CN113881358A - Impact protection adhesive tape - Google Patents

Impact protection adhesive tape Download PDF

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Publication number
CN113881358A
CN113881358A CN202010637026.2A CN202010637026A CN113881358A CN 113881358 A CN113881358 A CN 113881358A CN 202010637026 A CN202010637026 A CN 202010637026A CN 113881358 A CN113881358 A CN 113881358A
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China
Prior art keywords
sensitive adhesive
meth
pressure
adhesive layer
impact
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Pending
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CN202010637026.2A
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Chinese (zh)
Inventor
赵玉坤
侯猛
刘兵
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Nitto Denko Shanghai Songjiang Co Ltd
Nitto Denko Corp
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Nitto Denko Shanghai Songjiang Co Ltd
Nitto Denko Corp
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Priority to CN202010637026.2A priority Critical patent/CN113881358A/en
Publication of CN113881358A publication Critical patent/CN113881358A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides an impact protection adhesive tape. The impact protection tape comprises a base material layer and a pressure-sensitive adhesive layer laminated on at least one surface of the base material layer, and the adhesive force of the impact protection tape is more than 2.5N/20mm after the impact protection tape is stored under the condition of 80 ℃ for X3 days. The impact protection tape of the present invention has a low halogen content and is thus environmentally friendly, has excellent anchoring properties and holding power to a substrate, has excellent coatability and good resistance to plasticizers, and the adhesive polymer and halogen-containing compound contained therein have good compatibility.

Description

Impact protection adhesive tape
Technical Field
The present invention relates to an impact protection tape, and more particularly, to an impact protection tape having a low halogen content and thus being environmentally friendly, having excellent anchoring properties and holding power to a substrate, having excellent coatability and good resistance to plasticizers, and having an adhesive polymer and a halogen-containing compound contained therein with good compatibility.
Background
Conventional tapes, particularly polyvinyl chloride (PVC) tapes using a (meth) acrylic polymer-based adhesive, have poor impact resistance, and if the (meth) acrylic polymer-based adhesive is applied to a PVC base layer containing a plasticizer, the adhesive performance is rapidly reduced.
The main reason for this may be that the plasticizer is liable to migrate from the inside of the product to the external medium under the action of heat, pressure, solvent, etc. during the use of the product comprising the PVC substrate layer. In particular, small molecule plasticizers, whose migration occurs primarily in a manner of "diffusion from the interior to the surface of the PVC substrate-through the surface-into the external medium", cause problems such as softening of the pressure-sensitive adhesive layer containing the adhesive, deterioration of the tackiness, peeling-off, etc.
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the impact resistance of an adhesive tape can be improved by adding a modifier (for example, chlorinated polyethylene, MBS resin, or the like) to a base material layer; the present inventors have completed the present invention by adding a halogen-containing compound (chlorinated rubber, epichlorohydrin resin, chlorobenzene rubber, polyvinylidene chloride, etc.) which is more easily adsorbed and more resistant to plasticizers to the pressure-sensitive adhesive layer, whereby the plasticizer resistance of the adhesive can be improved.
Means for solving the problems
[1] The impact protection adhesive tape comprises a base material layer and a pressure-sensitive adhesive layer laminated on at least one surface of the base material layer, wherein after the impact protection adhesive tape is stored at 80 ℃ for 3 days, the adhesive force is more than 2.5N/20 mm; preferably, the thickness of the substrate layer is 100-500 μm; and preferably, the thickness of the pressure-sensitive adhesive layer is 15-45 μm.
[2] The impact protection adhesive tape according to [1], further comprising a release layer laminated on the pressure-sensitive adhesive layer, wherein the thickness of the release layer is 80-200 μm.
[3] The impact-protective tape according to [1] or [2], wherein the substrate layer comprises 100 parts by weight of polyvinyl chloride; 30-60 parts by weight of a plasticizer, preferably 45-55 parts by weight of a plasticizer; 1.5-3 parts by weight of a heat stabilizer; 5-40 parts of a modifier, preferably 15-25 parts of the modifier; and 10 to 35 parts by weight of a filler.
[4] The impact protection tape according to [3], wherein the plasticizer is a plasticizer having a molecular weight of 1000 or less, preferably at least one of dinonyl phthalate, dioctyl phthalate and di (2-ethyl) hexyl phthalate; the modifier is at least one of MBS resin, chlorinated polyethylene, ethylene-vinyl acetate copolymer, natural rubber and acrylic resin; the filler is at least one of calcium carbonate, silicon dioxide, kaolin, titanium dioxide, carbon black and glass fiber.
[5] The impact protection tape according to [4], wherein the chlorinated polyethylene has a chlorine content of 25 to 45% based on the total mass of the chlorinated polyethylene.
[6] The impact protection tape according to [1] or [2], wherein the pressure-sensitive adhesive layer comprises a (meth) acrylic polymer.
[7] The impact protection tape according to [6], wherein the pressure-sensitive adhesive layer further comprises a halogen-containing compound.
[8] The impact protection tape according to [7], wherein the halogen-containing compound is added in an amount of 4 to 45%, preferably 15 to 40%, based on the total mass of the pressure-sensitive adhesive layer.
[9] The impact-protective tape according to [7], wherein the halogen-containing compound comprises one or more of fluororubber, polyvinylidene fluoride, fluororesin, chlorinated rubber, chloroprene rubber, chlorobenzene rubber, polyvinylidene chloride, and epichlorohydrin resin.
