JP2016194042A - Pressure-sensitive adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive tape including a polyvinyl chloride (PVC) film containing a plasticizer, in which fogging is suppressed.SOLUTION: The pressure-sensitive adhesive tape comprises a PVC film comprising a plasticizer and a pressure-sensitive adhesive layer disposed on at least one surface of the film. The pressure-sensitive tape yields a condensation amount of 5 mg or less in a condensation amount measurement carried out by holding a piece of the pressure-sensitive adhesive tape having a surface area equivalent to a circle of 80 mm diameter at 120°C for 16 hours.SELECTED DRAWING: None

Description

  The present invention relates to an adhesive tape provided with a polyvinyl chloride (PVC) film.

  In general, a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive; the same shall apply hereinafter) is in the form of a soft solid (viscoelastic body) in a temperature range near room temperature, and has a property of being easily bonded by pressure. Taking advantage of such properties, the pressure-sensitive adhesive is, for example, in the form of a pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer is disposed on at least one surface of a substrate, and is widely used in various industrial fields such as home appliances, automobiles, and OA equipment. . An adhesive tape using a PVC film as the substrate (hereinafter also referred to as “PVC adhesive tape”) is used for various applications such as electrical insulation, packaging, and protection because of its good workability. Patent document 1 is mentioned as a technical literature regarding a PVC adhesive tape. Patent Document 2 is a technical document relating to a polyolefin wrapping foil.

JP 2009-249510 A Special table 2007-5110011 gazette

  Patent Document 2 points out a problem of the PVC adhesive tape in which the plasticizer contained in the PVC film evaporates and the vapor fogs the glass of the automobile, that is, the occurrence of “fogging”. In order to solve such a problem, Patent Document 2 employs a polyolefin substrate instead of a PVC film (claim 1, paragraphs 0002 to 0003, etc.). However, since PVC films have unique features that are difficult to replace with polyolefin films, there is a strong demand for PVC adhesive tapes. Therefore, it would be beneficial to provide a technique for reducing the above-described fogging in a PVC adhesive tape.

  This invention is made | formed in view of this situation, Comprising: It aims at providing the adhesive tape provided with the PVC film containing a plasticizer and with which fogging was suppressed.

  The pressure-sensitive adhesive tape provided by the present invention includes a polyvinyl chloride film (PVC film) containing a plasticizer and a pressure-sensitive adhesive layer disposed on at least one surface of the PVC film. The adhesive tape has an adhesion amount of 5 mg or less in an adhesion amount measurement performed by holding the adhesive tape having an area corresponding to a circle having a diameter of 80 mm at 120 ° C. for 16 hours. Thus, the structure provided with the PVC film containing a plasticizer by restrict | limiting the adhesion amount (henceforth only "adhesion amount") per adhesive tape of the area equivalent to a circle | round | yen with a diameter of 80 mm to 5 mg or less. An adhesive tape in which fogging is effectively suppressed can be realized.

  The technique disclosed here can be preferably implemented in an embodiment in which the content of the plasticizer in the PVC film is, for example, about 10 to 50% by weight. According to the PVC film having such a composition, good antifogging properties (that is, performance for suppressing fogging) and suitable flexibility tend to be realized at the same time.

  It is preferable that the PVC film which comprises the said PVC adhesive tape contains a fatty acid metal salt. By including a PVC film fatty acid metal salt, the amount of adhesion tends to decrease. As said fatty acid metal salt, what contains at least 1 sort (s) of metal element (however, except Pb) which belongs to either 1st group, 2nd group, 12th group, 13th group, and 14th group of a periodic table can be employ | adopted preferably. . Of these, fatty acid metal salts containing at least one metal element selected from the group consisting of Li, Na, Ca, Mg, Zn, Ba and Sn are preferred.

  The PVC film constituting the pressure-sensitive adhesive tape according to a preferred embodiment includes, as the plasticizer, a polyester plasticizer having a molecular weight of 1000 or more and a carboxylic acid ester having a molecular weight of less than 1000. The PVC pressure-sensitive adhesive tape having such a configuration is easy to achieve both antifogging properties and other characteristics (for example, initial adhesive strength and low-temperature characteristics) at a high level.

The PVC film has the following relationship between the weight W _PLH of the polyester plasticizer having a molecular weight of 1000 or more contained in the PVC film and the weight W _PLL of the carboxylic acid ester having a molecular weight of less than 1000 contained in the PVC film. Formula:
1 ≦ (W _PLH / W _PLL ) ≦ 50;
It is preferable to satisfy. The pressure-sensitive adhesive tape having such a PVC film easily achieves both antifogging properties and other characteristics (for example, initial adhesive strength and low temperature characteristics) at a higher level.

  It is preferable that the PVC film which comprises the adhesive tape disclosed here contains antioxidant. By using an antioxidant, the heat resistance of the PVC film is improved, and the amount of adhesion tends to decrease even under high temperature conditions.

  Moreover, according to this specification, the wire harness which has the structure by which any adhesive tape disclosed here was wound around the electric wire is provided. By comprising in this way, favorable fogging prevention property is realizable in the said wire harness.

It is sectional drawing which shows typically the structure of the adhesive tape which concerns on one Embodiment. It is sectional drawing which shows typically the structure of the adhesive tape which concerns on other embodiment.

  Hereinafter, preferred embodiments of the present invention will be described. Matters other than those specifically mentioned in the present specification and necessary for the implementation of the present invention are based on the teachings on the implementation of the invention described in the present specification and the common general technical knowledge at the time of filing. It can be understood by a trader. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

  The pressure-sensitive adhesive tape disclosed herein includes a PVC film containing a plasticizer, and a pressure-sensitive adhesive layer disposed on one surface or both surfaces of the PVC film.

<PVC film>
The PVC film is typically obtained by forming a PVC composition containing a predetermined component into a film by a known method. Here, the PVC composition refers to a composition in which the main component (refers to the most contained component, which may be contained in an amount exceeding 50% by weight) is PVC. According to such a PVC composition, a PVC film (typically a film made of a soft PVC resin) exhibiting suitable physical properties as a base material (support base material) of an adhesive tape can be formed. The content of PVC in the PVC film is typically more than 40% by weight, and usually 50% by weight or more is appropriate. The technique disclosed here can be preferably implemented in an embodiment in which the PVC content in the PVC film is more than 50% by weight (typically 55% by weight or more). The PVC content may be 60% by weight or more.

(PVC)
The PVC constituting the PVC composition may be various polymers having vinyl chloride as a main monomer (which is a main component of the monomer component and may be a monomer occupying more than 50% by weight of the monomer component). That is, the concept of PVC here includes not only a homopolymer of vinyl chloride but also copolymers of vinyl chloride and various comonomers. Examples of the comonomer include vinylidene chloride; olefins such as ethylene and propylene (preferably olefins having 2 to 4 carbon atoms); acrylic acid and methacrylic acid (hereinafter, acryl and methacryl are collectively referred to as “(meth) acryl”), Carboxyl group-containing monomers such as maleic acid and fumaric acid, or acid anhydrides thereof (maleic anhydride, etc.); (meth) acrylic acid esters such as (meth) acrylic acid and alkyl alcohols or cycloalkyl alcohols having about 1 to 10 carbon atoms And esters; vinyl ester monomers such as vinyl acetate and vinyl propionate; styrene monomers such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyltoluene; acrylonitrile; and the like. As the copolymer, those having a vinyl chloride copolymerization ratio of 70% by weight or more (more preferably 90% by weight or more) are preferable. PVC is obtained by polymerizing such monomers by an appropriate method (typically suspension polymerization).

  Although it does not specifically limit, the average degree of polymerization of PVC contained in a PVC composition may be about 800-1800 grade, for example. In consideration of the balance between workability (moldability) and strength, an average degree of polymerization of about 800 to 1600 (for example, about 900 to 1500) is usually appropriate. From the viewpoint of reducing the amount of adhesion, in one embodiment, PVC having an average degree of polymerization higher than 1000 (for example, an average degree of polymerization of 1100 or more, more preferably 1200 or more) can be preferably employed.

(Plasticizer)
As the plasticizer, various materials known to exhibit the plasticizing effect of PVC can be used without particular limitation. Examples of the plasticizer include aromatics such as benzoic acid esters (such as benzoic acid glycol esters), phthalic acid esters, terephthalic acid esters (such as di-2-ethylhexyl terephthalate), trimellitic acid esters, and pyromellitic acid esters. Carboxylic acid ester; Aliphatic carboxylic acid ester such as adipic acid ester, sebacic acid ester, azelaic acid ester, maleic acid ester, citrate ester (tributyl acetylcitrate, etc.); Polyester of polyvalent carboxylic acid and polyhydric alcohol: Other examples include polyether polyesters, epoxy polyesters (epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, epoxidized fatty acid alkyl esters, etc.), phosphate esters (tricresyl phosphate, etc.). Limited to There. A plasticizer can be used individually by 1 type or in combination of 2 or more types as appropriate.

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

  As the trimellitic acid ester (trimellitic acid ester plasticizer), for example, a trimester of trimellitic acid and an alkyl alcohol having 6 to 14 carbon atoms (typically 8 to 12) can be used. Preferable examples include tri-n-octyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, triisononyl trimellitic acid, tri-n-decyl trimellitic acid, triisodecyl trimellitic acid, and the like.

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

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

  Examples of the polyester (polyester plasticizer) include polyvalent carboxylic acids such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid. , (Poly) ethylene glycol (herein, “(poly) ethylene glycol” means generically ethylene glycol and polyethylene glycol, the same shall apply hereinafter), (poly) propylene glycol, (poly) butylene glycol, Polyester compounds obtained from (poly) hexanediol, (poly) neopentyl glycol, polyhydric alcohols such as polyvinyl alcohol can be used. As said polyvalent carboxylic acid, C4-C12 (typically 6-10) aliphatic dicarboxylic acid is preferable, and adipic acid and sebacic acid are mentioned as a suitable example. In particular, adipic acid is desirable in terms of versatility and price. The polyhydric alcohol is preferably an aliphatic diol having 2 to 10 carbon atoms, and preferred examples include ethylene glycol and butylene glycol (for example, 1,3-butanediol, 1,4-butanediol).

  The content of the plasticizer in the PVC film is not particularly limited. The content of the plasticizer can be appropriately set so that, for example, a desired plasticizing effect can be obtained and the amount of adhesion of the PVC adhesive tape can be suppressed to a predetermined value or less. The content of the plasticizer is usually suitably 1% by weight or more (typically 5% by weight or more, for example, 10% by weight or more) of the PVC film, from the viewpoint of obtaining a better plasticizing effect. It is preferable to set it as 15 weight% or more. The content of the plasticizer may be 20% by weight or more, and further may be 25% by weight or more (for example, 30% by weight or more). Further, the content of the plasticizer can be, for example, 60% by weight or less of the PVC film, and is usually preferably 50% by weight or less and 40% by weight or less from the viewpoint of reducing the amount of adhesion. It is more preferable. The technique disclosed herein can be preferably implemented in an embodiment in which the plasticizer content is 35% by weight or less (typically less than 35% by weight, for example, 33% by weight or less) of the PVC film.

  Although it does not specifically limit, the usage-amount of the plasticizer with respect to 100 weight part of PVC is usually suitably 15-75 weight part, It is preferable to set it as 20-60 weight part, 30-50 weight part More preferably.

  In a preferred embodiment of the technology disclosed herein, the PVC film includes a combination of a polyester plasticizer having a molecular weight of 1000 or more and a carboxylic acid ester having a molecular weight of less than 1000 as a plasticizer. According to such an embodiment, it is easy to obtain a PVC pressure-sensitive adhesive tape in which the amount of adhesion is suppressed to a predetermined value or less and which exhibits good flexibility.

