-dialkoxy-alkylsilanes (eg, vinyldimethoxymethylsilane, vinyldimethoxyethylsilane, vinyldiethoxymethylsilane, vinyldiethoxyethylsilane, etc.), Examples thereof include vinyl-alkoxy-dialkylsilanes (eg, vinylmethoxydimethylsilane, vinylmethoxydiethylsilane, vinylethoxydimethylsilane, vinylethoxydiethylsilane).

  Examples of the vinylalkylsilane derivative include a silane compound in which a silyl group having 1 to 3 alkoxy groups and a vinyl group are bonded via an alkylene group. Vinylalkyl-trialkoxysilane, vinylalkyl-dialkoxy-alkylsilane, vinylalkyl-alkoxy-dialkylsilane, and the like. Examples of the vinylalkyl-trialkoxysilane include vinylmethyltrimethoxysilane, vinylmethyltriethoxysilane, 2-vinylethyltrimethoxysilane, 2-vinylethyltriethoxysilane, 3-vinylpropyltrimethoxysilane, and 3-vinyl. Propyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 6-vinylhexyltrimethoxysilane, 6-vinylhexyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltri Examples include ethoxysilane, 10-vinyldecyltrimethoxysilane, 10-vinyldecyltriethoxysilane, 12-vinyldodecyltrimethoxysilane, and 12-vinyldodecyltriethoxysilane. Examples of the vinylalkyl-dialkoxy-alkylsilane and the vinylalkyl-alkoxy-dialkylsilane include those corresponding to the specific examples of the vinylalkyl-trialkoxysilane.

  The amount of the silane monomer used can be appropriately selected according to the type of (meth) acrylic acid ester, the degree of crosslinking of the acrylic polymer, the use of the pressure-sensitive adhesive composition, and the like. Specifically, as a ratio of the silane monomer, a monomer mixture excluding a silane monomer (monomer alone) in a monomer mixture mainly composed of (meth) acrylic acid ester. Including): appropriately selected from the range of 0.001 to 0.5 parts by weight (preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.01 parts by weight) with respect to 100 parts by weight. can do.

  In the present invention, the emulsion type acrylic polymer (A) is prepared by emulsifying an acrylic polymer (A) prepared by a polymerization method (solution polymerization method, etc.) other than the emulsion polymerization method, using an emulsifier if necessary. The emulsion type acrylic polymer prepared by the emulsion polymerization method can be suitably used.

  In the polymerization such as emulsion polymerization, the monomer component may be introduced into the reaction system by batch charging in advance, or may be introduced by dropping continuously or intermittently. Furthermore, it may be introduced by charging a part at a time and dropping the remaining part continuously or intermittently. That is, examples of the polymerization method such as emulsion polymerization include a general batch polymerization method, a continuous dropping polymerization method, a divided dropping polymerization method, and the like, and any method may be used. In addition, the polymerization reaction may be performed stepwise. Specifically, for example, after the polymerization is performed once, the monomer component may be further added to perform the polymerization.

  In the present invention, the emulsion type acrylic polymer (A) is an acrylic polymer in an acrylic emulsion having an average particle diameter of emulsion particles of 0.2 μm or less as described above. It is important to carry out the emulsion polymerization so that the average particle size of the emulsion particles is 0.2 μm or less. Therefore, the emulsion type acrylic polymer (A) can be prepared by carrying out emulsion polymerization under conditions such that the average particle size of the emulsion particles is 0.2 μm or less. Conditions for such emulsion polymerization can be appropriately selected according to a polymerization method such as a batch polymerization method, a continuous dropping polymerization method, or a divided dropping polymerization method. For example, when emulsion polymerization is performed by a batch polymerization method, it is possible to prepare an acrylic emulsion having an average particle size of emulsion particles of 0.2 μm or less in most cases, but the amount of emulsifier should be adjusted. The particle size can be adjusted to some extent. For example, the amount of emulsifier (parts by weight) with respect to 100 parts by weight of the resulting acrylic polymer / average particle size (μm) of emulsion particles in the acrylic emulsion = 2/0. 138, 3 / 0.121, 5 / 0.099, 10 / 0.092, and the like. In addition, when emulsion polymerization is performed by the batch polymerization method, the emulsified monomer component is converted into a predetermined reaction start temperature (for example, 80%) of the polymerization initiator from the viewpoint of temperature control and the effect of increasing the molecular weight. It is also effective to perform polymerization at a temperature lower than ˜90 ° C., preferably about 85 ° C., and gradually raise the temperature. On the other hand, when emulsion polymerization is performed by a continuous dropping polymerization method, a method of dropping an emulsified monomer component into an aqueous system to which an emulsifier has been added in advance is exemplified. Specifically, an emulsion is added to an aqueous system (aqueous phase) by adding an emulsifier in a proportion of 0.05 to 1 (preferably 0.1 to 0.5) parts by weight with respect to the obtained acrylic polymer. An acrylic emulsion having an average particle diameter of 0.2 μm or less can be prepared. In this case, if the dropping rate of the monomer component is increased, the average particle diameter of the polymer tends to be reduced, and if the amount of the emulsifier previously charged in the aqueous phase is increased, the average particle diameter of the polymer tends to be reduced. . Thus, the average particle diameter of the polymer can be controlled by appropriately adjusting the dropping rate of the monomer component and the amount of the emulsifier previously charged in the aqueous phase. Furthermore, in the case of performing emulsion polymerization by the divisional drop polymerization method, a method in which the method of performing the emulsion polymerization by the batch polymerization method as described above and the method of performing the emulsion polymerization by the continuous drop polymerization method as described above are combined. Can be mentioned.

  In addition, the temperature at the time of superposition | polymerization can be suitably selected from the range of 20-100 degreeC, for example according to the kind of initiator to be used.

  When the emulsion type acrylic polymer (A) is prepared by emulsion polymerization, known emulsifiers can be used alone or in combination of two or more. However, as an emulsifier, it is copolymerized with (meth) acrylic acid ester in order to suppress or prevent a decrease in the adhesive strength of the adhesive layer due to precipitation of the emulsifier on the surface of the adhesive layer and contamination of the adherend by the emulsifier. It is preferable to use a reactive emulsifier having a group capable of (for example, a group containing an ethylenically unsaturated bond site). Since the reactive emulsifier is bonded to the molecular chain in the pressure-sensitive adhesive composition (particularly, the molecular chain of the acrylic polymer (A)), precipitation or migration to the surface of the pressure-sensitive adhesive layer is suppressed or prevented. It is possible to effectively suppress or prevent a decrease in the adhesive strength of the pressure-sensitive adhesive layer and contamination of the adherend. Therefore, the emulsion type acrylic polymer (A) is preferably prepared by emulsion polymerization of a monomer component in the presence of a reactive emulsifier.