[10] The impact protection tape according to [1] or [2], the pressure-sensitive adhesive layer optionally containing a tackifier resin in an amount of 0 to 25%, preferably 0 to 15%, based on the total mass of the pressure-sensitive adhesive layer.
[11] The impact protection tape according to [7], wherein the halogen-containing compound is dissolved in toluene at 25 ℃ until the viscosity of a 20% strength liquid is 5 to 330 mPas, preferably 5 to 170 mPas, more preferably 5 to 100 mPas.
[12] The impact protection tape according to [1] or [2], wherein the halogen content of the pressure-sensitive adhesive layer is 1500 to 90000ppm based on the total mass of the pressure-sensitive adhesive layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The impact protection tape of the present invention has a low halogen content and is thus environmentally friendly, has excellent anchoring properties and holding power to a substrate, has excellent coatability and good resistance to plasticizers, and the adhesive polymer and halogen-containing compound contained therein have good compatibility.
Drawings
Fig. 1 is a sectional view schematically showing the structure of an impact protection tape according to the present embodiment.
Description of the reference numerals
1 impact protection tape
10 base material layer
20 pressure-sensitive adhesive layer
Detailed Description
< impact protection tape >
Referring to fig. 1, the impact protection tape 1 of the present invention includes a substrate layer 10 and a pressure sensitive adhesive layer 20 laminated on at least one surface of the substrate layer. The adhesive force of the impact protection tape is more than 2.5N/20mm after the impact protection tape is stored at 80 ℃ for 3 days. The upper limit of the adhesive force is not limited, but the adhesive force is preferably 6N/20mm or less from the viewpoints that the adherend is not easily peeled off, the peeling workability is good, and the occurrence of residual contamination is not easily caused. Preferably, the adhesive force of the impact protection tape is 2.5-5N/20 mm after the impact protection tape is stored at 80 ℃ for 3 days, and more preferably 2.5-4N/20 mm. If the adhesive force is less than 2.5N/20mm, the impact protection tape easily peels off from the adherend, fails to function as an anchor, and is poor in impact resistance.
In the present invention, the adhesive force of the impact protection tape at normal temperature (usually 23 ℃) is preferably 2 to 10N/20mm, more preferably 3 to 9N/20mm, and still more preferably 4 to 8N/20 mm.
Preferably, the impact protection tape 1 of the present invention further comprises a release layer (not shown in fig. 1) laminated on the pressure-sensitive adhesive layer 20, wherein the thickness of the release layer is 80 to 200 μm, preferably 100 to 150 μm.
The release layer is not particularly limited, and for example, there can be used: a release layer having a release treatment layer on the surface of a liner base material such as a resin film or paper; and release layers formed of low-adhesion materials such as fluorine-based polymers (e.g., polytetrafluoroethylene) and polyolefin-based resins (e.g., polyethylene and polypropylene). The release treatment layer may be formed by surface-treating the backing material with a release treatment agent such as silicone, long-alkyl, fluorine, or molybdenum sulfide.
Substrate layer
The thickness of the substrate layer is 100-500 mu m, preferably 150-480 mu m, and more preferably 200-450 mu m. If the thickness of the base material layer is too low or too high, the retention force of the impact protection tape is poor, and the impact resistance is poor.
The substrate layer comprises 100 parts by weight of polyvinyl chloride; 30-60 parts by weight of a plasticizer, preferably 45-55 parts by weight of a plasticizer; 1.5-3 parts by weight of a heat stabilizer; 5-40 parts of a modifier, preferably 15-25 parts of the modifier; and 10 to 35 parts by weight of a filler.
(plasticizer)
In the present invention, the base material layer contains a plasticizer having a molecular weight of 1000 or less. Examples of the plasticizer include: and plasticizers such as terephthalate esters, isophthalate esters, phthalate esters, trimellitate esters, adipate esters (e.g., dioctyl adipate, diisononyl adipate), adipate esters, phosphate esters (e.g., tricresyl phosphate), citrate esters (e.g., tributyl acetyl citrate), sebacate esters, azelate esters, maleate esters, benzoate esters, polyether polyesters, epoxy polyesters, and polyesters (e.g., low molecular weight polyesters of carboxylic acid and diol). Preferably at least one of dinonyl phthalate, dioctyl phthalate and di (2-ethyl) hexyl phthalate. The number of the plasticizer may be only 1, or may be 2 or more.
(Heat stabilizer)
Examples of the heat stabilizer include: calcium zinc stabilizers, lead stabilizers, organotin stabilizers, antimony stabilizers, organic auxiliary stabilizers (such as phosphites, epoxy compounds, polyols, etc.). The number of the heat stabilizers may be only 1, or may be 2 or more.
(modifying agent)
Examples of the modifier include: MBS resin (methyl methacrylate-butadiene-styrene copolymer resin), chlorinated polyethylene, ethylene-vinyl acetate copolymer, natural rubber and acrylic resin. The number of the modifier may be only 1, or may be 2 or more. For the chlorinated polyethylene, the chlorine content of the chlorinated polyethylene is 25-45%, preferably 30-40%, based on the total mass of the chlorinated polyethylene.
(Filler)
Examples of the filler include: at least one of calcium carbonate, silicon dioxide, kaolin, titanium dioxide, carbon black and glass fiber. The number of the fillers may be only 1, or may be 2 or more.