  In general, a polyester plasticizer having a molecular weight of 1000 or more is less likely to volatilize even at high temperatures, and is therefore suitable for reducing the amount of adhesion (and thus improving fogging prevention). On the other hand, polyester plasticizers having a molecular weight of 1000 or more have a lower plasticizing effect due to the viscosity of the plasticizer itself at low temperatures. For this reason, the flexibility required for the PVC adhesive tape tends to be insufficient. On the other hand, a carboxylic acid ester having a molecular weight of less than 1000 is excellent in the effect of developing flexibility even at low temperatures, but tends to volatilize at high temperatures and easily cause fogging.

  The present inventors show that by using a combination of a polyester plasticizer (PLH) having a molecular weight of 1000 or more and a carboxylic acid ester (PLL) having a molecular weight of less than 1000, volatilization of the PLL at a high temperature is suppressed. I found it. Furthermore, the present inventors have found that the amount of adhesion is effectively reduced in a PVC tape using a PVC film having a composition containing a plasticizer, and good antifogging properties can be obtained. In implementing the technique disclosed here, it is not necessary to clarify the reason why the above-described effect is obtained, but it is considered that the volatility of the PLL is probably lowered by the intermolecular interaction between the PLL and the PLH. In addition, the present inventors have found that the adhesive tape using a PVC film containing a combination of PLL and PLH has a change in adhesive force over time (typically compared to the case where a PVC film containing PLL alone is used as a plasticizer. In particular, it has been found that the decrease in adhesive strength is suppressed. This is considered to be due to the transition of the adhesive strength over time to the transition of the PLL to the adhesive layer. By using PLH in combination with the PLL, the intermolecular interaction between the PLL and the PLH is probably It is considered that the transition of the PLL to the pressure-sensitive adhesive layer was suppressed by the interaction between PLH and PVC, and the change with time of the adhesive force was suppressed. In this way, by using a combination of PLH and PLL, it is possible to achieve a higher level of antifogging properties and other characteristics as compared with a configuration using PLH or PLL alone.

  In this specification, “molecular weight” for a plasticizer means a weight average molecular weight ascertained based on “(2-2) molecular weight analysis by GPC” described later.

  As the carboxylic acid ester (PLL) having a molecular weight of less than 1000, one of the above aromatic carboxylic acid ester, aliphatic carboxylic acid ester and polyester having a molecular weight of less than 1000 may be used alone or in combination of two or more. They can be used in combination. For example, phthalic acid ester (di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, etc.), adipic acid ester (di-n-octyl adipate, di-2-adipate) Ethylhexyl, diisononyl adipate, etc.), trimellitic acid ester (trimellitic acid tri-n-octyl, trimellitic acid tri-2-ethylhexyl etc.), pyromellitic acid ester (pyromellitic acid tetra-n-octyl, pyromellitic acid) Tetra-2-ethylhexyl, pyromellitic acid tetra-n-decyl, etc.), citric acid ester, sebacic acid ester, azelaic acid ester, maleic acid ester, benzoic acid ester and the like can be used.

  As the PLL, an aromatic carboxylic acid ester can be preferably used. Of these, ester compounds derived from trifunctional or higher (typically trifunctional or tetrafunctional) aromatic carboxylic acids are preferred, and specific examples include trimellitic acid esters and pyromellitic acid esters. Such PLL is easy to exhibit the effect by the above-mentioned intermolecular interaction, and has good compatibility with PVC. Moreover, it is preferable also in the point which has a tendency for low volatility compared with the ester compound derived from monofunctional or bifunctional aromatic carboxylic acid.

  The molecular weight of PLL is typically 250 or more, preferably 400 or more, more preferably 500 or more from the viewpoint of suppressing volatilization and reducing the amount of adhesion. The technique disclosed herein can be preferably implemented in an embodiment using a PLL having a molecular weight of 600 or more (more preferably 650 or more, for example 700 or more). The upper limit of the molecular weight of PLL is not particularly limited as long as it is less than 1000. From the viewpoint of handling properties and the like, usually, a PLL having a molecular weight of 950 or less (for example, 900 or less) can be preferably used.

  6 or more are preferable and, as for carbon number of the ester residue in PLL, 8 or more are more preferable. Such a PLL is likely to exhibit the effect of the above-described intermolecular interaction. It is also preferable in that the volatility tends to decrease due to an increase in molecular weight. Furthermore, when the molecular chain is lengthened, the flexibility is increased and the liquid form is easily obtained at room temperature, and the handling property is improved. The upper limit of the number of carbon atoms of the ester residue is not particularly limited, but is usually 16 or less, preferably 14 or less, more preferably 12 or less (for example, 10 or less) from the viewpoints of handling properties and compatibility with PVC. . Preferable examples of the ester residue in PLL include n-octyl group, 2-ethylhexyl group, n-decyl group, isodecyl group and the like. In one embodiment, a PLL in which the ester residue is a branched alkyl group such as a 2-ethylhexyl group or an isodecyl group can be preferably used.

  Although it does not specifically limit, the compounding quantity of PLL with respect to 100 weight part of PVC (The total amount when using 2 or more types) is usually less than 75 weight part, Preferably it is less than 60 weight part, More preferably Less than 50 parts by weight. From the viewpoint of easily reducing the amount of adhesion, the blending amount of PLL with respect to 100 parts by weight of PVC is advantageously 30 parts by weight or less, preferably 20 parts by weight or less, and 15 parts by weight or less. Is more preferable. The technique disclosed here can also be preferably implemented in an embodiment where the blending amount of PLL with respect to 100 parts by weight of PVC is 10 parts by weight or less. The lower limit of the blending amount of PLL can be set so as to obtain desired flexibility, but is usually 1 part by weight or more (preferably 3 parts by weight or more, for example, 5 parts by weight or more with respect to 100 parts by weight of PVC. ) Is appropriate.

  As the polyester plasticizer (PLH) having a molecular weight of 1000 or more, those having a molecular weight of 1000 or more among the polyester plasticizers as described above can be used singly or in combination of two or more. From the viewpoint of plasticizing effect and flexibility at low temperature, polyesters of aliphatic dicarboxylic acids having 4 to 12 carbon atoms (typically 6 to 10 carbon atoms) and polyhydric alcohols are preferred. Of these, an adipic acid-based polyester plasticizer obtained from a dicarboxylic acid mainly composed of adipic acid and an aliphatic diol such as neopentyl glycol, propylene glycol, or ethylene glycol is preferable. This is because such adipic acid-based polyester plasticizers are rich in intermolecular interaction with PLL and PVC, thereby exhibiting the effect of suppressing the volatilization of PLL and further suppressing the volatility of PLH itself. .

  As commercial products that can be used as PLH in the technology disclosed herein, specifically, trade names “W-230H”, “W-1020EL”, “W-1410EL”, and “W-2050” of DIC Corporation. , “W-2300”, “W-2310”, “W-2360”, “W-360ELS”, “W-4010”, etc .; trade names “P-300”, “PN-250” of ADEKA Corporation “PN-400”, “PN-650”, “PN-1030”, “PN-1430” and the like; trade name “HA-5” of Kao Corporation and the like.

  The molecular weight of PLH is not particularly limited as long as it is 1000 or more. From the viewpoint of reducing the amount of adhesion, it is usually advantageous to use PLH having a molecular weight of 2000 or more (for example, 3000 or more). The technique disclosed herein can be preferably implemented in an embodiment using PLH having a molecular weight of 4000 or more (for example, 5000 or more). The upper limit of the molecular weight of PLH is not particularly limited, but it is usually suitably less than 100,000. From the viewpoint of better exhibiting the plasticizing effect of PVC and easily realizing the flexibility required for the PVC adhesive tape, the molecular weight of PLH is preferably less than 50000, more preferably less than 25000, and even more preferably less than 10,000 (for example, 7000 or less).

  Although not particularly limited, it is appropriate that the blending amount of PLH with respect to 100 parts by weight of PVC (the total amount thereof when two or more are used) is usually less than 75 parts by weight, and the amount of adhesion From the viewpoint of facilitating reduction, it is preferably less than 60 parts by weight, and more preferably less than 50 parts by weight (for example, less than 45 parts by weight). The lower limit of the blending amount of PLH can be set so as to obtain a desired flexibility, but is usually 5 parts by weight or more (preferably 8 parts by weight or more, for example, 10 parts by weight or more with respect to 100 parts by weight of PVC. ) Is appropriate. The technique disclosed herein can be preferably implemented in an embodiment in which the blending amount of PLH with respect to 100 parts by weight of PVC is 15 parts by weight or more, further 20 parts by weight or more (for example, 25 parts by weight or more, and further 30 parts by weight or more). .

The ratio of the amount of PLH to the amount of PLL is not particularly limited. For example, the ratio (W _PLH / W _PLL ) of the weight W _PLH of the PLH to the weight W _PLL of the PLL included in the PVC film can be about 0.1 to 500. From the viewpoint of reducing the amount of adhesion, it is usually advantageous to set W _PLH / W _PLL to 0.5 to 100, preferably 1 to 50. In a preferred embodiment, the anti-fogging property and other characteristics (inhibition of change in adhesive force with time, flexibility in a wide temperature range, etc.) can be achieved at a higher level. In one preferred embodiment, W _PLH / W _{PLL is set} to 1 to 25. 1 to 15 (for example, 1 to 10) is more preferable, and 1 to 8 (for example, 1 to 5) is further preferable.

(Elastomer)
The PVC film in the technology disclosed herein may contain an elastomer in addition to PVC and a plasticizer. Inclusion of an elastomer in the PVC film improves the low-temperature properties (for example, flexibility at low temperatures) of the PVC adhesive tape, and improves the mechanical strength of the PVC film (for example, the desired mechanical properties can be achieved even if the PVC film is made thinner). An effect such as that strength can be obtained can be realized.

  Various known polymer materials can be used as the elastomer. Non-limiting examples of such elastomers include chlorinated polyethylene (CPE), ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer (eg, vinyl acetate content of about 10% by weight or more, Specifically, it is about 10 to 25% by weight of vinyl chloride-vinyl acetate copolymer), (meth) acrylic ester-butadiene-styrene copolymer (for example, methyl methacrylate-butadiene-styrene copolymer), acrylonitrile. A butadiene-styrene copolymer, an acrylonitrile-butadiene copolymer, a styrene-butadiene copolymer (typically a styrene-butadiene block copolymer such as a styrene content of about 35% by weight or less, typically About 10 to 35% by weight of styrene-butadiene block copolymer), styrene-butyl Examples include diene-styrene block copolymers, chlorosulfonated polyethylene (CSM), polyester-based thermoplastic elastomers, thermoplastic polyurethanes, other synthetic rubbers (isoprene rubber, butadiene rubber, etc.), and composites and modified products thereof. It is done. An elastomer can be used individually by 1 type or in combination of 2 or more types.

  In the technique disclosed herein, it is preferable to select a material having good compatibility with PVC as the elastomer to be contained in the PVC film. Thereby, the low temperature characteristic of a PVC film and the PVC adhesive tape using this PVC film can be improved effectively. The elastomer is preferably used in a composition (content) within a range in which a good compatibility state is realized in the PVC film from the viewpoint of the appearance quality and the like of the PVC adhesive tape. The compatible state can be grasped by, for example, observing the presence or absence of white turbidity in a state where the PVC film is stretched as it is or stretched (for example, stretched about twice in the flow direction).