  The reactive emulsifier has only to have an emulsifying function and a group that can be copolymerized with (meth) acrylic acid ester. For example, sodium lauryl sulfate, ammonium lauryl sulfate, dodecylbenzenesulfone Anionic emulsifiers such as sodium acid, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl sulfosuccinate; polyoxyethylene alkyl ether, polyoxyethylene Nonionic emulsifiers such as alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer; polyoxyethylene Radical polymerization of propenyl group and allyl ether group to emulsifiers such as sodium alkyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene alkylsulfosuccinate and other nonionic anionic emulsifiers And reactive emulsifiers having a form in which a functional functional group (radical reactive group) is introduced (or corresponding to the form).

  In addition, it does not restrict | limit especially as emulsifiers (non-reactive emulsifier) other than a reactive emulsifier, It can select suitably from well-known emulsifiers. Specifically, as the non-reactive emulsifier, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sulfate Anionic emulsifiers such as sodium, sodium polyoxyethylene alkyl sulfosuccinate; Nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer; polyoxy Sodium ethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate Arm, polyoxyethylene alkyl phenyl ether sulfate, such as nonionic anionic emulsifiers such as polyoxyethylene alkyl sodium sulfosuccinate and the like.

  The amount of the emulsifier (especially the reactive emulsifier) to be used is appropriately selected depending on the emulsion, but is generally 0.1 to 20 parts per 100 parts by weight of the monomer mixture. Parts by weight (preferably 1 to 10 parts by weight).

  In the present invention, a polymerization initiator, a chain transfer agent, or the like may be used in the polymerization for obtaining the emulsion type acrylic polymer (A). Such polymerization initiators and chain transfer agents are not particularly limited, and can be appropriately selected from known ones. Specifically, as a polymerization initiator, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfide, 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis [2 -Methyl-N- (phenylmethyl) -propionamidine] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydride Azo polymerization initiators such as chloride and 2,2′-azobis [2- (2-imidazolin-2-yl) propane]; persulfate polymerization initiators such as potassium persulfate and ammonium persulfate; benzoyl peroxide; Hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5- Peroxide-based polymerization initiators such as trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 3,3,5-trimethylcyclohexanoyl peroxide, t-butylperoxypivalate; Examples thereof include a redox polymerization initiator composed of a salt and sodium bisulfite. A polymerization initiator can be used individually or in combination of 2 or more types. The amount of the polymerization initiator used is not particularly limited and can be appropriately selected depending on the polymerization method, the polymerization reactivity, the type and ratio of monomer components, the type of polymerization initiator, and the like. The monomer mixture: it can be appropriately selected from the range of 0.005 to 1 part by weight with respect to 100 parts by weight.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimethylcapto-1-propanol.

[Petroleum resin (B)]
The petroleum resin (B) is not particularly limited, and for example, a petroleum resin (hydrocarbon resin) that can be used as a tackifying resin can be used. Examples of the petroleum resin (B) include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, aliphatic / alicyclic rings. It can be used by appropriately selecting from known petroleum resins such as group petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins and the like. Petroleum resin (B) can be used alone or in combination of two or more.

  Specifically, in the petroleum resin (B), examples of the aromatic petroleum resin include vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (styrene, o-vinyltoluene, m-vinyltoluene). , P-vinyltoluene, α-methylstyrene, β-methylstyrene, indene, methylindene and the like) and the like, and the like. As the aromatic petroleum resin, an aromatic petroleum resin (so-called “C9 petroleum resin”) obtained from a fraction such as vinyltoluene or indene (so-called “C9 petroleum fraction”) can be preferably used.

  Examples of the aliphatic petroleum resin include olefins having 4 to 5 carbon atoms and dienes [olefins such as butene-1, isobutylene and pentene-1; dienes such as butadiene, piperylene (1,3-pentadiene) and isoprene. Etc.] are used alone or in combination of two or more. As the aliphatic petroleum resin, an aliphatic petroleum resin (so-called “C4 petroleum resin”) obtained from a fraction such as butadiene, piperylene or isoprene (so-called “C4 petroleum fraction” or “C5 petroleum fraction”). And “C5-based petroleum resin” and the like can be suitably used.

  As the alicyclic petroleum resin, for example, an alicyclic hydrocarbon obtained by cyclizing and dimerizing an aliphatic petroleum resin (so-called “C4 petroleum resin”, “C5 petroleum resin”, etc.) is used. Polymers, cyclic diene compounds (cyclopentadiene, dicyclopentadiene, ethylidene norbornene, dipentene, ethylidenebicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, limonene, etc.) or hydrogenated products thereof, Aromatic hydrocarbon resins, and alicyclic hydrocarbon resins obtained by hydrogenating the aromatic rings of the following aliphatic / aromatic petroleum resins.

  Examples of the aliphatic / aromatic petroleum resins include styrene-olefin copolymers. As the aliphatic / aromatic petroleum resin, so-called “C5 / C9 copolymer petroleum resin” or the like can be used.

  As the petroleum resin (B), an aliphatic petroleum resin can be suitably used, and a C5 petroleum resin is particularly preferred. As such a petroleum resin (B), for example, a commercial product such as a trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.) can be used.

  Although it does not restrict | limit especially as a softening point (softening temperature) of petroleum resin (B), For example, it is suitable that it is 70-130 degreeC. As the softening point of the petroleum resin (B), for example, a value measured according to JIS K 5601-2-2 (ring and ball method) can be adopted.

  In general, petroleum resins have low compatibility with acrylic polymers, and are greatly affected by the passage of time and storage temperature. Therefore, even though petroleum resins are exemplified as tackifying resins (tackifiers) that can be used for acrylic polymers, they are substantially used for acrylic polymers in terms of stability. It is very rare for petroleum resins to be favorably used for acrylic polymers. However, in the present invention, a petroleum resin having low compatibility with the acrylic polymer is used in combination with the acrylic polymer, and this is the point of the present invention. That is, the emulsion type acrylic pressure-sensitive adhesive composition having the emulsion type acrylic polymer (A) as a base polymer has a low compatibility with the acrylic polymer and a petroleum resin that is not substantially used, By adding, the effect of improving the rewinding force of the pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer by the emulsion-type acrylic pressure-sensitive adhesive composition can be exerted, and this effect has not been found so far. . In addition, by applying the adhesive tape for bundling where the rewinding workability is important, the rewinding workability can be greatly improved by rewinding with an appropriate rewinding force.