If the content of each of the plasticizer, the heat stabilizer, the modifier and the filler is out of the above range, the impact protection tape tends to have poor holding power and impact resistance, and the workability of forming a film of the base layer tends to be poor.
(formation of substrate layer)
The substrate layer may be formed by a known method, for example, by mixing polyvinyl chloride, a plasticizer, a heat stabilizer, a modifier, and a filler in the above-mentioned amounts, drying, and laminating. The substrate layer can be made in the form of a film, for example, by a known film-forming method.
Pressure-sensitive adhesive layer
The thickness of the pressure-sensitive adhesive layer is 15-45 μm, preferably 20-40 μm, and more preferably 20-30 μm. If the thickness of the pressure-sensitive adhesive layer is too low or too high, the retention force of the impact-protective tape is poor, and the impact resistance is poor.
The pressure sensitive adhesive layer of the present invention may be formed from an adhesive composition comprising an adhesive polymer, preferably further comprising a halogen-containing compound.
(adhesive Polymer)
As the adhesive polymer, for example, a (meth) acrylic polymer, a urethane polymer, a synthetic rubber polymer, a natural rubber polymer, a silicone polymer, or the like can be used, and among these, at least 1 selected from the group consisting of a (meth) acrylic polymer, a urethane polymer, and a silicone polymer is more preferable, and a (meth) acrylic polymer is particularly preferably used.
In the present specification, the term "(meth) acrylic polymer" means a methacrylic polymer and/or an acrylic polymer.
The adhesive polymer in the present invention is preferably a polymer of the following monomer components: the monomer component contains an adhesive monomer as a main monomer, and may further contain another monomer (copolymerizable monomer) copolymerizable with the main monomer as needed. The main monomer herein means a main component among monomer components constituting the adhesive polymer, that is, a component contained in the monomer components by more than 50% by weight.
In a preferred embodiment, the adhesive monomer comprises an alkyl (meth) acrylate. In the present specification, the term "alkyl (meth) acrylate" refers to an alkyl acrylate and/or an alkyl methacrylate.
The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate in which the alkyl group has 4 to 20 carbon atoms. Specific examples of the alkyl (meth) acrylate having an alkyl group of 4 to 20 carbon atoms are not particularly limited, and include: n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, decyl (meth) acrylate, and the like, Octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. Among these, n-Butyl Acrylate (BA) and 2-ethylhexyl acrylate (2EHA) are preferred. The alkyl (meth) acrylate may be used alone or in combination of two or more.
The content of the adhesive monomer is preferably 80 to 98 parts by weight, most preferably 92 to 97 parts by weight, based on 100 parts by weight of the total monomer components of the adhesive polymer. When the content of the adhesive monomer is within the above range, excellent adhesive retention can be obtained.
As the copolymerizable monomer, a monomer having a polar group can be suitably used. The monomer having a polar group is useful for introducing a crosslinking point into the adhesive polymer or for improving the cohesive force of the adhesive polymer. The copolymerizable monomers may be used alone in 1 kind or in combination of 2 or more kinds.
Non-limiting specific examples of the copolymerizable monomer include a hydroxyl group-containing monomer (hydroxyl group-containing monomer), a carboxyl group-containing monomer (carboxyl group-containing monomer), a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, an epoxy group-containing monomer, a cyano group-containing monomer, an isocyanate group-containing monomer, an amide group-containing monomer, a monomer having a nitrogen atom-containing ring, a monomer having a succinimide skeleton, a maleimide group, an itaconimide group, an aminoalkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate, a vinyl ester, a vinyl ether, an aromatic vinyl compound, an olefin, and the like. Among these, at least 1 selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-containing monomers is preferable.
In a preferred embodiment, the hydroxyl group-containing monomer preferably comprises a hydroxyl group-containing monomer having a primary hydroxyl group and/or a hydroxyl group-containing monomer having a secondary hydroxyl group. In a preferred embodiment, the hydroxyl group-containing monomer comprises a hydroxyl group-containing (meth) acrylate and/or an unsaturated alcohol.
Examples of hydroxyl group-containing (meth) acrylates include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, polycaprolactone acrylate, and the like. Examples of unsaturated alcohols include: vinyl alcohol, allyl alcohol, and the like.
The content of the hydroxyl group-containing monomer is not particularly limited, and for example, the content of the hydroxyl group-containing monomer is 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total monomer components of the adhesive polymer.
As carboxyl group-containing monomers, ethylenically unsaturated monocarboxylic acids and/or ethylenically unsaturated dicarboxylic acids and anhydrides thereof are preferably contained. Examples of ethylenically unsaturated monocarboxylic acids include: acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, isocrotonic acid, and the like. Examples of ethylenically unsaturated dicarboxylic acids and anhydrides thereof include, for example: fumaric acid, itaconic acid, maleic acid, citraconic acid, maleic anhydride, and itaconic anhydride, and the like. Among these, acrylic acid, methacrylic acid and maleic acid are preferable. The carboxyl group-containing monomers may be used singly or in combination of 2 or more.
The content of the carboxyl group-containing monomer is not particularly limited, and is, for example, preferably 1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the total monomer components of the adhesive polymer.
Examples of the sulfonic acid group-containing monomer include: styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide-propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid, and the like.
Examples of the monomer having a phosphoric acid group include: 2-hydroxyethyl acryloyl phosphate, and the like.
Examples of the epoxy group-containing monomer include: epoxy group-containing acrylates such as glycidyl (meth) acrylate and 2-ethyl glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl (meth) acrylate, and the like.