  Non-limiting examples of elastomers that may be preferably used in the art disclosed herein include chlorinated polyethylene (eg, having a chlorine content of about 25-50% by weight, typically about 30-45% by weight, preferably Chlorinated polyethylene which is approximately 35 to 45% by weight), (meth) acrylic acid ester-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer (for example, acrylonitrile content is approximately 15 to 50% by weight, typically Is about 25 to 45% by weight, preferably about 30 to 40% by weight acrylonitrile-butadiene copolymer), ethylene-vinyl acetate copolymer (eg, vinyl acetate content is about 30 to 75% by weight, typical The ethylene-vinyl acetate copolymer is approximately 40 to 70% by weight, preferably approximately 50 to 65% by weight) And the like.

  The content of the elastomer in the PVC film is not particularly limited, and can be set so as to obtain a desired effect. Usually, the content of the elastomer in the PVC film is suitably about 0.5% by weight or more, and preferably about 1% by weight or more from the viewpoint of obtaining a higher effect. From the viewpoint of compatibility and the like, the content of the elastomer in the PVC film is usually suitably less than about 40% by weight, preferably about 35% by weight or less, and about 30% by weight (for example, About 25% by weight or less) is more preferable. In the technique disclosed herein, the content of the elastomer in the PVC film is about 1 to 20% by weight (typically about 1 to 15%) from the viewpoint of easily balancing the effects of using the elastomer with other properties. %, Preferably about 1 to 10% by weight, for example about 3 to 8% by weight).

  The elastomer content is not particularly limited. The content of the elastomer with respect to 100 parts by weight of PVC can be, for example, 0.5 parts by weight or more, usually 1 part by weight or more is appropriate, and 2 parts by weight or more is preferable from the viewpoint of obtaining a higher effect. In addition, from the viewpoint of easily balancing the effects of the use of the elastomer with other characteristics, the content of the elastomer with respect to 100 parts by weight of PVC is usually 40 parts by weight or less, and 30 parts by weight or less is appropriate. preferable. In a preferred embodiment, the content of the elastomer with respect to 100 parts by weight of PVC can be 3 to 20 parts by weight (for example, 5 to 15 parts by weight).

(Fatty acid metal salt)
The PVC film in the technology disclosed herein preferably contains a fatty acid metal salt in addition to PVC and a plasticizer. The PVC film receives physical energy such as heat, ultraviolet rays or shearing force when the PVC film or the PVC adhesive tape is processed or in the usage environment of the adhesive tape. May be discolored by a chemical reaction or the like, or may deteriorate physical, mechanical, or electrical characteristics. By containing a fatty acid metal salt in the PVC film, the fatty acid metal salt can function as a stabilizer for preventing or suppressing the chemical reaction. Further, preventing or suppressing the above chemical reaction (typically desorption of hydrogen chloride) can advantageously contribute to the reduction of the adhesion amount measured for the PVC adhesive tape, and thus the improvement of fogging prevention property. .

  As a fatty acid metal salt, the compound which can function as a stabilizer of a PVC film can be used individually by 1 type or in combination of 2 or more types. For example, the fatty acid constituting the fatty acid metal salt is a saturated or unsaturated fatty acid (hydroxy fatty acid) having about 10 to 20 carbon atoms (typically 12 to 18), such as lauric acid, ricinoleic acid, and stearic acid. Preferably). From the viewpoint of moldability and workability of the PVC film, a stearic acid metal salt can be preferably used. Moreover, lauric acid metal salt can be preferably used from a viewpoint of the temporal change suppression of a PVC film or a PVC pressure-sensitive adhesive tape, flexibility at a low temperature, and the like. In a preferred embodiment, a metal stearate and a metal laurate can be used in combination. In this case, the ratio of the amount of the lauric acid metal salt to the amount of the stearic acid metal salt used is not particularly limited, but can be, for example, 0.1 to 10 on a weight basis, usually 0.2 to 5 (Typically about 0.5 to 2, for example, about 0.8 to 1.2) is appropriate.

  As the metal constituting the fatty acid metal salt, metals other than lead (non-lead metal) are preferably used in consideration of the recent increase in awareness of environmental health. According to the technology disclosed herein, a PVC pressure-sensitive adhesive tape exhibiting good antifogging properties can be realized even in an embodiment in which a stabilizer containing lead is not used. As the metal, for example, a metal element belonging to any of Group 1, Group 2, Group 12, Group 13 and Group 14 (excluding Pb) of the periodic table can be selected, and Li, Na, Ca, Mg, Zn, Ba and Sn are mentioned. As said fatty acid metal salt, Ca salt and Ba salt can be preferably employ | adopted from viewpoints, such as cost and availability. Moreover, Zn salt can be preferably employ | adopted from viewpoints, such as the moldability of a PVC film, workability. In a preferred embodiment, a Ca salt and a Zn salt can be used in combination. In this case, the ratio of the used amount of the Zn salt to the used amount of the Ca salt is not particularly limited, but can be, for example, about 0.1 to 10 on a weight basis, and usually about 0.2 to 5 (typically In particular, it is appropriate to set to about 0.5 to 2, for example, about 0.8 to 1.2). The technology disclosed herein can be preferably implemented, for example, in an embodiment that includes Ca stearate and Zn laurate in the above weight ratio or an embodiment that includes Zn stearate and Ca laurate in the above weight ratio. Moreover, the aspect which contains either stearate Ca, Zn stearate, lauric acid Ca, and lauric acid Zn (for example, Ca stearate) independently may be implemented preferably. In applications where the use of the fatty acid Pb salt is allowed, the PVC film can contain the fatty acid Pb salt.

  The amount of fatty acid metal salt used (when two or more types are used, the total amount thereof) is not particularly limited, and can be, for example, an amount that is about 0.01% by weight or more of the PVC film. From the viewpoint of obtaining a higher effect, it is usually appropriate that the content of the fatty acid metal salt is about 0.02% by weight or more of the PVC film, preferably about 0.05% by weight or more. More preferably, it is 0.08% by weight or more. The technique disclosed herein is an embodiment in which the content of the fatty acid metal salt in the PVC film is about 0.10% by weight (typically about 0.12% by weight or more, for example, about 0.15% by weight or more). However, it can be preferably implemented. The upper limit of the content of the fatty acid metal salt is not particularly limited, but usually it is suitably about 5% by weight or less of the PVC film, and preferably about 3% by weight or less from the viewpoint of flexibility at low temperatures. More preferably, it is about 1% by weight or less (typically about 0.5% by weight or less, for example, about 0.3% by weight or less).

(Antioxidant)
The PVC film in the technology disclosed herein can contain an antioxidant in addition to PVC and a plasticizer. By containing an antioxidant in the PVC film, the heat resistance of the PVC film can be improved, and for example, an event in which the PVC film deteriorates (degenerates) and causes decomposition products thereof can be suppressed. Thereby, it is possible to suppress an increase in the amount of adhesion due to volatilization of the decomposed material and the like, thereby improving the fogging prevention property.

  As the antioxidant, a known material capable of exhibiting an antioxidant function can be used without particular limitation. Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, and the like. An antioxidant can be used individually by 1 type or in combination of 2 or more types.

  Preferable examples of the antioxidant include phenolic antioxidants such as hindered phenolic antioxidants. As the hindered phenol-based antioxidant, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name “Irganox 1010”, manufactured by Ciba Japan) , Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name “Irganox 1076”, manufactured by Ciba Japan), 4,6-bis (dodecylthiomethyl) -o-cresol (Trade name “Irganox 1726”, manufactured by Ciba Japan), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name “Irganox 245”, Ciba Japan ), Screw (2,2,6,6-tetra) Til-4-piperidyl) sebacate (trade name “TINUVIN770”, manufactured by Ciba Japan), polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol ( And dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate) (trade name “TINUVIN622”, manufactured by Ciba Japan). Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name “Irganox 1010”, manufactured by Ciba Japan), triethylene glycol-bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name “Irganox 245”, manufactured by Ciba Japan) is preferable.

  The amount of antioxidant used (the total amount when two or more are used) is not particularly limited. For example, the amount of the antioxidant in the PVC film is about 0.001% by weight or more. can do. From the viewpoint of obtaining a higher effect, it is usually appropriate that the content of the antioxidant in the PVC film is about 0.005% by weight or more, and preferably about 0.01% by weight or more. It is more preferable to set it as 0.05 weight% or more. In a preferred embodiment, the content of the antioxidant in the PVC film can be about 0.1% by weight or more, can be about 0.5% by weight or more, and further can be about 1% by weight (for example, about 1% by weight). .5% by weight or more). The upper limit of the content of the antioxidant is not particularly limited, but it is usually appropriate to set it to about 10% by weight or less (typically about 5% by weight or less, for example, about 3% by weight or less) of the PVC film. .

  The PVC film in the technology disclosed herein may further contain a known additive that can be used for a PVC film (particularly, a PVC film for a PVC adhesive tape), as long as the effects of the present invention are not significantly hindered. It can be included. Examples of such additives include colorants such as pigments and dyes, stabilizers other than fatty acid metal salts (eg, organotin compounds such as dioctyltin laurate), and stabilizing aids (eg, trialkyl phosphites) Phosphites, inorganic compounds such as hydrotalcite and zeolite), light stabilizers, ultraviolet absorbers, modifiers, flame retardants, antistatic agents, antifungal agents, lubricants and the like. These additives can be used in amounts common in the field of PVC films.

  A PVC film having such a composition is typically obtained by molding a PVC composition having a corresponding composition into a film shape by a method known in the field of thermoplastic resin films. As such a known molding method, for example, a melt extrusion molding method (inflation method, T-die method, etc.), a melt-flow method, a calendar method, or the like can be used. The technique disclosed here is also preferable in an embodiment in which the PVC film is not subjected to a treatment that intentionally increases the crosslinkability of the entire PVC film, such as addition of a crosslinking agent or irradiation of active energy rays. Can be implemented. According to such a PVC film, a more flexible PVC adhesive tape tends to be obtained.

As an example, an outline of a typical film production procedure when the calendar method is used is shown below.
(1) Weighing: PVC, plasticizer and other materials used as needed are weighed according to the target composition.
(2) Mixing: Each weighed material is stirred and mixed to prepare a uniform mixture (typically a powdery mixture, that is, a mixed powder).
(3) Kneading: The mixture prepared in (2) above is heated and melted, and kneaded with two to three or more kneading rolls (typically metal rolls). The temperature of the kneading roll is suitably set to, for example, 100 ° C. to 250 ° C. (preferably 150 ° C. to 200 ° C.).
(4) Calendar molding: The kneaded product obtained in (3) above is charged into a calendar molding machine to mold a PVC film having an arbitrary thickness. The thickness can be controlled by adjusting the gap between the calender rolls and / or the speed ratio between the rolls.

  In the pressure-sensitive adhesive tape disclosed herein, the PVC film may constitute a single-layer or multilayer support substrate made of the PVC film, and a support substrate including other layers in addition to the PVC film. You may comprise. In a preferred embodiment, the other layer may be an auxiliary layer such as a printing layer, a release treatment layer, or a primer layer provided on the surface of the PVC film. Or the said PVC film may comprise the support base material of the structure by which this PVC film was laminated | stacked with resin films other than a PVC film. As a preferable embodiment, there may be mentioned a configuration in which an adhesive layer is disposed on one side of a supporting substrate made of a single layer PVC film.