  When the ratio of the petroleum resin (B) is too small, the effect of improving the rewinding property of the adhesive tape is reduced, while when too large, the compatibility with the emulsion type acrylic polymer (A) as the base polymer is reduced. Therefore, the stability of the emulsion-type acrylic pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer is lowered. For example, the adhesive force of the pressure-sensitive adhesive tape greatly changes with time, or is glued when the pressure-sensitive adhesive tape is rewound. May occur. Therefore, in the proportion of the petroleum resin (B), the proportion capable of maximizing the effect of developing an appropriate unwinding force is as follows: Emulsion-type acrylic polymer (A): 100 parts by weight 1 to 50 parts by weight, preferably 5 to 40 parts by weight.

[Rosin resin (C)]
The rosin resin (C) is not particularly limited, and for example, a rosin resin that can be used as a tackifying resin can be used. Examples of the rosin resin (C) include unmodified rosin (raw rosin) such as gum rosin, wood rosin and tall oil rosin, and modified rosin modified by polymerization, disproportionation, hydrogenation, and the like. (Polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, and other chemically modified rosins) and other known rosin resins such as various rosin derivatives It can be used by appropriately selecting among them. Examples of the rosin derivative include rosin ester compounds obtained by esterifying unmodified rosin with alcohols (unmodified rosin ester), polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, and partially hydrogenated rosin. Rosin esters such as rosin and other modified rosin ester compounds (polymerized rosin ester, stabilized rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, partially hydrogenated rosin ester, etc.) Resin: Unmodified rosin or modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.) modified with unsaturated fatty acid, unsaturated fatty acid modified rosin resin; rosin ester Unsaturated fatty acid-modified rosin ester resin modified with unsaturated fatty acid Reduction of carboxyl groups in gin, modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin), unsaturated fatty acid modified rosin resins and unsaturated fatty acid modified rosin ester resins Treated rosin alcohol resins; unmodified rosins, modified rosins, and metal salts of rosin resins (particularly rosin ester resins) such as various rosin derivatives. The rosin resin (C) can be used alone or in combination of two or more.

  Examples of alcohols used for preparing the rosin ester-based resin include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1, Divalent alcohols such as 6-hexanediol; Trivalent alcohols such as glycerin, trimethylolethane, trimethylolpropane, triethylolethane; Tetravalent alcohols such as pentaerythritol and diglycerin; Dipentaerythritol, etc. Polyhydric alcohols such as hexavalent alcohols are preferably used, but monohydric alcohols such as methanol and ethanol may be used. As alcohols, amino alcohols such as triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, Nn-butyldiethanolamine can also be used.

  Examples of the unsaturated fatty acid used in preparing the unsaturated fatty acid-modified rosin resin and the unsaturated fatty acid-modified rosin ester resin include fumaric acid, maleic acid or its anhydride, itaconic acid, citraconic acid or its Examples include α, β-unsaturated carboxylic acids such as anhydrides, acrylic acid, and methacrylic acid.

  In the present invention, a rosin ester resin can be suitably used as the rosin resin (C), and a polymerized rosin ester or a stabilized rosin ester is particularly suitable. As such rosin resin (C), for example, a commercial product such as a trade name “E-865” (manufactured by Arakawa Chemical Co., Ltd.) can be used.

  Although it does not restrict | limit especially as a softening point (softening temperature) of rosin-type resin (C), For example, it is preferable that it is 80-180 degreeC, and it is especially suitable that it is 120-170 degreeC. As the softening point of the rosin resin (C), for example, a value measured according to JIS K 5601-2-2 (ring and ball method) can be adopted.

  The ratio of the rosin resin (C) is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the emulsion type acrylic polymer (A). Terminal which prevents peeling from the terminal when the ratio of the rosin-based resin (C) is less than 1 part by weight with respect to 100 parts by weight of the emulsion-type acrylic polymer (A) when bound with an adhesive tape. However, if the amount exceeds 50 parts by weight, the emulsion-type acrylic pressure-sensitive adhesive composition becomes too hard and there is no adequate tackiness, and the unwinding force is small. It becomes too much.

  The total amount (total amount) of the petroleum resin (B) and the rosin resin (C) is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the emulsion type acrylic polymer (A). In particular, the amount is preferably 10 to 50 parts by weight. When the total amount of the petroleum resin (B) and the rosin resin (C) exceeds 60 parts by weight with respect to 100 parts by weight of the emulsion type acrylic polymer (A), the emulsion type acrylic pressure-sensitive adhesive composition There is a tendency that the influence of the tackifying resin in the inside becomes large and the tack becomes small. Further, when a tackifying resin having extremely low compatibility is used, the tackifying resin having extremely low compatibility may be segregated on the surface of the pressure-sensitive adhesive, which may cause trouble in use of the pressure-sensitive adhesive tape.

  Specific amounts of use of the petroleum resin (B) and the rosin resin (C) are the above-mentioned proportions (emulsion type acrylic polymer (A): 1 to 50 parts by weight with respect to 100 parts by weight). However, it can be appropriately selected depending on the thickness and hardness of the polyolefin-based substrate used, the composition of the emulsion-type acrylic pressure-sensitive adhesive composition, and the like. For example, when a thick polyolefin base material or a hard polyolefin base material is used as the base material, the terminal peeling prevention property tends to be lowered. Therefore, the blending amount of the rosin resin (C) is as described above. It is preferable to increase in the range of the ratio of this, and, thereby, the adhesive tape with favorable terminal peeling prevention property can be obtained. In addition, when a polyolefin-based substrate having a small thickness or a polyolefin-based substrate that is relatively soft and has an advantage in preventing terminal peeling is used as the substrate, petroleum resin (B) and rosin-based resin ( C) and the total amount can be suppressed. Furthermore, when the unwinding force of the pressure-sensitive adhesive tape is small, it can be dealt with by increasing the blending amount of the petroleum resin (B) within the above-mentioned ratio range, thereby expressing an appropriate unwinding force. The adhesive tape which can be made to be obtained can be obtained.