Examples of the cyano group-containing monomer include: acrylonitrile, methacrylonitrile, and the like.
Examples of the isocyanate group-containing monomer include: 2-isocyanatoethyl (meth) acrylate, and the like. Examples of the amide group-containing monomer include: (meth) acrylamide; n, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-di (N-butyl) (meth) acrylamide, and N, N-di (tert-butyl) (meth) acrylamide; n-alkyl (meth) acrylamides such as N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-N-butyl (meth) acrylamide; n-vinylcarboxylic acid amides such as N-vinylacetamide; n, N-dimethylaminopropyl (meth) acrylamide, hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- (meth) acryloylmorpholine and the like.
Examples of the monomer having a nitrogen atom-containing ring include: n-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1, 3-oxazin-2-one, N-vinyl-3, 5-morpholinodione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, N-vinylpyridazine and the like.
Examples of the monomer having a succinimide skeleton include: n- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxohexamethylene succinimide, N- (meth) acryloyl-8-oxohexamethylene succinimide, and the like.
Examples of the maleimide group include: n-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
Examples of the itaconimides include: n-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexyl itaconimide, N-cyclohexylitaconimide, N-lauryl itaconimide, etc.
Examples of aminoalkyl (meth) acrylates include: aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate.
Examples of alkoxyalkyl (meth) acrylates include: methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, and the like.
Examples of the vinyl esters include: vinyl acetate, vinyl propionate, vinyl laurate, and the like.
Examples of the vinyl ethers include: and vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
Examples of the aromatic vinyl compound include: styrene, alpha-methylstyrene, vinyltoluene, chlorostyrene, chloromethylstyrene, and the like.
Examples of olefins include: ethylene, butadiene, isoprene, isobutylene, and the like.
The method for obtaining the adhesive polymer is not particularly limited, and various known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization can be suitably used.
The initiator used in the polymerization may be appropriately selected from conventionally known polymerization initiators depending on the kind of the polymerization method. For example, one or two or more kinds of azo polymerization initiators such as 2, 2' -Azobisisobutyronitrile (AIBN) can be preferably used. As other examples of the polymerization initiator, there can be cited: persulfates such as potassium persulfate; peroxide initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane initiators such as phenyl-substituted ethane; aromatic carbonyl compounds, and the like. The amount of the polymerization initiator to be used may be a usual amount, and for example, may be selected from the range of about 0.005 to about 1 part by weight (typically about 0.01 to about 1 part by weight) based on 100 parts by weight of the total monomer components.
In the present invention, the weight average molecular weight (Mw) of the adhesive polymer (preferably, acrylic polymer) is not particularly limited, and may be, for example, 1,000,000 or less, preferably 400,000 or more. On the other hand, the weight average molecular weight (Mw) of the soluble portion of the adhesive polymer (preferably, acrylic polymer) is preferably 80,000 or less, and more preferably 5,000 or more.
Here, the weight average molecular weight (Mw) is a value in terms of standard polystyrene obtained by Gel Permeation Chromatography (GPC). The GPC apparatus may be, for example, the type "HLC-8320 GPC" (column: TSKgelGMH-H (S), manufactured by Tosoh corporation).
In the present invention, the adhesive composition preferably contains a crosslinking agent for the purpose of adjusting cohesion and the like. The crosslinking agent may be a commonly used crosslinking agent, and examples thereof include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, a melamine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents may be used alone or in combination of two or more.
In a preferred embodiment, the crosslinking agent preferably comprises an epoxy-based crosslinking agent and/or an isocyanate-based crosslinking agent. By using these two crosslinking agents, an appropriate crosslinking reaction can be generated, cohesive force can be sufficiently increased, good adhesion can be secured, and breakage of an adherend during a peeling operation can be effectively prevented.
As the epoxy-based crosslinking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. Preferably an epoxy crosslinking agent having 3 to 5 epoxy groups in one molecule. The epoxy crosslinking agent may be used singly or in combination of two or more.
Specific examples of the epoxy crosslinking agent are not particularly limited, and include, for example: n, N' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, and the like. Commercially available epoxy crosslinking agents include trade name "TETRAD-C" and trade name "TETRAD-X" manufactured by Mitsubishi gas chemical company, "EPICLON CR-5L" manufactured by DIC company, "DENACOL EX-512" manufactured by Rex chemical company, and "TEPIC-G" manufactured by Nissan chemical industry company.
The amount of the epoxy crosslinking agent used is not particularly limited, and is preferably 0.1 to 2 parts by weight based on 100 parts by weight of the adhesive polymer. In the embodiment containing the epoxy crosslinking agent, the epoxy equivalent of the epoxy crosslinking agent is preferably 80 to 120 g/eq.
As the isocyanate-based crosslinking agent, polyfunctional isocyanates (which mean compounds having an average of two or more isocyanate groups per molecule, including compounds having an isocyanurate structure) can be preferably used. The isocyanate-based crosslinking agent may be used singly or in combination of two or more.
Examples of the polyfunctional isocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
Specific examples of the aliphatic polyisocyanate include: 1, 2-ethylene diisocyanate; 1, 2-butylene diisocyanate, 1, 3-butylene diisocyanate, 1, 4-butylene diisocyanate and the like; hexamethylene diisocyanate such as 1, 2-hexamethylene diisocyanate, 1, 3-hexamethylene diisocyanate, 1, 4-hexamethylene diisocyanate, 1, 5-hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 5-hexamethylene diisocyanate, etc.; 2-methyl-1, 5-pentanediisocyanate, 3-methyl-1, 5-pentanediisocyanate, lysine diisocyanate, and the like.