  The thickness of the support substrate is not particularly limited. The thickness of the supporting substrate (for example, a supporting substrate made of a single-layer PVC film) is typically 500 μm or less, usually 300 μm or less, and preferably 200 μm or less from the viewpoint of the handleability of the PVC adhesive tape. 150 μm or less is more preferable, for example, 120 μm or less may be used. The thickness of the supporting substrate is typically 10 μm or more, usually 25 μm or more, preferably 50 μm or more, more preferably 60 μm or more (for example, 75 μm or more) from the viewpoint of strength and handling properties. The thickness of the support substrate is, for example, protection and bundling of electric wires and pipes, covering of a corrugated tube that surrounds and protects electric wires, covering a bundle of multiple electric wires (focusing electric wires), electrical insulation It can be preferably applied to an adhesive tape used for, etc.

  Corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of primer (primer), antistatic treatment, etc., as necessary, on the surface of the support substrate on which the pressure-sensitive adhesive layer is disposed The conventionally known surface treatment may be applied. Such a surface treatment may be a treatment for improving the adhesion between the base material and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material. The composition of the primer is not particularly limited and can be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, but is usually preferably 0.01 μm or more and 1 μm or less, more preferably 0.1 μm or more and 1 μm or less.

  In the PVC pressure-sensitive adhesive tape having a configuration in which the pressure-sensitive adhesive layer is disposed only on one surface of the supporting base material, on the surface (back surface) on the side where the pressure-sensitive adhesive layer is not disposed, the printability is improved, the light reflectivity is reduced, and the overlap is performed. For the purpose of improving adhesiveness, the back surface may be subjected to treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment. Moreover, conventionally well-known surface treatments, such as a peeling process and an antistatic process, may be given to the back surface of the PVC adhesive tape as needed. For example, by providing a long-chain alkyl-based or silicone-based release treatment layer on the back surface of the substrate, the unwinding force of the PVC pressure-sensitive adhesive tape wound in a roll shape can be reduced. The PVC adhesive tape disclosed here can be preferably implemented even in a form in which the back surface of the PVC adhesive tape is not subjected to the above-described peeling treatment.

<Adhesive layer>
The pressure-sensitive adhesive layer in the technology disclosed herein typically exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature, and has a property of easily adhering to an adherend by pressure ( It is a layer composed of an adhesive. The adhesive here is generally defined as “CA Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”, and generally has a complex tensile modulus E ^* (1 Hz). <10 < ⁷ > dyne / cm < ² > material (typically a material having the above properties at 25 [deg.] C.).

  The pressure-sensitive adhesive layer in the technology disclosed herein includes a water-dispersed pressure-sensitive adhesive composition, a water-soluble pressure-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, a hot-melt pressure-sensitive adhesive composition, and an active energy ray-curable pressure-sensitive adhesive composition. It can be a pressure-sensitive adhesive layer formed from various forms of pressure-sensitive adhesive compositions. Here, the “active energy ray” refers to an energy ray having an energy that can cause a chemical reaction such as a polymerization reaction, a crosslinking reaction, or a decomposition of an initiator, and light such as ultraviolet rays, visible rays, infrared rays, and α rays. , Β-ray, γ-ray, electron beam, neutron beam, X-ray radiation and other concepts. A pressure-sensitive adhesive layer formed from a water-dispersed pressure-sensitive adhesive composition is preferred because it prevents the plasticizer in the PVC film from being transferred to the pressure-sensitive adhesive layer and easily suppress changes in adhesive strength over time.

  The kind of pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. The above-mentioned pressure-sensitive adhesives are various rubbery polymers such as rubber polymers, acrylic polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, fluorine polymers and the like known in the field of pressure-sensitive adhesives. 1 type or 2 types or more may be included as a base polymer (the main component of the polymer component). Here, the rubber-based pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a rubber-based polymer as a base polymer. The same applies to acrylic pressure-sensitive adhesives and other pressure-sensitive adhesives. The acrylic polymer refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule (acrylic monomer) in the polymer structure. A polymer containing a monomer unit derived from a monomer in a proportion exceeding 50% by weight. In addition, the said (meth) acryloyl group is the meaning which points out an acryloyl group and a methacryloyl group comprehensively.

  As the pressure-sensitive adhesive layer of the PVC pressure-sensitive adhesive tape disclosed herein, a pressure-sensitive adhesive layer (rubber-based pressure-sensitive adhesive layer) mainly composed of a rubber-based pressure-sensitive adhesive can be preferably used. The rubber-based pressure-sensitive adhesive may contain one or more rubber-based polymers selected from natural rubber and synthetic rubber. In the present specification, the “main component” refers to a component that is contained in the largest amount unless otherwise specified, and typically refers to a component that is contained in an amount exceeding 50% by weight. As the rubber-based polymer, both natural rubber and synthetic rubber can be used. As the natural rubber, known materials that can be used for the pressure-sensitive adhesive composition can be used without particular limitation. The term “natural rubber” as used herein is not limited to unmodified natural rubber, but is a concept including, for example, modified natural rubber modified with acrylic acid ester or the like. Unmodified natural rubber and modified natural rubber may be used in combination. As the synthetic rubber, known materials that can be used for the pressure-sensitive adhesive composition can be used without any particular limitation. Preferable examples include styrene-butadiene rubber (SBR), styrene-isoprene rubber, chloroprene rubber and the like. These synthetic rubbers may be unmodified or modified (for example, carboxy-modified). A rubber-type polymer can be used individually by 1 type or in combination of 2 or more types.

  A PVC pressure-sensitive adhesive tape according to a preferred embodiment has a rubber-based pressure-sensitive adhesive layer formed from a water-dispersed rubber-based pressure-sensitive adhesive composition obtained by blending a rubber-based latex with a tackifying resin or other additives as necessary. . The rubber latex may be one in which various known rubber polymers are dispersed in water. Either natural rubber latex or synthetic rubber latex can be used. As the natural rubber latex, known materials that can be used for the pressure-sensitive adhesive composition can be used without any particular limitation. The natural rubber latex as used herein is not limited to an unmodified natural rubber latex, and is a concept including a modified natural rubber latex modified with, for example, an acrylate ester. An unmodified natural rubber latex and a modified natural rubber latex may be used in combination. As the synthetic rubber latex, known materials that can be used for the pressure-sensitive adhesive composition can be used without any particular limitation. Preferable examples include styrene-butadiene rubber latex (SBR latex), styrene-isoprene rubber latex, chloroprene rubber latex and the like. The synthetic rubber contained in these synthetic rubber latexes may be unmodified or modified (for example, carboxy-modified). The rubber latex can be used alone or in combination of two or more.

  A rubber-based pressure-sensitive adhesive composition according to a preferred embodiment (for example, a water-dispersed rubber-based pressure-sensitive adhesive composition) contains both natural rubber and synthetic rubber as a rubber-based polymer. According to such a pressure-sensitive adhesive composition, a PVC pressure-sensitive adhesive tape showing good pressure-sensitive adhesive properties can be formed. For example, a PVC pressure-sensitive adhesive tape having adhesive properties suitable for applications such as protection and bundling of electric wires and pipes, coating of corrugated tubes as described above, covering of converging wires, and electrical insulation can be formed. The weight ratio of natural rubber to synthetic rubber (natural rubber: synthetic rubber) is preferably in the range of about 10:90 to 90:10, more preferably in the range of about 20:80 to 80:20, and about 30:70. The range of ˜70: 30 is more preferable. SBR can be preferably adopted as the synthetic rubber.

  The pressure-sensitive adhesive layer (typically a rubber-based pressure-sensitive adhesive layer) in the technology disclosed herein can contain a tackifying resin in addition to the base polymer as described above. As the tackifier resin, an appropriate one can be selected from various known tackifier resins. For example, 1 type (s) or 2 or more types selected from various tackifier resin, such as rosin resin, petroleum resin, terpene resin, phenol resin, coumarone indene resin, and ketone resin, can be used.

  Examples of the rosin resin include disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, rosin derivatives such as fumarated rosin, phenol-modified rosin, rosin ester, and the like. Examples of the phenol-modified rosin include those obtained by adding a phenol to a natural rosin or rosin derivative, or a phenol-modified rosin obtained by reacting a resole-type phenol resin with a natural rosin or rosin derivative. It is done. Examples of the rosin ester include esterified products obtained by reacting the rosin resin with a polyhydric alcohol. Note that the rosin phenol resin may be an esterified product.

  Examples of terpene resins include terpene resins (α-pinene resin, β-pinene resin, limonene resin, etc.), terpene phenol resins, aromatic modified terpene resins, hydrogenated terpene resins, and the like.

  Examples of petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, aliphatic / aromatic copolymer (C5 / C9) petroleum resins, and hydrogenated products thereof ( Examples thereof include alicyclic petroleum resins obtained by hydrogenating aromatic petroleum resins) and various modified products thereof (for example, maleic anhydride modified products).

  Examples of phenolic resins include condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin and formaldehyde. Other examples of phenolic resins include resole obtained by addition reaction of the above phenols with formaldehyde in the presence of an alkali catalyst, and novolak obtained by condensation reaction of the above phenols with formaldehyde in the presence of an acid catalyst. It is done.

  Examples of the coumarone indene resin include coumarone indene resin, hydrogenated coumarone indene resin, phenol-modified coumarone indene resin, epoxy-modified coumarone indene resin, and the like.

  Examples of the ketone resin include ketone resins obtained by condensation of ketones (for example, aliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, and alicyclic ketones such as cyclohexanone and methylcyclohexanone) and formaldehyde.

  The softening temperature of the tackifying resin used is not particularly limited. For example, a tackifying resin having a softening point of 60 to 160 ° C. can be used. Moreover, you may use liquid tackifying resin at normal temperature. A tackifying resin having a softening point of about 60 to 140 ° C. (more preferably about 80 to 120 ° C.) from the viewpoint of achieving a good balance between cohesion and low temperature characteristics (for example, unwinding properties and adhesive strength at low temperatures). It can be preferably used. For example, it is preferable to use a petroleum resin having a softening point in the above range. In addition, the softening point of tackifying resin can be measured based on the softening point test method (ring ball method) prescribed | regulated to JISK2207.

  The ratio of the polymer component contained in the pressure-sensitive adhesive layer and the tackifier resin is not particularly limited, and can be appropriately determined depending on the application. The content of the tackifier resin with respect to 100 parts by weight of the polymer component can be, for example, about 20 parts by weight or more, usually about 50 parts by weight or more, based on the nonvolatile content. From the viewpoint of obtaining a higher use effect, the amount of the tackifier resin used relative to 100 parts by weight of the polymer component can be about 80 parts by weight or more, or about 100 parts by weight or more. On the other hand, from the viewpoint of low-temperature characteristics and the like, usually, the amount of tackifying resin used is suitably about 200 parts by weight or less, preferably about 150 parts by weight or less, based on 100 parts by weight of the polymer component.

  In addition, the pressure-sensitive adhesive layer comprises a viscosity modifier (thickener, etc.), leveling agent, plasticizer, softener, filler, colorant such as pigment or dye, light stabilizer, anti-aging agent, antioxidant. In addition, various additives that are common in the field of pressure-sensitive adhesives such as water-resistant agents, antistatic agents, foaming agents, antifoaming agents, surfactants, preservatives, and crosslinking agents may be contained as necessary. .

  The pressure-sensitive adhesive layer can be formed by appropriately adopting various conventionally known methods. For example, a method (direct method) in which a pressure-sensitive adhesive composition is directly applied (typically applied) to a base material (typically a PVC film) as described above, and then dried to form a pressure-sensitive adhesive layer is employed. can do. Also, a method for forming a pressure-sensitive adhesive layer on the surface by applying a pressure-sensitive adhesive composition to a surface having a peelable property (peeling surface) and drying it, and transferring the pressure-sensitive adhesive layer to a substrate (transfer method) May be adopted. These methods may be combined. As the release surface, the surface of the release liner, the back surface of the support substrate subjected to the release treatment, or the like can be used.