[Emulsion-type acrylic pressure-sensitive adhesive composition]
In the emulsion acrylic pressure-sensitive adhesive composition of the present invention, a plasticizer may be used. That is, a plasticizer can be used arbitrarily. When a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the emulsion-type acrylic pressure-sensitive adhesive composition is prepared by adding a plasticizer to the emulsion-type acrylic pressure-sensitive adhesive composition, the plasticizer in the pressure-sensitive adhesive layer is polyolefin. Since this shifts to the base material, the effect of softening the polyolefin base material is exhibited. Thus, by making the polyolefin-based substrate soft, the terminal peeling prevention property of the pressure-sensitive adhesive tape can be improved. From this viewpoint, the terminal peeling prevention property of the pressure-sensitive adhesive tape can be further improved. . Examples of the plasticizer include phthalic acid plasticizers [for example, dibutyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate, diisodecyl phthalate (DIDP), ditridecyl phthalate. (DTDP), ditriisodecyl phthalate, butyl lauryl phthalate, butyl benzyl phthalate], trimellitic acid plasticizers [for example, trioctyl trimellitic acid (TOTM), tri-n-octyl trimellitate, etc.] Fatty acid plasticizers such as tributyl citrate, dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS), methyl acetyl lysylate, etc. Phosphoric plasticizers [for example, Riku registration Le phosphate (TCP), trioctyl phosphate (TOP), etc.], an epoxy-based plasticizers, can also be used such as polyester plasticizer. A plasticizer can be used individually or in combination of 2 or more types. The blending amount of the plasticizer is not particularly limited. However, if the blending amount of the plasticizer is too large, the pressure-sensitive adhesive becomes soft and causes adhesion failure or adhesive residue. Therefore, the emulsion type acrylic polymer (A): It is preferably 30 parts by weight or less (for example, 1 to 30 parts by weight) with respect to 100 parts by weight. When there are few compounding quantities of a plasticizer, the softening effect of the polyolefin-type base material by a plasticizer will fall.

  In addition, a crosslinking agent may be used in the emulsion type acrylic pressure-sensitive adhesive composition. The crosslinking agent is not particularly limited, and examples thereof include an epoxy crosslinking agent, an isocyanate crosslinking agent, and an oxazoline crosslinking agent. A crosslinking agent can be used individually or in combination of 2 or more types. The blending amount of the crosslinking agent is not particularly limited, and may be a normal amount used for the pressure-sensitive adhesive composition.

  Furthermore, in the emulsion type acrylic pressure-sensitive adhesive composition, a tackifying resin other than petroleum resin (B) and rosin-based resin (C) is used as a tackifying resin within a range not impairing the effects of the present invention (for example, Terpene tackifier resins, phenol tackifier resins, epoxy tackifier resins, polyamide tackifier resins, ketone tackifier resins, elastomer tackifier resins, and the like).

  In the present invention, the emulsion type acrylic pressure-sensitive adhesive composition may contain various additives as necessary. Examples of such additives include plasticizers (softeners), tackifying resins and crosslinking agents as described above, thickeners, ultraviolet absorbers, antioxidants, fillers, colorants, and antistatic agents. Can be appropriately selected from known additives such as an agent, a foaming agent, and a surfactant.

  The emulsion-type acrylic pressure-sensitive adhesive composition includes, for example, the emulsion-type acrylic polymer (A), the petroleum resin (B), the rosin-based resin (C), and a plasticizer as necessary. In addition to the crosslinking agent, it can be prepared by further mixing with other additives.

[Base material]
In the pressure-sensitive adhesive tape of the present invention, as the substrate, a polyolefin substrate formed of an olefin resin composition containing a polyolefin resin and a metal hydroxide is used. Examples of the polyolefin-based resin in the polyolefin-based substrate include α-olefins such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA) as monomer components. And polyolefin resin to be used. Polyolefin resins can be used alone or in combination of two or more.

  In the present invention, a polyolefin-based substrate that does not substantially contain a halogen atom is suitable as the substrate. Here, “substantially does not contain a halogen atom” means that a substance containing a halogen atom in the molecule is not used as a constituent material of the polyolefin-based substrate (olefin-based resin composition). ing. Therefore, when a composition analysis of the substrate is performed by instrumental analysis means, a halogen atom detected by a trace amount level (for example, a halogen atom by a halogen atom-containing substance used as a catalyst during the synthesis of a compound (a constituent material of the substrate)) However, as a result of mixing in the constituent material of the base material, the inclusion of a trace amount of halogen atoms detected from the base material) is permitted.

  More specifically, examples of the polyolefin resin in the polyolefin base material include polyethylene (for example, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, medium density polyethylene, high density polyethylene, and the like), polypropylene. In addition to polybutene, polybutylene, polybutadiene, ethylene and / or copolymers of propylene and other α-olefins (particularly random copolymers) such as ethylene-propylene copolymers (random copolymers), and the like. . As the polyolefin resin, polyethylene and polypropylene are preferable, and polyethylene is particularly preferable. Polyolefin resins can be used alone or in combination of two or more.

  The polyolefin resin can be used in combination with other resins. As such a resin, a thermoplastic resin having a carbonyl oxygen atom in the molecule (in the molecular skeleton) can be suitably used from the viewpoint of imparting appropriate flexibility to the substrate. As such a thermoplastic resin having a carbonyl oxygen atom (oxygen atom belonging to a carbonyl group) in the molecule, a soft polyolefin resin having a carbonyl oxygen atom in the molecule (“carbonyl group-containing polyolefin resin”). May be suitably used. Of course, since the carbonyl group-containing polyolefin resin is a polyolefin resin, it can be used as a polyolefin resin as a constituent material of the adhesive tape substrate. That is, the carbonyl group-containing polyolefin-based resin may be used alone as a polyolefin-based resin, or may be used together with other polyolefin-based resins.

  Preferable examples of the carbonyl group-containing polyolefin resin include, for example, ethylene, vinyl ester compound and / or α, β-unsaturated carboxylic acid or derivative thereof (anhydride, ester, chloride, etc.) as a monomer component. And an ethylene-based copolymer having a carbonyl group or a metal salt thereof (ionomer). The ethylene copolymer having a carbonyl group or a metal salt thereof (ionomer) generally has a melting point of 120 ° C. or less, preferably 40 to 100 ° C. The melting point can be measured by a differential scanning calorimeter (DSC).