Specific examples of the alicyclic polyisocyanate include: isophorone diisocyanate; cyclohexyl diisocyanates such as 1, 2-cyclohexyl diisocyanate, 1, 3-cyclohexyl diisocyanate, and 1, 4-cyclohexyl diisocyanate; cyclopentyl diisocyanates such as 1, 2-cyclopentyl diisocyanate and 1, 3-cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, and the like.
Specific examples of the aromatic polyisocyanate include: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 4 '-diphenylether diisocyanate, 2-nitrobiphenyl-4, 4' -diisocyanate, 2 '-diphenylpropane-4, 4' -diisocyanate, 3 '-dimethyldiphenylmethane-4, 4' -diisocyanate, 4 '-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1, 4-diisocyanate, naphthalene-1, 5-diisocyanate, 3' -dimethoxybiphenyl-4, 4' -diisocyanate, xylylene-1, 4-diisocyanate, xylylene-1, 3-diisocyanate, and the like.
In the embodiment containing the isocyanate-based crosslinking agent, the isocyanate group content (NCO content) in the isocyanate-based crosslinking agent is preferably 7 to 15%.
The amount of the isocyanate-based crosslinking agent used is not particularly limited, and is preferably 1 to 5 parts by weight based on 100 parts by weight of the adhesive polymer.
As the crosslinking agent, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are preferably used in combination. By using the isocyanate-based crosslinking agent in the above amount in combination with the epoxy-based crosslinking agent in the above amount, both adhesion to an adherend and cohesion can be achieved at a high level. This enables the adhesive layer to exhibit excellent holding performance (cohesive force of the adhesive layer).
Examples of the aziridine-based crosslinking agent include: trimethylolpropane tris [3- (1-aziridinyl) propionate ], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl propionate) ]. As the aziridine-based crosslinking agent, commercially available products can be used. For example, Chemite series (Nippon Shokubai Co., Ltd.) such as Chemite PZ-33 and Chemite DZ-22E can be used.
Examples of the melamine-based crosslinking agent include: hexamethylol melamine, butylated melamine resin (for example, available from DIC under the trade name "SUPER BECKAMINE J-820-60N"), and the like.
Examples of the metal chelate-based crosslinking agent include: an aluminum chelate compound, a titanium chelate compound, a zinc chelate compound, a zirconium chelate compound, an iron chelate compound, a cobalt chelate compound, a nickel chelate compound, a tin chelate compound, a manganese chelate compound, a chromium chelate compound, and the like.
In order to more efficiently perform the above crosslinking reaction, a crosslinking catalyst may also be used. As the crosslinking catalyst, for example, a tin-based catalyst (e.g., dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst used is not particularly limited, and is preferably 0.0001 to 1 part by weight per 100 parts by weight of the adhesive polymer.
The adhesive composition may further comprise any suitable additive. Examples of the additives include adhesion imparting agents, anti-aging agents, fillers, coloring agents, antistatic agents, and surfactants. The above additives may be used alone, or 2 or more of them may be used in combination. When 2 or more additives are used, 1 or 1 of the additives may be added, or 2 or more additives may be added simultaneously. The amount of the additive can be set to any appropriate amount.
(halogen-containing Compound)
The adhesive composition of the present invention has excellent anchoring properties and holding power to a substrate, has excellent coatability and good plasticizer resistance by containing the halogen-containing compound, and the adhesive polymer and the halogen-containing compound have good compatibility.
In the present invention, the type of halogen in the halogen-containing compound is not particularly limited, and may be, for example, fluorine, chlorine, bromine, or iodine. The type of the halogen-containing compound is also not particularly limited, but a halogen-containing polymer, rubber, or resin is preferable. For example, the halogen-containing compound includes one or more of fluororubber, polyvinylidene fluoride, fluororesin, chlorinated rubber, chloroprene rubber, chlorobenzene rubber, polyvinylidene chloride, and epichlorohydrin resin.
In the invention, the addition amount of the halogen-containing compound is 4-45%, preferably 15-40%, based on the total mass of the pressure-sensitive adhesive layer. If the amount of the halogen-containing compound added is less than 4%, the plasticizer contained in the base material layer cannot be effectively inhibited from moving (transferring) to the pressure-sensitive adhesive layer because the amount added is too small, thereby resulting in a decrease in the modulus of the pressure-sensitive adhesive layer and a poor plasticizer resistance of the pressure-sensitive adhesive layer. On the other hand, if the amount of the halogen-containing compound added is more than 45%, the adhesive composition has a high Tg due to an excessive amount of the halogen-containing compound added, and the pressure-sensitive adhesive layer is hard, so that the wettability to an adherend is deteriorated, and the sticking is difficult, and the workability is deteriorated. In the present invention, the viscosity of the liquid in which the halogen-containing compound is dissolved to a concentration of 20% using toluene at 25 ℃ is not particularly limited, and may be, for example, 5 to 330 mPas, preferably 5 to 170 mPas, and more preferably 5 to 100 mPas. If the viscosity is less than 5 mPas or more than 330 mPas, the anchoring property and holding power of the pressure-sensitive adhesive layer to the substrate and the compatibility between the adhesive polymer and the halogen-containing compound are maintained excellent, but not as good as the effect when the viscosity is within the above range.