  Application of the pressure-sensitive adhesive composition can be carried out using a known or conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater and the like. The pressure-sensitive adhesive layer is typically formed continuously, but may be formed in a regular or random pattern such as a dot or stripe depending on the purpose and application.

  Although not particularly limited, the thickness of the pressure-sensitive adhesive layer is typically 2 to 150 μm, usually 5 to 100 μm is appropriate, preferably 10 to 80 μm, more preferably 10 to 50 μm (for example, 15-40 μm). The range of the thickness of the pressure-sensitive adhesive layer is preferably applied to, for example, PVC pressure-sensitive adhesive tapes used for protection and bundling of electric wires, pipes, etc., corrugated tube coating, converging electric wire coating, electrical insulation, etc. obtain.

<Adhesive tape>
One structural example of the adhesive tape disclosed here is shown in FIG. A PVC pressure-sensitive adhesive tape 1 shown in FIG. 1 includes a support substrate (for example, a single-layer PVC film) 11 having a first surface 11A and a second surface 11B, and a pressure-sensitive adhesive layer 21 disposed on the first surface 11A. It is comprised as a single-sided adhesive tape provided with these. In a preferred embodiment, the adhesive tape 1 before use (that is, before being attached to the adherend) is wound on the second surface 11B of the support substrate by being wound in the longitudinal direction, for example, as shown in FIG. It may be in the form of an adhesive tape roll in which the pressure-sensitive adhesive layer 21 is in contact and the surface (adhesive surface) 21A is protected. Alternatively, the surface 21A of the pressure-sensitive adhesive layer 21 may be protected by a release liner in which at least the side facing the pressure-sensitive adhesive layer 21 is a release surface. As the release liner, known or conventional ones can be used without particular limitation. For example, a release liner having a release treatment layer on the surface of a substrate such as a plastic film or paper, or a release made of a low adhesive material such as a fluorine polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, polypropylene, etc.) A liner or the like can be used.

  Another configuration example of the pressure-sensitive adhesive tape disclosed herein is shown in FIG. In the pressure-sensitive adhesive tape 2 shown in FIG. 2, a first pressure-sensitive adhesive layer 21 and a second pressure-sensitive adhesive layer 22 are arranged on the first surface 11 </ b> A and the second surface 11 </ b> B of a support base (for example, a single layer PVC film) 11. It is configured as a double-sided adhesive tape. The technology disclosed herein can be preferably implemented in the form of such a double-sided pressure-sensitive adhesive tape.

  The pressure-sensitive adhesive tape disclosed herein typically has an adhesion amount measured by the following method of 5 mg or less. By limiting the amount of adhesion to 5 mg or less, even when a PVC film containing a plasticizer is used, good fogging prevention properties tend to be exhibited. From this viewpoint, the adhesion amount of the adhesive tape is preferably 4 mg or less, and more preferably 3 mg or less (for example, 2.5 mg or less). From the viewpoint of suppression of fogging, the amount of adhesion is more advantageous as it is closer to zero. Therefore, the lower limit of the adhesion amount is not particularly limited. From the viewpoint of facilitating compatibility between antifogging properties and other characteristics (low temperature characteristics, etc.) at a high level, the adhesive tape disclosed herein has an adhesion amount of 0.1 mg or more or 0.5 mg or more (for example, 1 mg or more). ) Can also be preferably implemented.

(Measurement method of adhesion amount)
Measured according to German Industrial Standard DIN75201-W. Specifically, an adhesive tape having an area corresponding to a circle having a diameter of 80 mm is bonded to the aluminum foil with the adhesive layer surface (adhesive surface) of the adhesive tape (double-sided adhesive in which both surfaces are adhesive surfaces) In the sheet, a beaker (outer diameter 90 mm, inner diameter 83.6 mm, height 190 mm beaker, 130 mm) heated with an oil bath at 120 ° C. with both adhesive surfaces bonded to an aluminum foil. It is soaked in an oil bath at 120 ° C. up to the height of). Further, an aluminum plate (Al plate) that is always cooled to 21 ° C. is installed in the upper end opening of the beaker. After standing in this state for 16 hours, the weight of the Al plate (weight of the Al plate after the test) W1 is measured. The weight W0 of the Al plate before the test is measured in advance. Then, the adhesion amount (mg) is calculated by the following formula (I).
Adhesion amount (mg) = W1-W0 (I)

  The fogging prevention property can be evaluated by the fogging degree (%) measured by the following method. A larger value of the degree of fogging (%) means that the glass plate has less fogging. Therefore, it can be said that the larger the numerical value of the fogging degree (%), the higher the fogging prevention property.

(Foging degree measurement method)
Carry out in accordance with German Industrial Standard DIN75201-R. Specifically, an adhesive tape having an area corresponding to a circle having a diameter of 80 mm is bonded to the aluminum foil with the adhesive layer surface (adhesive surface) of the adhesive tape (double-sided adhesive in which both surfaces are adhesive surfaces) In the sheet, a beaker (outer diameter 90 mm, inner diameter 83.6 mm, height 190 mm beaker, 130 mm) heated with an oil bath at 120 ° C. with both adhesive surfaces bonded to an aluminum foil. It is soaked in an oil bath at 120 ° C. up to the height of). Further, a glass plate that is always cooled to 21 ° C. is installed in the upper end opening of the beaker. After leaving in this state for 3 hours, the glass plate was removed, and the reflectance when the incident light was incident on the glass plate surface facing the inside of the beaker at an incident angle of 60 ° (hereinafter referred to as “60 ° incident reflection”). R1 (%) may be expressed by the following formula: 60 ° incident reflectance R1 (%) of the glass plate after the test = (intensity of incident light on the glass plate after the test / after the test) The intensity of reflected light when incident light is incident on the glass plate) × 100; The 60 ° incidence reflectance R0 (%) of the glass plate surface before the test is expressed by the following formula: 60 ° incidence reflectance R0 (%) of the glass plate before the test = incident light on the glass plate before the test. Strength / reflected light intensity when incident light is incident on the glass plate before the test × 100; For the measurement of the 60 ° incident reflectance (%), for example, a gloss meter manufactured by Konica Minolta Co., Ltd., model “GM-268plus” can be used. Then, the fogging degree (%) is calculated by the following formula (II).
Fogging degree (%) = (R1 / R0) × 100 (II)

  Although it does not specifically limit, the fogging degree of the adhesive tape disclosed here may be 60% or more (typically 65% or more), for example. The fogging degree of the adhesive tape is preferably 70% or more, more preferably 75% or more. According to one aspect of the technology disclosed herein, an adhesive tape having the fogging degree of 80% or more (for example, 85% or more) can be provided. The upper limit of the fogging degree is not particularly limited, but is usually 100% or less.

  Although it does not specifically limit, As for the adhesive tape disclosed here, it is preferable that the retention strength measured by the following method is 50 minutes or more. The pressure-sensitive adhesive tape having the above-mentioned holding power has an appropriate cohesiveness, so that it is easy to handle during production and use. From this viewpoint, the holding force of the adhesive tape is more preferably 90 minutes or more, and further preferably 120 minutes or more (for example, 150 minutes or more).

(Retention force measurement method)
Measured according to the method described in JIS Z0237: 2009. Specifically, the adhesive tape is allowed to stand at room temperature (23 ° C. ± 2 ° C.) for 1 hour, and then cut into a size having a width of 10 mm and a length of 100 mm. In order to suppress the elongation of the supporting base material by applying a load to be described later, a commercially available single-sided adhesive tape of the same size as above is attached to the back surface of the adhesive tape and backed to prepare a measurement sample. As the above-mentioned commercially available single-sided adhesive tape, a tape suitable for the purpose of suppressing the elongation of the supporting substrate with respect to the load can be selected. For example, the product name “No. 31B” (25 μm thick polyester film manufactured by Nitto Denko Corporation) Can be suitably used. One end of the short side of the measurement sample is attached to a bakelite plate (thickness 5 mm, width 25 mm, length 100 mm) as an adherend with a 2 kg roller so as to have an adhesive area of 10 mm width and 20 mm length. Reciprocate and crimp. A 300 g weight is connected to the other end on the short side of the measurement sample, and the measurement sample is held horizontally and held in an environment of 40 ° C. for 30 minutes. Thereafter, the same bakelite plate is held in the vertical direction with the weight on the lower side in the same 40 ° C. environment, thereby applying a load of 300 g to the measurement sample attached to the bakelite plate. The sample is left in this state, and the time (minutes) until the measurement sample peels off from the bakelite plate is measured. This measured value is defined as a holding force.

<Analysis>
The composition of the PVC pressure-sensitive adhesive tape and the PVC film constituting the pressure-sensitive adhesive tape in the technology disclosed herein can be analyzed using general analysis techniques generally used for chemical analysis. Specifically, by using an appropriate combination of analytical instruments and techniques described in the literature on analytical chemistry, identification of each chemical species, specification of the mixing amount and mixing ratio, measurement of molecular weight, and the like can be performed. Hereinafter, although the suitable example of the analysis method of the PVC adhesive tape and PVC film disclosed here is demonstrated in detail, it is not the intention which limits the scope of the present invention.

(1) Analysis technique (1-1) Preparation of sample used for analysis As a sample used for analysis, a PVC adhesive tape, a PVC film before being used for the production of the adhesive tape, and the above-mentioned adhesive tape are used as a supporting substrate (typically Specifically, each solid sample separated into a PVC film) and an adhesive, or a sample prepared by subjecting them to an appropriate treatment is prepared according to the analysis method and analysis purpose. In addition, the suitable example of the method of isolate | separating a PVC adhesive tape into a support base material and an adhesive is mentioned later.

For analysis, when a solution sample is required, for example, an appropriate solvent is added to the sample, and stirring or heating is performed as necessary to dissolve the component to be analyzed in the solvent (typically extracted from the sample). Thus, the solution sample can be prepared. Solvents include chloroform (CHCl ₃ ), methylene chloride (CH ₂ Cl ₂ ), tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), methanol in consideration of polarity and the like. Any one solvent selected from ethanol, toluene, water and the like, or a mixed solvent containing two or more in any ratio can be used.

  As a solution sample, typically, about 30 mL of solvent is added to about 0.2 g of the sample (solid content), and the sample is stirred for 30 minutes to 12 hours in a temperature range from room temperature to about the boiling point of the solvent. A solution obtained by fractionating a solution in which the components contained in the solvent are eluted can be used. If necessary, for example, when the extraction efficiency of the component to be analyzed is low, the sample after separating the solution is added with approximately the same amount of solvent as the separated solution and stirred, and the solution It is also possible to prepare a solution sample by repeating the operation of fractionating one or more times.

When it is necessary to adjust the concentration of the analysis target component contained in the solution sample thus obtained, or a solution sample in which the analysis target component is dissolved in a solvent having a composition different from that of the solvent used for extraction is required. In some cases, after evaporating a part or all of the solvent contained in the solution sample, a solution sample having a desired concentration and solvent composition can be prepared by adding a solvent having a composition and amount according to the purpose. it can.
When it is necessary to remove insoluble matter from the solution sample, the solution sample from which the insoluble matter has been removed can be obtained by filtering with a filter paper or a membrane filter.
When it is necessary to obtain a solution sample containing only some types (typically about one or two or five specific components) from a solution sample containing a plurality of components, In addition to purification or isolation by the column chromatograph described, it is possible to obtain a target solution sample using high performance liquid chromatography (HPLC) or gel permeation chromatography (GPC) described later.