  Examples of the vinyl ester compounds include esters of vinyl alcohols such as vinyl acetate and lower carboxylic acids (vinyl esters of lower carboxylic acids). Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of α, β-unsaturated carboxylic acid derivatives include α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Examples of the α, β-unsaturated carboxylic acid ester include (meth) acrylic acid ester [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate (Meth) acrylic acid alkyl ester such as (meth) acrylic acid cyclohexyl ester; (meth) acrylic acid cycloalkyl ester; (meth) acrylic acid aryl ester; (meth) acrylic acid glycidyl, (meth) acrylic acid 2-hydroxy Functional group-containing (meth) acrylic acid esters such as ethyl], maleic acid esters [for example, maleic acid (mono or di) alkyl esters such as monomethyl maleate, monoethyl maleate, diethyl maleate, etc.], fumaric acid esters [ Examples thereof include fumaric acid (mono or di) alkyl esters such as monomethyl fumarate and monoethyl fumarate]. As vinyl ester compounds and / or α, β-unsaturated carboxylic acids or derivatives thereof, vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid esters are preferable, and (meth) acrylic acid esters include (meta ) Acrylic acid alkyl ester [especially ethyl (meth) acrylate, especially ethyl acrylate] is preferred. The vinyl ester compound and / or the α, β-unsaturated carboxylic acid or derivative thereof can be used alone or in combination of two or more.

  Preferable specific examples of the ethylene copolymer having a carbonyl group or a metal salt thereof (ionomer) include, for example, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-ethyl acrylate copolymer. , Ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-acrylic acid Examples thereof include ethyl copolymers and their metal salts (ionomers). The ethylene-based copolymer having a carbonyl group or a metal salt (ionomer) thereof can be used alone or in combination of two or more.

  Furthermore, as the polyolefin-based resin, a polymer alloy containing an ethylene component and a propylene component can be used. The configuration (form) of the polymer alloy is not particularly limited. For example, (1) a polymer blend (physical mixture) in which two or more polymers are physically mixed, and (2) two or more types. Block copolymers and graft copolymers in which polymers are covalently bonded, (3) IPN (Interpenetrating Polymer Network) structures in which two or more polymers are intertwined without being covalently bonded to each other, etc. There are various configurations (forms). In addition, the polymer alloy may not necessarily be uniform in composition (may have a distribution), or may be a mixture of two or more polymers (compatible polymer alloy). Those in which the coalescence is incompatible and forms a phase separation structure (incompatible polymer alloy) may be used. Further, it may be one having a heat characteristic having a plurality of exothermic or endothermic peaks as measured by a differential scanning calorimeter (DSC measurement).

  Examples of the polymer alloy containing the ethylene component and the propylene component include a mixture (physical of polypropylene (homopolypropylene, random polypropylene) and polyethylene (including a copolymer of ethylene and a small amount of other α-olefin). Mixture), propylene / ethylene copolymer, terpolymer of propylene, ethylene and other α-olefins other than these (as other α-olefins, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like are preferable, and 1-butene is preferable. The “homopolypropylene” means a polymer (a propylene homopolymer) in which the monomer component is substantially composed only of propylene (consisting of 100%), and “random polypropylene” It means a polypropylene random copolymer in which about several percent of the ethylene component is randomly copolymerized with propylene.

  When the polymer alloy is a copolymer (particularly a block copolymer), the polymer alloy is preferably a copolymer copolymerized by two or more stages of polymerization, and more preferably a propylene / ethylene copolymer. It is. As described in JP-A-4-224809 and JP-A-2001-192629, the copolymer copolymerized by such multistage polymerization is, for example, a catalyst composed of a titanium compound and an organoaluminum compound. In the presence, first, propylene or propylene and another α-olefin are preliminarily polymerized in the first stage of the multistage polymerization, and then polypropylene (a homopolymer of propylene) or propylene-α-olefin copolymer (propylene). And other α-olefin copolymer), and then in the presence of the resin composition obtained in the first stage prepolymerization in the second stage and thereafter, propylene, ethylene and If necessary, it can be prepared by copolymerizing with another α-olefin. As a result, a polymer (polypropylene or propylene-α-olefin copolymer) produced by the first stage prepolymerization and a polymer (propylene-ethylene copolymer or propylene-propylene-polymer produced by the second stage or later copolymerization). A polymer alloy obtained by blending ethylene-other α-olefin copolymer) at the molecular level in the polymerization process in the second and subsequent stages is obtained.

  Examples of the titanium compound include a spherical shape obtained by co-grinding titanium trichloride and magnesium chloride and treating with n-butyl orthotitanate, 2-ethylhexanol, ethyl p-toluate, silicon tetrachloride, diisobutyl phthalate, or the like. Examples thereof include a solid catalyst having an average particle size of 15 μm. In addition, as the organoaluminum compound, for example, an alkylaluminum compound such as triethylaluminum can be used. Further, in the polymerization layer, a silicon compound such as diphenyldimethoxysilane or an iodine compound such as ethyl iodide can be added as an electron donor.

  As such a polymer alloy containing an ethylene component and a propylene component, for example, the dynamic storage elastic modulus (E ′) at 23 ° C. is 20 MPa or more and less than 400 MPa (preferably 200 MPa or more and less than 400 MPa), and 80 ° C. The dynamic storage elastic modulus (E ′) at 40 ° C. or more and less than 180 MPa (preferably 45 to 160 MPa) and the dynamic storage elastic modulus (E ′) at 120 ° C. is 12 MPa or more and less than 70 MPa (preferably 15 to It is preferable that the pressure is 65 MPa. By having such a dynamic storage elastic modulus (E ′), the substrate can exhibit good flexibility.

  In addition, the dynamic storage elastic modulus (E ') of a polymer alloy produces the test piece (Thickness 0.2mm, width 10mm, length 20mm) by a polymer alloy, and the dynamic storage elastic modulus by the temperature dispersion | distribution of the said test piece. It is possible to adopt a value obtained by measuring the behavior using a trade name “DMS200 (manufactured by Seiko Instruments Inc.)” as a measuring instrument under the measurement method: tensile mode, heating rate: 2 ° C./min, frequency: 1 Hz. it can.

  Specific examples of the polymer alloy having such a dynamic storage elastic modulus (E ′) include, for example, a series of catalloy products (ADFLEX) manufactured by Sun Allomer Co., Ltd. (for example, trade name “KS-353P”, product Name “KS-021P”, product name “C200F”, product name “Q200F”, etc.).

  In the polyolefin-based substrate, examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconium hydroxide. A metal hydroxide can be used individually or in combination of 2 or more types.