The viscosity can be measured using a conventional viscosity measurement method, and for example, can be measured using a measurement method in examples described later.
(tackifying resin)
The adhesive composition used to form the pressure sensitive adhesive layer of the present invention optionally contains a tackifying resin. As the tackifier resin that can be contained in the adhesive composition, 1 or 2 or more kinds selected from known various tackifier resins such as a phenol-based tackifier resin, a terpene-based tackifier resin, a modified terpene-based tackifier resin, a rosin-based tackifier resin, a hydrocarbon-based tackifier resin, an epoxy-based tackifier resin, a polyamide-based tackifier resin, an elastic-based tackifier resin, and a ketone-based tackifier resin can be used. By using a tackifier resin, the adhesion is improved.
Examples of the phenolic tackifying resins include terpene phenol resins, hydrogenated terpene phenol resins, alkyl phenol resins, and rosin phenol resins.
The terpene-phenol resin is a polymer containing a terpene residue and a phenol residue, and is a concept including both a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin) and a resin obtained by phenol-modifying a terpene or a homopolymer or a copolymer thereof (phenol-modified terpene resin). Suitable examples of terpenes constituting such a terpene-phenol resin include: monoterpenes such as α -pinene, β -pinene, limonene (including d-isomer, l-isomer, and d/l-isomer (dipentene)). The hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. Sometimes also referred to as hydrogenated terpene phenol resins.
The alkylphenol resin is a resin (oleo-phenolic resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include novolak type and resol type.
The rosin phenol resin is typically a rosin or a phenol-modified product of the above rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). Examples of the rosin phenol resin include rosin phenol resins obtained by a method of adding phenol to rosins or the above various rosin derivatives with an acid catalyst and performing thermal polymerization, and the like.
Among these phenolic tackifying resins, terpene phenol resins, hydrogenated terpene phenol resins, and alkylphenol resins are preferable, terpene phenol resins and hydrogenated terpene phenol resins are more preferable, and terpene phenol resins are particularly preferable.
Examples of the terpene-based tackifier resin include polymers of terpenes (for example, monoterpenes) such as α -pinene, β -pinene, d-limonene, l-limonene, and dipentene. The terpene may be a homopolymer of 1 kind of terpene, or a copolymer of 2 or more kinds of terpenes. Examples of the homopolymer of 1 terpene include an α -pinene polymer, a β -pinene polymer, and a dipentene polymer.
Examples of the modified terpene resin include those obtained by modifying the above terpene resins. Specifically, a styrene-modified terpene resin, a hydrogenated terpene resin, and the like can be exemplified.
The rosin-based tackifier resin referred to herein includes both rosin-based resins and rosin derivative resins. Examples of rosins include: unmodified rosins (raw rosins) such as gum rosin, wood rosin, tall oil rosin and the like; modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, other chemically modified rosins, etc.) obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc.
Rosin derivative resins are typically derivatives of such rosins as described above. The rosin-based resin referred to herein includes derivatives of unmodified rosins and derivatives of modified rosins (including hydrogenated rosins, disproportionated rosins and polymerized rosins). Examples thereof include: rosin esters such as an unmodified rosin ester as an ester of an unmodified rosin and an alcohol, and a modified rosin ester as an ester of a modified rosin and an alcohol; for example, unsaturated fatty acid-modified rosins obtained by modifying rosins with unsaturated fatty acids; for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; for example, rosin alcohols obtained by reducing carboxyl groups of rosins or the various rosin derivatives described above (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters); for example, metal salts of rosins or various rosin derivatives described above; and the like. Specific examples of rosin esters include: methyl esters, triethylene glycol esters, glycerol esters, pentaerythritol esters, and the like of unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, and the like).
Examples of the hydrocarbon-based tackifier resin include: various hydrocarbon-based resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene/olefin copolymers, etc.), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone/indene-based resins.
The softening point of the tackifier resin is not particularly limited. From the viewpoint of improving the cohesive force, a tackifier resin having a softening point (softening temperature) of about 80 ℃ or higher (preferably about 100 ℃ or higher) may be preferably used. For example, a phenolic tackifying resin (terpene phenol resin or the like) having such a softening point can be preferably used. In a preferred embodiment, a terpene-phenol resin having a softening point of about 135 ℃ or higher (further about 140 ℃ or higher) can be used. The upper limit of the softening point of the tackifier resin is not particularly limited. From the viewpoint of adhesion to an adherend or a base film, a tackifier resin having a softening point of about 180 ℃ or less (more preferably about 150 ℃ or less) can be preferably used. The softening point of the tackifier resin can be measured according to a softening point test method (ring and ball method) specified in JIS K2207.
A preferable embodiment includes an embodiment in which the tackifier resin contains 1 or 2 or more kinds of phenol-based tackifier resins (for example, terpene-phenol resins). The present invention can be preferably carried out in such a manner that, for example, about 25% by weight or more (more preferably about 30% by weight or more) of the total amount of the tackifier resin is a terpene-phenol resin. About 50 wt% or more of the total amount of the tackifier resin may be the terpene-phenol resin, or about 80 wt% or more (for example, about 90 wt% or more) may be the terpene-phenol resin. Substantially all (for example, about 95 wt% or more and 100 wt% or less, and further about 99 wt% or more and 100 wt% or less) of the tackifier resin may be the terpene-phenol resin.