(References)
All of the following, edited by The Chemical Society of Japan, Maruzen Publishing Co., Ltd., 5th edition Experimental Chemistry Course, Volume 8 NMR / ESR (issued in 2006)
Volume 9 Material Structure I (issued in 2005)
Volume 10 Material structure II (issued in 2005)
20-1 Analytical Chemistry (issued in 2007)
Volume 20-2 Environmental Chemistry (issued in 2007)
Volume 26 Polymer Chemistry (issued in 2005)

(1-2) Method of separating the PVC adhesive tape into the supporting substrate and the adhesive The method of separating the PVC adhesive tape into the supporting substrate and the adhesive is not particularly limited. As a simple and convenient method, the pressure-sensitive adhesive layer on one side folded is obtained by folding the PVC pressure-sensitive adhesive tape so that the pressure-sensitive adhesive layer is on the inside, bonding the pressure-sensitive adhesive layers together, and then peeling them off. A method of transferring onto the pressure-sensitive adhesive layer on the other side can be employed. By transferring the pressure-sensitive adhesive layer on the one side onto the pressure-sensitive adhesive layer on the other side, the pressure-sensitive adhesive layer can be removed from the support substrate on the one side. The pressure-sensitive adhesive layer that overlaps the two layers on the other side can be further stacked by repeating the same folding and peeling as necessary. According to this method, the support base material and the pressure-sensitive adhesive can be separated without using an organic solvent, heat treatment or the like by utilizing the self-adhesive property of the pressure-sensitive adhesive. Therefore, the composition of the adhesive tape can be analyzed with high accuracy. It should be noted that conditions such as the time until the pressure-sensitive adhesive layers are bonded to each other, the speed of peeling, and the peeling angle can be appropriately set so that those skilled in the art can easily transfer the pressure-sensitive adhesive layer. it can. Also, instead of bending one PVC adhesive tape, the adhesive layers of two PVC adhesive tapes are bonded together, and then peeled off, so that the adhesive layer of one adhesive tape becomes the adhesive of the other adhesive tape. It may be transferred onto the layer.

(1-3) Fourier transform infrared spectroscopy (FT-IR)
The Fourier transform infrared spectroscopic analysis of the solid sample obtained by removing the solvent from the above-described solid sample or the above-described solution sample can be performed by the ATR method under the following apparatus and conditions. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio.
(Equipment and conditions)
Equipment: Thermo Fisher Scientific, Nicolet 6700
Condition: Single reflection ATR method (Smart iTR, Ge45 °)
Resolution: 4 cm ^-1
Detector: DTGS
Integration count: 64 times

(1-4) Fourier transform nuclear magnetic resonance spectroscopy (FT-NMR)
A solid sample obtained by removing the solvent from the above-described solid sample or the above-described solution sample may be any deuterated solvent (CDCl ₃ , CDCl ₂ , THF-d8, acetone-d6, DMSO-d6, DMF- d7, methanol-d4, ethanol-d6, D ₂ O, etc.) and subjected to Fourier transform nuclear magnetic resonance spectroscopy ( ¹ H-NMR and / or ¹³ C-NMR) with the following apparatus and conditions. it can. For the analysis, a sample whose concentration is adjusted so that the deuterated solvent is 0.06 to 6 mL with respect to 0.1 g of the solid sample may be used. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio.
(Equipment and conditions)
Equipment: Bruker Biospin, AVANCE III-600 with Cryo Probe
Observation frequency: 600 MHz ( ¹ H), 150 MHz ( ¹³ C)
Measurement temperature: 300 K

(1-5) Gas chromatography / gravimetric analysis (GC / MS)
The gas chromatography / gravimetric analysis of the solution sample described above can be performed with the following apparatus and conditions. The concentration of the solution sample is suitably adjusted so that the solvent is 0.6 to 60 mL with respect to 0.1 g of the solid sample, and this is preferably used as the sample for analysis. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio. Of the peaks that appear in the chromatogram, the peaks identified for the composition are identified by creating a calibration curve using the identified product or a compound having a molecular structure similar to the identified product as a standard. The content in the sample can be calculated.
(Equipment and conditions)
Equipment: Thermo Finnigan, Trace GC ultra (GC), PolarisQ (MS)
GC conditions / column: Ultra ALLOY-5 (0.25 μm, 0.25 mmφ × 30 m)
・ Carrier gas: He (1.0mL / min)
・ Inlet: Split (Split ratio; 50: 1)
・ Inlet temperature: 250 ℃
Column temperature: 40 ° C (3 min)-(+ 20 ° C / min) → 300 ° C (24 min)
MS conditions ・ Ionization method: Select EI, FI or CI as appropriate ・ Electron energy: 70 eV
・ Ion source temperature: 210 ℃
・ Interface temperature: 300 ℃
・ Weight range: m / z = 20-800

(1-6) Gas chromatography (GC)
The gas chromatography of the solution sample described above can be performed with the following apparatus and conditions. The concentration of the solution sample is suitably adjusted so that the solvent is 0.6 to 60 mL with respect to 0.1 g of the solid sample, and this is preferably used as the sample for analysis. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio. Of the peaks appearing in the chromatogram, the peak relating to the component whose composition has been identified is prepared by preparing a calibration curve using the identified product or a compound having a molecular structure similar to the identified product as a standard. The content of the identified component in the sample can be calculated.
(Equipment and conditions)
Equipment: Aglient Technologies 6890Plus
Column: HP-1, 30 m × 0.250 mm id × 1.0 μm film thickness
Column temperature: 100 ℃ → (+ 20 ℃ / min) → 300 ℃ (Hold)
Column pressure: 101.7 kPa (constant flow mode)
Carrier gas: He (1.0 mL / min)
Inlet: Split (split ratio; 20: 1)
Inlet temperature: 250 ° C
Detector: FID
Detector temperature: 250 ° C
Injection volume: 1μL

(1-7) Liquid chromatography / Fourier transform gravimetric analysis (LC / FT-MS)
The liquid chromatography / Fourier transform gravimetric analysis of the solution sample described above can be performed with the following apparatus and conditions. The concentration of the solution sample is suitably adjusted so that the solvent is 0.6 to 60 mL with respect to 0.1 g of the solid sample, and this is preferably used as the sample for analysis. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio. Of the peaks appearing in the chromatogram, the peak relating to the component whose composition has been identified is prepared by preparing a calibration curve using the identified product or a compound having a molecular structure similar to the identified product as a standard. The content of the identified component in the sample can be calculated.
(Equipment and conditions)
Equipment: ThermoFisher Scientific UltiMate 3000 (LC), LTQ orbitrap XL (FT-MS)
LC conditions / column: Agilent Technologies Zorbax Eclipse PlusC8 (3.0 mmφ × 100 mm, 1.8 μm)
-Eluent composition: ACN (acetonitrile) / ammonium acetate aqueous solution gradient-Flow rate: 0.5 mL / min
・ Column temperature: 40 ℃
・ Injection volume: 5μL
FT-MS conditions and ionization method: ESI (Negative, Positive)
・ Ion spray voltage: 3 kV

(1-8) High performance liquid chromatography (HPLC)
The above-described high performance liquid chromatography of a solution sample can be performed with the following apparatus and conditions. The concentration of the solution sample is suitably adjusted so that the solvent is 0.6 to 60 mL with respect to 0.1 g of the solid sample, and this is preferably used as the sample for analysis. By this analysis method alone or in combination with other analysis methods, it is possible to identify the composition of the components contained in the PVC pressure-sensitive adhesive tape or the pressure-sensitive adhesive layer and to calculate the composition ratio. Of the peaks appearing in the chromatogram, the peak relating to the component whose composition has been identified is prepared by preparing a calibration curve using the identified product or a compound having a molecular structure similar to the identified product as a standard. The content of the identified component in the sample can be calculated. In addition, by separating the eluate corresponding to the peak appearing in the chromatogram, it is possible to separate the components contained in the adhesive tape as a simple substance or a mixture with a simplified composition. Can also be used as a sample for analysis in other analysis methods.
(Equipment and conditions)
Equipment: Agilent Technologies 1100
Column: Inertsil C8-4 (4.6 mmφ × 150 mm, 5μm)
Eluent composition: Distilled water / acetonitrile gradient flow rate: 1.0 mL / min
Detector: DAD (190-400 nm, 230 nm extraction)
Column temperature: 40 ° C
Injection volume: 10μL

(1-9) Gel permeation chromatography (GPC)
The above-described gel permeation chromatography of the solution sample can be performed with the following apparatus and conditions. The concentration of the solution sample may be adjusted as appropriate so that the solvent is 0.1 to 10 mL with respect to 1 mg of the solid sample, and the solution sample may be used as the sample for analysis. The sample for analysis is filtered through an appropriate filter (for example, a membrane filter having an average pore diameter of about 0.45 μm) and injected into the apparatus. By this analysis, the molecular weight of the peak appearing in the chromatogram can be calculated as a standard polystyrene equivalent value described below. In addition, by separating the eluate corresponding to the peak appearing in the chromatogram, it is possible to separate the components contained in the adhesive tape as a simple substance or a mixture with a simplified composition. Can also be used as a sample for analysis in other analysis methods.
(Equipment and conditions)
Equipment: Tosoh Corporation HLC-8120GPC
Pump: Enshine Scientific Corporation CO-150
Pump flow rate: 1 mL / min
Column: Tosoh Corporation HXL Guard Column, TSKgel G4000HXL, TSKgel G5000HXL, TSKgel GMHXL mixed-bed are used.
Column oven temperature: 40 ° C
Detector: Differential refractive index detector RID-10A manufactured by Shimadzu Corporation
Developing solvent: THF
Injection volume: 100μL
Standard polystyrene: Tosoh Corporation Tsk gel standard polystyrene F-288, F-40, F-4, A-5000, A-500

(2) Analysis of plasticizer (2-1) Quantitative analysis by ¹ H-NMR Support base material (typically PVC film) obtained by removing the pressure-sensitive adhesive from the PVC pressure-sensitive adhesive tape by the above method (1-2) After 0.2 g is immersed in 30 mL of chloroform and stirred at room temperature for 30 minutes, the solution is collected. The supporting substrate is immersed in 30 mL of new chloroform, stirred for 30 minutes at room temperature, and then the operation of separating the solution is repeated twice. In this manner, 90 mL of a chloroform solution from which the plasticizer in the supporting base material is extracted is recovered. CDCl ₃ is added to the solid content obtained by evaporating chloroform from this solution so as to achieve the concentration described in (1-4) above, thereby obtaining a sample for analysis.
¹ H-NMR measurement is performed using the apparatus and conditions described in (1-4) above. A peak derived from the plasticizer is obtained with reference to the obtained spectrum and results obtained by other analysis techniques, and the content of the plasticizer is obtained from the integral ratio of these peaks. When two or more kinds of plasticizers are contained in the analysis sample, the content of each plasticizer is determined in the same manner. When a peak derived from a certain plasticizer overlaps with a peak derived from another component (other plasticizer or a component other than a plasticizer), the plastic ratio is calculated from the integration ratio excluding the contribution of the other component. The content of the agent is determined.