  In addition, as a metal hydroxide, the surface-treated thing may be given. Examples of such surface treatment include silane coupling treatment. In the silane coupling treatment, a known or common silane coupling agent such as an amino silane coupling agent can be used. Therefore, a metal hydroxide surface-treated with a silane coupling agent can be used as the metal hydroxide.

  The ratio of the metal hydroxide is not particularly limited, and is, for example, about 10 to 200 parts by weight (preferably 50 to 150 parts by weight) with respect to 100 parts by weight of polyolefin resin. If the ratio of the metal hydroxide is less than 10 parts by weight based on the polyolefin resin: 100 parts by weight, the flame retardancy of the base material (or adhesive tape) decreases, while if it exceeds 200 parts by weight, The flexibility and extensibility of the material (or adhesive tape) are reduced.

  The olefin-based resin composition for forming the polyolefin-based substrate includes a filler (for example, an inorganic filler such as titanium oxide and zinc oxide) and an anti-aging agent (for example, an amine-based anti-aging agent) as necessary. Agents, quinoline anti-aging agents, hydroquinone anti-aging agents, phenolic anti-aging agents, phosphorus anti-aging agents, phosphite anti-aging agents, etc.), antioxidants, UV absorbers (eg salicylic acid derivatives, Benzophenone UV absorbers, benzotriazole UV absorbers, hindered amine UV absorbers, etc.), lubricants, plasticizers, colorants (eg pigments, dyes, etc.), nucleating agents, heavy metal deactivators, etc. May be blended.

  The method for producing the polyolefin base material is not particularly limited. A polyolefin resin, a metal hydroxide, and various additives such as a filler, if necessary, are dry blended, and the mixture is kneaded using a Banbury mixer, roll, extruder, etc. The kneaded product can be formed into a film or sheet by a known or conventional molding method (for example, compression molding method, calendar molding method, injection molding method, extrusion molding method, etc.). Can be obtained. As a method for producing a polyolefin-based substrate, a calendar rolling method or a flat die extrusion method (flat die extrusion method) can be suitably employed.

  The polyolefin-based substrate has a film-like or sheet-like form. The thickness of the film- or sheet-like polyolefin-based substrate (polyolefin-based film or sheet) is not particularly limited and is generally 0.01 to 1 mm (preferably 0.05 to 5 mm) although it varies depending on the use of the adhesive tape. Degree. In addition, the polyolefin-type base material may have a single layer form, and may have a multiple layer form. The polyolefin-based substrate may be subjected to various treatments such as back treatment, antistatic treatment, and undercoating treatment as necessary.

[Adhesive tape]
The pressure-sensitive adhesive tape of the present invention has a configuration in which a pressure-sensitive adhesive layer is formed on at least one surface of a base material, and the base material is made of an olefin-based resin composition containing a polyolefin-based resin and a metal hydroxide. The pressure-sensitive adhesive layer is formed of an emulsion-type acrylic pressure-sensitive adhesive composition containing an acrylic emulsion having an average particle diameter of emulsion particles of 0.2 μm or less. The pressure-sensitive adhesive tape may have a form in which a pressure-sensitive adhesive layer made of an emulsion-type acrylic pressure-sensitive adhesive composition is formed on only one surface of a polyolefin-based substrate. You may have the form in which the adhesive layer by a system adhesive composition was formed.

  In the case where the pressure-sensitive adhesive tape has a form in which the pressure-sensitive adhesive layer made of the emulsion-type acrylic pressure-sensitive adhesive composition is formed only on one surface of the polyolefin-based base material, the pressure-sensitive adhesive tape is, for example, a polyolefin-based base material and A pressure-sensitive adhesive layer formed on one surface of the polyolefin-based substrate and formed of the emulsion-type acrylic pressure-sensitive adhesive composition; and a back treatment layer formed on the other surface of the polyolefin-based substrate. When configured, the pressure-sensitive adhesive layer can be superimposed on the back of the sheet (the surface of the back treatment layer) and wound into a roll to produce a pressure-sensitive adhesive tape wound or rolled. it can. At this time, the pressure-sensitive adhesive layer is protected by the back treatment layer on the back side of the sheet.

  Of course, when the pressure-sensitive adhesive tape is a double-sided pressure-sensitive adhesive tape, or when the back surface of the base material is not a release treatment surface, the pressure-sensitive adhesive layer is wound into a roll while being protected by a release liner (separator). Thus, an adhesive tape can be produced.

  The pressure-sensitive adhesive tape may have other layers (for example, an intermediate layer and an undercoat layer) as long as the effects of the present invention are not impaired.

  The pressure-sensitive adhesive layer may have any form of a single layer or a laminate. The thickness of the pressure-sensitive adhesive layer (thickness after drying) is, for example, about 10 to 50 μm (preferably 15 to 40 μm).

  The pressure-sensitive adhesive layer can be formed by a known or conventional method, and can be formed by using, for example, a casting method, a roll coater method, a reverse coater method, a doctor blade method, or the like.

  As described above, the pressure-sensitive adhesive tape of the present invention is excellent in adhesiveness and terminal peeling prevention properties, and can exhibit an appropriate rewinding force. Accordingly, the pressure-sensitive adhesive tape of the present invention can be rewound with an appropriate rewinding force when used, and after being applied, exhibits excellent terminal peeling prevention properties and is applied with good adhesiveness. This state can be maintained for a long time.

  In addition, by using a polyolefin base material that does not substantially contain a halogen atom as the base material, it is possible to prevent the generation of toxic gas when incinerated after using the adhesive tape. Therefore, the pressure-sensitive adhesive tape of the present invention is excellent in heat resistance and can be a pressure-sensitive adhesive tape that does not generate toxic gas during incineration.

  Therefore, the pressure-sensitive adhesive tape of the present invention can be suitably used as a binding pressure-sensitive adhesive tape, and in particular, a binding pressure-sensitive adhesive tape used in a place requiring electrical insulation (particularly, a wiring pressure-sensitive adhesive tape for wiring). Can be suitably used. The wirings may be any wirings such as various electric wires and cables, and among them, electric wires for electric appliances and electric wires for automobiles (particularly, electric wires for automobiles) are preferably used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Preparation Example 1 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.03 part by weight is blended, and these are reactive emulsifiers (trade name “Aqualon BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer A”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a batch polymerization method. In this acrylic emulsion polymer A, the average particle size of the emulsion particles was 0.128 μm.