In the embodiment using a tackifier resin, the content of the tackifier resin is not particularly limited. Based on the total mass of the pressure-sensitive adhesive layer, the addition amount of the tackifying resin is 0-25%, preferably 0-15%, and more preferably 3-15%.
In the invention, the halogen content of the pressure-sensitive adhesive layer is 1500-90000 ppm, and preferably 1800-85000 ppm. In the present invention, the pressure-sensitive adhesive layer is formed of the adhesive composition, and thus the halogen content of the pressure-sensitive adhesive layer is the same as that of the adhesive composition. The halogen content of the pressure-sensitive adhesive layer was measured by the method in the examples described later.
< formation of impact protection tape >
The pressure-sensitive adhesive layer may be formed by a conventionally known method. For example, a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically, coating) the adhesive composition onto a base material layer and drying it can be employed. In addition, a method (transfer method) of forming a pressure-sensitive adhesive layer on a surface having releasability (release surface) by applying the pressure-sensitive adhesive composition to the surface and drying the same, and transferring the pressure-sensitive adhesive layer onto a base material layer may also be employed.
The present invention is described in more detail below with reference to examples, but it should be noted that the present invention is not construed as being limited by the examples. The components used in the examples are commercially available.
Example 1
< preparation of adhesive composition >
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 97 parts by weight of n-Butyl Acrylate (BA), 2.8 parts by weight of Acrylic Acid (AA), 0.2 parts by weight of 2-hydroxyethyl acrylate (HEA) and 60 parts by weight of ethyl acetate as a polymerization solvent were charged, and after stirring at 60 to 65 ℃ for 1 hour under a nitrogen atmosphere, 0.15 parts of 2, 2' -Azobisisobutyronitrile (AIBN) was charged as a thermal polymerization initiator, and a reaction was carried out at 60 to 65 ℃ for 6 hours to obtain a solution of an acrylic polymer.
To the acrylic polymer solution, 20 parts by weight of a chlorinated rubber as a halogen-containing compound and 3 parts by weight of an isocyanate-based crosslinking agent as a crosslinking agent were added, and the mixture was stirred and mixed, relative to 100 parts by weight of the acrylic polymer contained in the solution, to prepare an adhesive composition.
< preparation of base Material layer >
100 parts by weight of polyvinyl chloride (HS-1000), 25 parts by weight of diisononyl phthalate (DINP), 2.5 parts by weight of a calcium-zinc heat stabilizer, 20 parts by weight of chlorinated polyethylene and 25 parts by weight of calcium carbonate were mixed together and dried, and a base film was produced by a calendering method.
Examples 2 to 9 and comparative examples 1 to 4
The acrylic monomer components and the amounts used were set as shown in tables 1 to 3, and the other contents were carried out in the same manner as in example 1 to prepare acrylic polymer solutions of examples 2 to 9 and comparative examples 1 to 4, respectively; adhesive compositions of examples 2 to 9 and comparative examples 1 to 4 were prepared by setting the kinds and amounts of the halogen-containing compound, the isocyanate-based crosslinking agent and the polymerized rosin resin (tackifying resin) in the manners shown in tables 1 to 3, respectively.
The components and the amounts of the base material layer were set as shown in tables 1 to 3, and the other contents were carried out in the same manner as in example 1 to prepare base material layers of examples 2 to 9 and comparative examples 1 to 4, respectively.
< preparation of impact protection tape >
In examples 1 to 9 and comparative examples 1 to 4, the adhesive compositions prepared were each applied to one surface of the base film, dried at 120 ℃ for 5 minutes, and cured at 50 ℃ for 24 hours. The thicknesses of the pressure sensitive adhesive layer and the substrate layer were set in the manner shown in tables 1 to 3, ready for testing.
The resulting adhesive tape was evaluated by the following test methods.
(1) [ measurement of viscosity of halogen-containing Compound ]
1g of a halogen-containing compound was precisely weighed, and 100mL of toluene was added at 25 ℃ to dissolve the halogen-containing compound in a 20% concentration liquid, and the measurement was performed at 25 ℃ using a BL type viscometer.
(2) [ measurement of halogen content in pressure-sensitive adhesive layer ]
And (3) sticking a polyethylene terephthalate substrate with the surface energy of more than 60dyn/cm on the surface of the pressure-sensitive adhesive layer of the tape to be tested, and quickly peeling off the pressure-sensitive adhesive layer of the tape to be tested to the polyethylene terephthalate substrate. The halogen content in the pressure sensitive adhesive layer on the polyethylene terephthalate substrate was tested using an X-ray fluorescence spectrometer.
(3) [ measurement of adhesive force of adhesive tape at Normal temperature ]
The adhesive tape was adhered to an SUS304 plate (adhesive area 200mm × 20mm) by reciprocating the tape once by a 2kg roller, and then left to stand at 23 ℃ for 20 to 40 minutes, and the peel strength when the tape was peeled off was measured in a 180 ° peeling direction at a tensile speed of 300mm/min by a tensile tester, and this was used as the adhesive force of the tape at normal temperature.
(4) [ measurement of adhesive force of adhesive tape after storage at 80 ℃ for 3 days ]
The adhesive tape was adhered to an SUS304 plate (adhesive area 200mm × 20mm) by reciprocating the tape once by a 2kg roller, and then left to stand in an environment of 80 ℃ for 3 days, and the peel strength when the tape was peeled off was measured in a 180 ° peeling direction at a tensile speed of 300mm/min by a tensile tester, and this was used as the adhesive force after the tape was stored at 80 ℃ for X3 days.