(2-2) Molecular weight analysis by GPC By the same operation as the above (2-1), 90 mL of chloroform solution from which the plasticizer in the supporting base material is extracted is recovered. The chloroform solution recovered in (2-1) above can also be used for this analysis. To the solid content obtained by evaporating chloroform from this solution, THF is added to obtain the concentration described in (1-9) above to obtain a sample for analysis.
The analysis sample is analyzed using the apparatus and conditions described in (1-9) above to obtain a chromatogram. With reference to the obtained chromatogram and the results obtained by other analysis techniques, the peak derived from the plasticizer is specified from the chromatogram. The molecular weight of the plasticizer is determined using the line connecting both hems of the peak (the vicinity where the peak starts rising and the vicinity where it converges) as the base line. When two or more kinds of plasticizers are contained in the analysis sample, the molecular weight is obtained in the same manner for each plasticizer.

(2-3) Blending amount and blending ratio of PLH and PLL The blending amount of PLH and PLL ( _WPLH , _WPLL ) and blending ratio based on weight ( _WPLH / _WPLL ) are determined as follows.
(I) A plasticizer (PLL, PLH) is extracted from the support substrate by the method described in (2-1) above. At this time, the weight of the solvent-insoluble matter and the weight of the solvent-soluble matter (that is, the extract by the solvent) are weighed separately.
(Ii) About the said extract, ¹ H-NMR and ¹³ C-NMR of said (1-4) and the analytical method as described in said (1-3), (1-5), (1-7) are used. Appropriately adopted, the chemical structure of the component contained in the extract is specified, and the formula weight (molecular weight) is obtained. In specifying the chemical structure, a known spectrum data collection or the like can be used as necessary.
(Iii) In the ¹ H-NMR spectrum of (1-4) above, the molar ratio of each component is determined from the number of protons (integration ratio) derived from each of PLH, PLL and other components contained in the extract. The weight ratio of each component can be calculated by applying the formula amount obtained in (ii) above to the result. A blending ratio (W _PLH / W _PLL ) is determined from this weight ratio.
(Iv) From the weight ratios of (i) and (iii) above, the weight ratio of PLH and PLL to the total weight of the support substrate is determined.
In some cases, as an alternative method, the molecular weight of each component ascertained from the GPC in (2-2) is applied to the molar ratio of each component obtained from the integral ratio in the ¹ H-NMR spectrum of (ii) above. By doing so, you may obtain _| require a compounding ratio ( _WPLH / _WPLL ).
As another method, when PLH and PLL can be accurately separated in the analysis of (1-7) in (ii) above (when the peaks related to these components are well separated), the above (1 -8) may be used to fractionate PLH and PLL, and the blending ratio (W _PLH / W _PLL ) may be determined from their dry weight.

In addition, the molecular weight of the plasticizer (plasticizer before use, that is, the plasticizer raw material) used for the production of the PVC film is for the analysis of (2-2) above, which is prepared by extracting the plasticizer in the support substrate. Instead of the sample, for example, it can be obtained using an analytical sample prepared by directly dissolving the plasticizer raw material in THF. More specifically, an analytical sample was prepared by dissolving the plasticizer raw material in THF at the concentration described in (1-9) above (for example, a concentration of 10 mL of THF with respect to 10 mg of the plasticizer raw material). From the chromatogram obtained by analysis with the apparatus and conditions described in (1-9), it can be obtained in the same manner as in (2-2) above. Although it does not specifically limit, the PVC film which satisfy | fills the preferable compounding ratio ( _WPLH / _WPLL ) disclosed here is the plasticizer classified into PLH based on the molecular weight grasped | ascertained by said method, for example It can be obtained by selecting a plasticizer classified as a _PLL and blending them according to the desired W _PLH / W _PLL . However, the description in this paragraph is merely an example, and does not limit the scope of the invention disclosed herein.

(3) Analysis of antioxidant (3-1) Composition analysis By the same operation as the above (2-1), 90 mL of chloroform solution from which the antioxidant in the supporting base material is extracted is recovered. The chloroform solution recovered in (2-1) or (2-2) can be used for this analysis. Using this chloroform solution, ^{one of the} appropriate analytical methods can be used alone or in combination of two or more from the above-mentioned HPLC, FT-IR, ¹ H-NMR, ¹³ C-NMR and LC / FT-MS. Thus, the antioxidant is identified and the composition is analyzed.
(3-2) Quantitative analysis 0.2 g of a supporting substrate (typically PVC film) obtained by removing the adhesive from the PVC adhesive tape was immersed in 30 mL of THF and stirred at room temperature for 30 minutes, and then the solution was collected. To do. The support substrate is immersed in 30 mL of fresh THF and stirred at room temperature for 30 minutes, and then the operation of separating the solution is repeated twice. In this way, 90 mL of the THF solution from which the antioxidant in the supporting base material is extracted is recovered. Reprecipitation operation is performed by adding the THF solution to 100 times the volume (volume basis) of methanol in this THF solution, and the resulting supernatant is filtered through a membrane filter and then analyzed by HPLC to obtain a chromatogram. . An antioxidant-derived peak appearing in the chromatogram is used to prepare a calibration curve using the antioxidant identified by the composition analysis as a standard, and the antioxidant is quantified.

(4) Analysis of fatty acid metal salt The metal species constituting the fatty acid metal salt can be qualitatively analyzed by fluorescent X-ray analysis (XRF) performed with the following apparatus and conditions. Specifically, the adhesive surface of the PVC adhesive tape (the surface of the adhesive layer) is attached to a filter paper having a diameter of 20 mm, and X-rays are irradiated from the support substrate side.
(Equipment and conditions)
Equipment: Rigaku ZSX100e
X-ray source: Vertical Rh tube Analytical elements: B to U
Analysis area: 20 mmφ
X-ray output and spectral crystal: as shown in Table 1.

<Application>
The pressure-sensitive adhesive tape disclosed herein can be used for, for example, protection and bundling of electric wires and pipes, covering a corrugated tube that surrounds and protects electric wires, electric insulation, and the like. In particular, as a preferable application utilizing good antifogging properties, a wire harness (typically, for example, a wire harness of an automobile or other vehicles, particularly a wire harness of a vehicle equipped with an internal combustion engine) is used. Specifically, there is an application in which the wire is wound around a plurality of electric wires). Here, examples of the aspect in which the PVC adhesive tape is wound around the electric wire constituting the wire harness include an aspect in which the PVC adhesive tape is wound around the electric wire, and a cylinder (for example, A mode in which a PVC adhesive tape is wound around the corrugated tube) is included. Moreover, the adhesive tape disclosed here is not limited to the above-mentioned uses, and various fields in which PVC adhesive tape has been conventionally used, such as layers between electrical components (transformers, coils, etc.), electronic components, etc. It can also be suitably used in the fields of external insulation, fixing, display, identification, and the like.

The matters disclosed by this specification include the following.
(1) a polyvinyl chloride film containing a plasticizer;
An adhesive tape comprising an adhesive layer disposed on at least one surface of the film,
An adhesive tape having an adhesion amount of about 5 mg or less in an adhesion amount measurement performed by holding the adhesive tape having an area corresponding to a circle having a diameter of 80 mm at 120 ° C. for 16 hours.
(2) The pressure-sensitive adhesive tape according to (1), wherein the content of the plasticizer in the polyvinyl chloride film is about 10 to 50% by weight.
(3) The said polyvinyl chloride film is an adhesive tape as described in said (1) or (2) containing a fatty-acid metal salt.
(4) The fatty acid metal salt contains at least one metal element belonging to any one of Groups 1, 2, 12, 13, and 14 (excluding Pb) of the periodic table (3) ) Adhesive tape.
(5) The adhesive according to (3) or (4), wherein the fatty acid metal salt includes at least one metal element selected from the group consisting of Li, Na, Ca, Mg, Zn, Ba, and Sn. tape.
(6) The adhesive according to any one of (3) to (5), wherein the fatty acid metal salt is a stearic acid metal salt, a lauric acid metal salt, or a combination of a stearic acid metal salt and a lauric acid metal salt. tape.
(7) The pressure-sensitive adhesive tape according to any one of (3) to (6), wherein the content of the fatty acid metal salt in the PVC film is about 0.02 wt% or more and about 1 wt% or less.
(8) The said polyvinyl chloride film is an adhesive tape in any one of said (1)-(7) containing antioxidant (for example, hindered phenol type antioxidant).
(9) The pressure-sensitive adhesive tape according to (8), wherein the content of the antioxidant in the PVC film is about 0.05% by weight or more and about 10% by weight or less.

(10) The polyvinyl chloride film according to any one of (1) to (9), wherein the plasticizer includes a polyester plasticizer having a molecular weight of 1000 or more and a carboxylic acid ester having a molecular weight of less than 1000. Adhesive tape.
(11) The polyvinyl chloride film has a relationship between the weight W _PLH of the polyester plasticizer having a molecular weight of 1000 or more contained in the film and the weight W _PLL of the carboxylic acid ester having a molecular weight of less than 1000 contained in the film. But the following formula:
1 ≦ (W _PLH / W _PLL ) ≦ 50;
The adhesive tape according to (10), wherein
(12) The pressure-sensitive adhesive tape according to (10) or (11), wherein the carboxylic acid ester having a molecular weight of less than 1000 contains an aromatic carboxylic acid ester.
(13) The pressure-sensitive adhesive tape according to (12), wherein the aromatic carboxylic acid ester includes at least one of trimellitic acid ester and pyromellitic acid ester.
(14) The pressure-sensitive adhesive tape according to any one of (10) to (13), wherein the carboxylic acid ester having a molecular weight of less than 1000 includes an ester of a carboxylic acid and an alkyl alcohol having 6 to 14 carbon atoms.
(15) The content of the carboxylic acid ester having a molecular weight of less than 1000 in the PVC film is approximately 1 part by weight or more and approximately 10 parts by weight or less with respect to 100 parts by weight of PVC, and any of (10) to (14) above Crab adhesive tape.
(16) The pressure-sensitive adhesive tape according to any one of (10) to (15), wherein the polyester plasticizer having a molecular weight of 1000 or more includes an adipic acid-based polyester plasticizer.
(17) The pressure-sensitive adhesive tape according to any one of (10) to (16), wherein the polyester plasticizer having a molecular weight of 1000 or more comprises an adipic acid polyester plasticizer having a molecular weight of about 3000 or more and about 7000 or less.
(18) The content of the polyester plasticizer having a molecular weight of 1000 or more in the PVC film is about 25 parts by weight or more and less than about 60 parts by weight with respect to 100 parts by weight of PVC. The adhesive tape in any one.

(19) The adhesive tape according to any one of (1) to (18), wherein the polyvinyl chloride film includes an elastomer.
(20) The pressure-sensitive adhesive tape according to any one of (1) to (19), wherein the content of the elastomer in the PVC film is about 1% by weight or more and about 30% by weight or less.
(21) The elastomer is
(A) a chlorinated polyethylene having a chlorine content of about 25 to 50% by weight (for example, about 35 to 45% by weight),
(B) (meth) acrylic acid ester-butadiene-styrene copolymer,
(C) an acrylonitrile-butadiene copolymer having an acrylonitrile content of about 15-50% by weight (eg, about 30-40% by weight), and (D) a vinyl acetate content of about 30-75% by weight (eg, about 50%). The pressure-sensitive adhesive tape according to (20), which comprises one or more selected from ethylene-vinyl acetate copolymers that are (˜65 wt%).

(22) The pressure-sensitive adhesive tape according to any one of (1) to (21), wherein the pressure-sensitive adhesive layer is a rubber-based pressure-sensitive adhesive layer containing a rubber-based pressure-sensitive adhesive as a main component.
(23) The pressure-sensitive adhesive layer according to any one of (1) to (22), wherein the pressure-sensitive adhesive layer contains natural rubber and synthetic rubber (for example, SBR) in a weight ratio of about 10:90 to 90:10. .
(24) The pressure-sensitive adhesive layer contains one or more tackifying resins selected from rosin resins, petroleum resins, terpene resins, phenol resins, coumarone indene resins, and ketone resins. The adhesive tape according to any one of (1) to (23).
(25) The pressure-sensitive adhesive layer contains a rubber polymer and a tackifier resin,
Content of the said tackifying resin is an adhesive tape in any one of said (1)-(24) which is about 50-150 weight part with respect to 100 weight part of said rubber-type polymers.