(Emulsion type acrylic polymer preparation example 2)
A mixture consisting of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 28.75% by weight, and methacrylic acid: 1.25% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “Aqualon BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer B”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer B, the average particle size of the emulsion particles was 0.141 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 100 parts by weight of the emulsifier is 0.05 to 1 part by weight (preferably 0.1 to 0.5 part by weight) is added, and by appropriately adjusting the dropping speed at which the emulsion is dropped, an acrylic particle having an average particle diameter of 0.141 μm as a result. An emulsion of the polymer was obtained.

(Preparation Example 3 of Emulsion Type Acrylic Polymer)
Mixture consisting of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 28.75% by weight, and methacrylic acid: 1.25% by weight: 100 parts by weight of the silane coupling agent (trade name “KBM- 503 "manufactured by Shin-Etsu Silicone Co., Ltd.): 0.005 parts by weight, water-soluble azo initiator as a polymerization initiator (trade name" V-50 "manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 parts by weight, These are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): emulsified with 2 parts by weight, polymerized at about 60 ° C. for 2 hours, and then an acrylic polymer emulsion (“acrylic emulsion polymer” C ") may be prepared. In this acrylic emulsion polymer C, the average particle size of the emulsion particles was 0.158 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 100 parts by weight of the emulsifier is 0.05 to 1 part by weight (preferably 0.1 to 0.5 part by weight) is added, and by appropriately adjusting the dropping speed at which the emulsion is dropped, an acrylic particle having an average particle diameter of 0.158 μm as a result is obtained. An emulsion of the polymer was obtained.

(Preparation Example 4 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer D”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer D, the average particle size of the emulsion particles was 0.180 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 100 parts by weight of the emulsifier is 0.05 to 1 part by weight (preferably 0.1 to 0.5 part by weight) is added, and by appropriately adjusting the dropping speed at which the emulsion is dropped, the average particle diameter of the emulsion particles is 0.180 μm. An emulsion of acrylic polymer was obtained.

(Preparation Example 5 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer E”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer E, the average particle size of the emulsion particles was 0.216 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 0.05 wt. Less than 1 part or more than 1 part by weight, and by appropriately adjusting the dropping speed at which the emulsion is dropped, an acrylic polymer emulsion having an average particle diameter of 0.216 μm is obtained as a result. It was.

(Preparation Example 6 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer F”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer F, the average particle size of the emulsion particles was 0.489 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 0.05 wt. Less than 1 part or more than 1 part by weight, and by appropriately adjusting the dropping speed at which the emulsion is dropped, an acrylic polymer emulsion having an average particle diameter of the emulsion particles of 0.489 μm is obtained as a result. It was.

(Preparation Example 7 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer G”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer G, the average particle size of the emulsion particles was 0.626 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 0.05 wt. Add an amount of less than 1 part or more than 1 part by weight, and by appropriately adjusting the dropping speed for dropping the emulsion, an acrylic polymer emulsion having an average particle diameter of 0.626 μm is obtained as a result. It was.

(Preparation Example 8 of Emulsion Type Acrylic Polymer)
A mixture of n-butyl acrylate: 70% by weight, 2-ethylhexyl acrylate: 29.5% by weight, and methacrylic acid: 0.5% by weight: 100 parts by weight of water-soluble azo initiator as a polymerization initiator (Trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight, and these are reactive emulsifiers (trade name “AQUALON BC-2020”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 2 weights An emulsion of an acrylic polymer (sometimes referred to as “acrylic emulsion polymer H”) was prepared by emulsion polymerization at about 60 ° C. for 2 hours by an emulsion polymerization method using a continuous dropping polymerization method. In this acrylic emulsion polymer H, the average particle size of the emulsion particles was 0.948 μm. In addition, in the aqueous system (aqueous phase) in which the emulsion containing the monomer component is dropped, a mixture composed of n-butyl acrylate, 2-ethylhexyl acrylate and methacrylic acid: 0.05 wt. Add an amount of less than 1 part or more than 1 part by weight, and by appropriately adjusting the dropping speed for dropping the emulsion, an acrylic polymer emulsion having an average particle diameter of 0.948 μm is obtained as a result. It was.

(Example 1)
As shown in Table 1, with respect to acrylic emulsion polymer A: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 5 parts by weight as rosin resin as solid resin. Trade name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 25 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co., Ltd .; epoxy cross-linking agent): 0.03 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the following polyolefin base material so that the thickness after drying is 30 μm, dried and cured to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive The layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate, to produce an adhesive tape.

Polyolefin base material:
-Ethylene-vinyl acetate copolymer (EVA) [Melting point: 84 ° C, trade name "Evaflex P-1905" manufactured by Mitsui DuPont Polychemical Co., Ltd.]: 20 parts by weight-Polymer alloy containing an ethylene component and a propylene component [Trade name “Cataloy KS-353P” manufactured by Montel SDK / Sunrise Co., Ltd.]: 80 parts by weight Magnesium hydroxide [Mg (OH) ₂ ] [treated with silane coupling agent, trade name “Kisuma 5NH” “Kyowa Chemical Industry Co., Ltd.”: 170 parts by weight Carbon black [trade name “Seast 3H” Tokai Carbon Co., Ltd.]: 4 parts by weight Each of the above materials (ethylene-vinyl acetate copolymer, polymer alloy, hydroxylation) Magnesium and carbon black) are dry blended, then kneaded at 180 ° C. in a 3 L pressure kneader and pelletized. It was. The pelletized composition is formed into a 0.2 mm-thick film by a calender rolling machine to produce a tape substrate, and a polyolefin-based substrate obtained by subjecting one side of the tape substrate to corona discharge treatment. Material

(Example 2)
As shown in Table 1, with respect to acrylic emulsion polymer B: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 15 parts by weight as rosin resin, as a petroleum resin. Product name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 15 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co .; epoxy system cross-linking agent): 0.01 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Example 3)
As shown in Table 1, with respect to acrylic emulsion polymer C: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 15 parts by weight as a petroleum resin, and rosin resin Product name “E-865” (manufactured by Arakawa Chemical Co., Ltd .; rosin ester resin): 15 parts by weight is blended and rotated at about 1,000 to 2,000 rpm with a homomixer at room temperature (20 to 25 ° C.). The mixture was mixed at a speed for about 10 minutes to obtain an emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

Example 4
As shown in Table 1, with respect to acrylic emulsion polymer D: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 15 parts by weight as rosin resin as solid resin. Product name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 15 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co .; epoxy system cross-linking agent): 0.01 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Comparative Example 1)
As shown in Table 1, with respect to acrylic emulsion polymer E: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.) as petroleum resin: 5 parts by weight as rosin resin Trade name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 25 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co., Ltd .; epoxy cross-linking agent): 0.03 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Comparative Example 2)
As shown in Table 1, with respect to acrylic emulsion polymer F: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 5 parts by weight as rosin resin as solid resin. Trade name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 25 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co., Ltd .; epoxy cross-linking agent): 0.03 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Comparative Example 3)
As shown in Table 1, with respect to acrylic emulsion polymer G: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 5 parts by weight as rosin resin as solid resin. Trade name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 25 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co., Ltd .; epoxy cross-linking agent): 0.03 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Comparative Example 4)
As shown in Table 1, with respect to acrylic emulsion polymer H: 100 parts by weight (solid content), trade name “AP-1085” (manufactured by Arakawa Chemical Co., Ltd.): 5 parts by weight as rosin resin as solid resin. Trade name “E-865” (Arakawa Chemical Co., Ltd .; rosin ester resin): 25 parts by weight, and trade name “Tetrad C” (Mitsubishi Gas Chemical Co., Ltd .; epoxy cross-linking agent): 0.03 wt. The emulsion-type acrylic pressure-sensitive adhesive composition (emulsion-type acrylic) is mixed with a homomixer at room temperature (20-25 ° C.) at a rotational speed of about 1,000-2,000 rpm for about 10 minutes. System pressure-sensitive adhesive composition).

  The emulsion-type acrylic pressure-sensitive adhesive composition is applied to one side of the same polyolefin-based substrate as in Example 1 so that the thickness after drying is 30 μm, and dried and cured to form a pressure-sensitive adhesive layer. After that, the pressure-sensitive adhesive layer was wound so as to overlap the back surface (self-back surface) of the polyolefin-based substrate to produce a pressure-sensitive adhesive tape.

(Evaluation)
About the adhesive tape obtained in Examples 1-4 and Comparative Examples 1-4, adhesive force, terminal peeling prevention property, and unwinding force were evaluated with the following measuring method or evaluation method.

(Measurement method of adhesive strength)
Each adhesive tape according to Examples 1 to 4 and Comparative Examples 1 to 4 was cut into a size of 19 mm in width and 100 mm in length, and this 19 mm × 100 mm adhesive tape was applied to the following adherend with a 2 kg roller. After being reciprocated by one reciprocation, the sample was left under the following standing conditions, and then peeled off by a 180 ° peel peel test (peel angle: 180 °, tensile speed: 300 mm / min, 23 ° C., 50% RH). The required force (180 ° peeling force) (N / 19 mm) was measured to evaluate the adhesive force. The measurement results are shown in the columns of “Adhesive strength against SUS plate (N / 19 mm)” and “Adhesive strength on the back surface (N / 19 mm)” in Table 1 for each adherend.
Substrate: Stainless steel plate (SUS plate), self-back surface (polyolefin base material surface)
Standing condition: 23 ° C x 20 minutes

(Evaluation method of device peeling prevention)
An adhesive tape cut to a width of 6.4 mm was wound around a 3.2 mmφ metal rod according to the “ASTM terminal peeling test”, and the distance (mm) of terminal peeling after 1 week (after 7 days) was measured. The evaluation results are shown in the column of “terminal peeling prevention (mm)” in Table 1. Note that the shorter the distance of terminal peeling, the better the terminal peeling prevention property.

(Measurement method of unwinding force)
The pressure-sensitive adhesive tape cut to a width of 19 mm is rewound using a pressure-sensitive adhesive tape rewinding tester (device name “rewinding tester” manufactured by Imada Seisakusho Co., Ltd.) at room temperature (23 ° C.) at a pulling speed of 30 mm / min. Then, the tension (rewinding force) (N / 19 mm) at that time was measured. The measurement results are shown in the column of “Rewinding force (N / 19 mm)” in Table 1.

  As is clear from Table 1, it was confirmed that all of the pressure-sensitive adhesive tapes according to Examples 1 to 4 had a good balance between the terminal peeling prevention property and the rewinding force and also had good adhesiveness.

  In addition, when the adhesive tape which concerns on Example 1 and the adhesive tape which concerns on Comparative Examples 1-3 are compared, terminal peeling will be so small that the average particle diameter of the emulsion particle | grains in the emulsion of an acrylic polymer (emulsion type acrylic polymer) is small. It was confirmed that the prevention property was good.

  Moreover, since the base material in the adhesive tape which concerns on an Example is comprised by the olefin resin, it does not contain a halogen atom and does not generate | occur | produce a harmful gas at the time of incineration. Further, it contains a metal hydroxide and has good heat resistance. Therefore, the adhesive tape according to the example can be suitably used as an adhesive tape for binding wirings, and is particularly useful as an adhesive tape for binding electric wires for automobiles that require heat resistance.

Claims (5)

  An adhesive tape or sheet having a configuration in which an adhesive layer is formed on at least one surface of a substrate, wherein the substrate is formed of an olefin resin composition containing a polyolefin resin and a metal hydroxide. The pressure-sensitive adhesive tape is characterized in that the pressure-sensitive adhesive layer is formed of an emulsion-type acrylic pressure-sensitive adhesive composition containing an acrylic emulsion having an average particle diameter of emulsion particles of 0.2 μm or less. The emulsion type acrylic pressure-sensitive adhesive composition comprises the following component (A), component (B) and component (C): component (A): 100 parts by weight, component (B) 1 to 50 parts by weight, The pressure-sensitive adhesive tape according to claim 1, comprising (C) component in a proportion of 1 to 50 parts by weight.
(A): Emulsion type acrylic polymer (B): Petroleum resin (C): Rosin resin   Emulsion-type acrylic polymer (A) is an acrylic polymer obtained by copolymerization of a monomer mixture containing at least a (meth) acrylic acid ester and an ethylenically unsaturated monomer having a hydrolyzable silicon atom-containing group The pressure-sensitive adhesive tape according to claim 2, which is a polymer.   An emulsion type obtained by emulsion polymerization of a monomer component in the presence of a reactive emulsifier in which an emulsion type acrylic polymer (A) has a group capable of copolymerization with a (meth) acrylic acid ester The pressure-sensitive adhesive tape according to claim 2 or 3, which is an acrylic polymer.   The pressure-sensitive adhesive tape according to any one of claims 2 to 4, wherein the total amount of the component (B) and the component (C) is 10 to 60 parts by weight with respect to 100 parts by weight of the component (A).