  (26) A wire harness including an electric wire and the adhesive tape according to any one of (1) to (25) wound around the electric wire.

  Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to the specific examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.

<Materials used>
The materials and their abbreviations used in the following examples are as follows.

(Polyvinyl chloride (PVC))
A: Shin-Etsu Chemical Co., Ltd. product, degree of polymerization 1300, trade name “TK-1300”
C: Shin-Etsu Chemical Co., Ltd. product, polymerization degree 1000, trade name “TK-1000”

(Antioxidant)
A: BASF products, phenolic antioxidant, trade name “Irganox 1010”

(Fatty acid metal salt)
A: Calcium stearate (Kishida Chemical Co., Ltd. product)
B: Zinc laurate (Mitsuwa Chemical Co., Ltd. product)

(Plasticizer)
H1: DIC Corporation product, adipic acid polyester plasticizer, trade name “W-360ELS”, molecular weight 2800 (measured value based on the above-mentioned method)
H2: DIC Corporation product, adipic acid polyester plasticizer, trade name “W-2300”, molecular weight 3200 (measured value based on the above-mentioned method)
H3: DIC Corporation product, adipic acid-based polyester plasticizer, trade name “W-4010”, molecular weight 5800 (measured value based on the above-mentioned method)
L1: J Plus Co., Ltd., diisononyl phthalate, trade name “DINP”, molecular weight 504 (measured value based on the method described above)
L3: DIC Corporation product, trimellitic acid tri-2-ethylhexyl, trade name “W-705”, molecular weight 750 (measured value based on the above-mentioned method)
L4: Kao Corporation product, trimisodecyl trimellitate, trade name “Trimex T-10”, molecular weight 810 (measured value based on the above-described method)
L5: ADEKA Co., Ltd., pyromellitic acid tetra-2-ethylhexyl, trade name “UL-80”, molecular weight 834 (measured value based on the above-mentioned method)

(Elastomer)
A: Showa Denko Co., Ltd. product, chlorinated polyethylene, chlorine content 30.0-33.0%, trade name "Eraslen 301A"
C: Nippon Zeon Co., Ltd. product, acrylonitrile-butadiene rubber, nitrile content of about 36%, trade name “Zetpol 2000”

<Production of adhesive tape>
Example 1
60 parts of SBR latex (product of Nippon Zeon Co., Ltd., trade name “Nipol LX426”), 40 parts of natural rubber latex (product of GOLDEN HOPE, trade name “HYTEX HA”) and 120 parts of petroleum resin emulsion are mixed on a solid basis. Thus, a water-dispersed rubber-based pressure-sensitive adhesive composition was prepared. As the above-mentioned petroleum resin emulsion, 75 parts of petroleum resin (Exxon product, aliphatic hydrocarbon resin, trade name “Escollets 1202”, softening point 100 ° C.) is dissolved in 25 parts of toluene, and a surfactant (Kao) Product, product name “Emulgen 920”) and 3.5 parts of water and 46.5 parts of water were added and used after stirring and emulsifying with a homomixer. Hereinafter, the pressure-sensitive adhesive composition is referred to as “pressure-sensitive adhesive composition A”.

  Composition shown in Table 2 for each raw material shown in Table 2 (ie, a ratio of 0.10% for antioxidant A, 0.20% for fatty acid metal salt A, 23% for plasticizer H3, and 3% for plasticizer L5) The mixture was weighed, mixed and kneaded so that the balance was composed of polyvinyl chloride A), and then formed into a long film shape having a thickness of 110 μm at a molding temperature of 150 ° C. with a calendar molding machine. In this way, a PVC film according to Example 1 was obtained.

  The pressure-sensitive adhesive composition A was applied to one surface of the PVC film using a comma direct coater and dried. The coating amount of the pressure-sensitive adhesive composition A was adjusted so that the thickness of the pressure-sensitive adhesive layer formed after drying was 20 μm. This was cut (slit) into a width of 19 mm to obtain an adhesive tape according to Example 1 having an adhesive layer on one surface of the PVC film.

(Examples 2-5 and Comparative Examples 1-2)
Adhesives according to Examples 2 to 5 and Comparative Examples 1 and 2 in the same manner as in Example 1 except that the composition of the PVC film, the thickness of the PVC film and the thickness of the adhesive layer are as shown in Table 2, respectively. Each tape was produced.

<Measurement and evaluation>
(Adhesion amount)
It measured according to the adhesion amount measuring method mentioned above. More specifically, an adhesive tape was placed on an Al foil (product name “Sunfoil”, manufactured by Toyo Aluminum Echo Products Co., Ltd.) with no gap in the width direction, and then cut into a circular shape having a diameter of 80 mm together with the Al foil. This prepared the test sample by which the adhesive surface of the adhesive tape of the area equivalent to a circle | round | yen with a diameter of 80 mm was bonded together to the said Al foil. The test sample was desiccator (standard desiccator manufactured by AS ONE Co., Ltd., product name “SD”) conditioned with silica gel (silica gel in nonwoven fabric bag manufactured by Toyoda Chemical Co., Ltd., product name “N100G”) with the Al foil side as the upper side. -UTG ") for 1 hour. Using a fogging tester manufactured by Thermo Electron Corporation, model “HAAKE Phoenix II”, setting the temperature of the oil bath at 120 ° C. and holding it for 1 hour, the inside of the beaker was adjusted in advance, The test sample was placed on the bottom. An Al plate (made by Namegawa Light Steel Co., Ltd., A5052, length 110 mm, width 110 mm, thickness 3 mm) was installed in the upper end opening of the beaker, and the Al plate was always kept in a state cooled to 21 ° C. . After the lapse of 16 hours, the Al plate was removed, the surface facing the inside of the beaker was held up and held horizontally in a fume hood, and allowed to stand for 24 hours, and then the weight of the Al plate (Al plate after the test) Weight). The weight of the Al plate was measured using a measuring instrument manufactured by METTLER TOLEDO, model “XP504DRV” both before and after the test. From the result, the amount of adhesion (mg) was calculated by the above formula (I).

(Foging degree measurement)
It measured according to the fogging degree measuring method mentioned above. More specifically, a test sample in which the adhesive surface of an adhesive tape having an area equivalent to a circle having a diameter of 80 mm is bonded to an Al foil is prepared in the same manner as the test sample for measuring the amount of adhesion, and stored in a desiccator for 1 hour. did. Using a fogging tester manufactured by Thermo Electron Corporation, model “HAAKE Phoenix II”, setting the temperature of the oil bath at 120 ° C. and holding it for 1 hour, the inside of the beaker was adjusted in advance, The test sample was placed on the bottom, and a steel ring with a diameter of 80 mm was placed and fixed. An O-ring (trade name “Viton Seal” manufactured by Eihiro Seiki Co., Ltd., inner diameter 95 mm, thickness 4 mm, Shore A hardness 60 ± 5) is placed in the upper opening of the beaker, and a glass plate (Eihiro Seiki Co., Ltd.) The glass plate was always cooled to 21 ° C., and the glass plate was kept at a temperature of 21 ° C. After the elapse of 3 hours, the glass plate was removed, held horizontally in a draft with the surface facing the inside of the beaker facing up, and allowed to stand for 1 hour. Then, the 60 degree incident reflectance R1 (%) of the glass plate after a test was measured about the surface which faced the inside of the said beaker. The 60 ° incidence reflectance (%) of the glass plate was measured before and after the test using a gloss meter manufactured by Konica Minolta, Inc., model “GM-268plus”. From the result, the fogging degree (%) was calculated by the above formula (II).

(Initial adhesive strength)
The adhesive tape according to each example (width 19 mm) is cut to an appropriate length, and a 2 kg roller is reciprocated once on a stainless steel plate (SUS304BA plate) as an adherend in an environment of 23 ° C. and 50% RH. And crimped. After leaving this in an environment of 23 ° C. and 50% RH for 30 minutes, in accordance with JIS Z0237: 2009, using a tensile tester, a 180 ° peel strength (N / 19 mm) at a tensile speed of 300 mm / min. Was measured.

(Holding power)
According to the holding force measuring method described above, the holding force of the adhesive tape according to each example was measured.

  The obtained results are shown in Table 2 together with the schematic configuration of the adhesive tape according to each example.

  As shown in Table 2, the adhesive tapes of Examples 1 to 5 in which the adhesion amount is suppressed to 5 mg or less are clearly compared to the adhesive tapes of Comparative Examples 1 and 2 in which the adhesion amount exceeds 5 mg. Good anti-fogging property was shown. Moreover, since the adhesive tape of Examples 1-5 contains a suitable amount of plasticizers in a PVC film, it showed the softness | flexibility suitable as a PVC adhesive tape. On the other hand, the pressure-sensitive adhesive tape of Comparative Example 2 using a PVC film not containing a plasticizer lacked the flexibility generally required for PVC pressure-sensitive adhesive tapes.

  Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

1, 2 PVC adhesive tape (adhesive tape)
DESCRIPTION OF SYMBOLS 11 Support base material 11A 1st surface 11B 2nd surface 21,22 Adhesive layer 21A Surface (adhesion surface)

Claims (10)

A polyvinyl chloride film containing a plasticizer;
An adhesive tape comprising an adhesive layer disposed on at least one surface of the film,
An adhesive tape having an adhesion amount of 5 mg or less in an adhesion amount measurement performed by holding the adhesive tape having an area corresponding to a circle having a diameter of 80 mm at 120 ° C. for 16 hours.   The pressure-sensitive adhesive tape according to claim 1, wherein the content of the plasticizer in the polyvinyl chloride film is 10 to 50% by weight.   The pressure-sensitive adhesive tape according to claim 1, wherein the polyvinyl chloride film contains a fatty acid metal salt.   4. The fatty acid metal salt according to claim 3, wherein the fatty acid metal salt contains at least one metal element belonging to any one of Group 1, Group 2, Group 12, Group 13, and Group 14 (excluding Pb) of the periodic table. Adhesive tape.   The pressure-sensitive adhesive tape according to claim 3 or 4, wherein the fatty acid metal salt contains at least one metal element selected from the group consisting of Li, Na, Ca, Mg, Zn, Ba, and Sn.   The pressure-sensitive adhesive tape according to any one of claims 1 to 5, wherein the polyvinyl chloride film includes, as the plasticizer, a polyester plasticizer having a molecular weight of 1000 or more and a carboxylic acid ester having a molecular weight of less than 1000. In the polyvinyl chloride film, the relationship between the weight W _PLH of the polyester plasticizer having a molecular weight of 1000 or more contained in the film and the weight W _PLL of the carboxylic acid ester having a molecular weight of less than 1000 contained in the film is as follows. Formula:
1 ≦ (W _PLH / W _PLL ) ≦ 50;
The adhesive tape according to claim 6, wherein   The pressure-sensitive adhesive tape according to any one of claims 1 to 7, wherein the polyvinyl chloride film contains an antioxidant.   The pressure-sensitive adhesive tape according to any one of claims 1 to 8, wherein the polyvinyl chloride film contains an elastomer.   The wire harness containing the electric wire and the adhesive tape as described in any one of Claim 1 to 9 currently wound around the electric wire.

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