(5) Evaluation of anchoring property of pressure-sensitive adhesive layer to substrate layer
The adhesive tape was attached to an SUS304 plate (attachment area 200 mm. times.20 mm) by reciprocating the tape once by a 2kg roller, and then left to stand at 23 ℃ for 20 to 40 minutes, and when the tape was peeled off in a 180 DEG peeling direction at a tensile speed of 300mm/min by a tensile tester, the condition of residual adhesive was checked. The evaluation criteria are as follows:
complete absence of adhesive residue on SUS304 plate surface
The surface of delta SUS304 plate has an area ratio of less than 10% of residual glue
The surface of the XSUS 304 plate has residual glue with area ratio of more than or equal to 10 percent
(6) Evaluation of holding force of pressure-sensitive adhesive layer to adhered object
One surface of the pressure-sensitive adhesive layer of the adhesive tape is attached to a phenolic resin plate, and the attaching area is 10mm x 20 mm; a500 g weight was hung on the tape at 40 ℃ for 1 hour, and the tape was then examined for slippage on the phenolic plate. The evaluation criteria are as follows:
o sliding distance is less than or equal to 3mm
The sliding distance is more than 3mm when the triangle is more than or equal to 15mm
X fall off
(7) Evaluation of compatibility between adhesive Polymer and halogen-containing Compound
The solutions of the acrylic polymers prepared in examples 1 to 9 and comparative examples 1 to 4 were each mixed with a halogen-containing compound in the formulation ratios of the acrylic polymer and the halogen-containing compound in tables 1 to 3 to obtain mixed solutions. Using a BL type viscometer, a viscosity test was performed at 25 ℃ and then the condition of the mixed solution was checked. The evaluation criteria are as follows:
the mixed solution was uniform and transparent, and the viscosity of the acrylic polymer was increased by 30% or less (not including 30%) compared with the viscosity before mixing
The delta mixed solution is uniform and transparent, and the viscosity of the acrylic polymer is increased by more than 30 percent compared with that before mixing
X the mixed solution was stratified and opaque
(8) Evaluation of coating workability
The mixed solution was prepared in the same manner as in (7) above, and was applied to the adhesive tapes prepared in the respective examples and comparative examples using a coater equipped with a doctor blade roll, and then the surface condition of the adhesive side of the adhesive tape was examined. The evaluation criteria are as follows:
good leveling of the mixed solution and uniform thickness of the adhesive film finally formed
The mixed solution has poor micro-leveling and the finally formed adhesive film has uneven thickness
X poor leveling of the mixed solution and no application
(9) Evaluation of impact resistance of adhesive tape
The tape was removed from the release layer and attached to a smooth stone slab, the stone slab with the tape attached was impacted with a sand blasting machine (nozzle distance 5mm, pressure 2.0kg), and then the surface condition of the tape and the surface condition of the stone slab after the tape was removed were confirmed. The evaluation criteria are as follows:
good adhesive tape surface without damage, and stone plate surface without visual damage
The surface of the delta adhesive tape is damaged but not broken, and the surface of the stone slab is good or slightly damaged
The surface of the stone slab is seriously damaged due to the broken holes on the surface of the X adhesive tape
(10) Evaluation of film Forming workability of base Material layer
The components of the base material layers in examples 1 to 9 and comparative examples 1 to 4 were mixed in a mixer according to the formulation ratios of the components of the base material layers in tables 1 to 3, and the resulting mixture was banburied in a banbury mixer. The mixture after banburying was formed into a film on a calender, and then appearance of the film was confirmed. The evaluation criteria are as follows:
o film surface smooth and flat, color homogeneous
The surface of the delta film has slight convex points, but the flatness is still good, and the color is more uniform
X film surface roughness and poor flatness, surface color obvious non-uniformity
The evaluation results of each example and comparative example are shown in the following table.
Wherein BA is n-butyl acrylate, 2EHA is 2-ethylhexyl acrylate, AA is acrylic acid, HEA is 2-hydroxyethyl acrylate, DINP is diisononyl phthalate, CPE is chlorinated polyethylene
TABLE 1
Figure BDA0002568551650000211
TABLE 2
Figure BDA0002568551650000221
TABLE 3
Figure BDA0002568551650000231
As can be seen from tables 1 to 3, the impact protection tape of the present invention has a low halogen content and is thus environmentally friendly, has excellent anchoring properties and holding power to a substrate, has excellent coatability and good plasticizer resistance, and the adhesive polymer and halogen-containing compound contained therein have good compatibility, and impact resistance and film-forming workability of the substrate layer are excellent. On the other hand, comparative examples 1 to 4 do not contain a halogen-containing compound, and as a result, the obtained adhesive tapes cannot have excellent holding power, and both impact resistance and film forming workability of the base material layer are poor, and the object of the present invention cannot be achieved.

Claims (12)

1. An impact-protective tape comprising a base material layer and a pressure-sensitive adhesive layer laminated on at least one surface of the base material layer, characterized in that the impact-protective tape has an adhesive force of 2.5N/20mm or more after being stored at 80 ℃ for 3 days; preferably, the thickness of the substrate layer is 100-500 μm; and preferably, the thickness of the pressure-sensitive adhesive layer is 15-45 μm.
2. The impact-protective tape according to claim 1, further comprising a release layer laminated on the pressure-sensitive adhesive layer, wherein the release layer has a thickness of 80 to 200 μm.
3. The impact protection tape of claim 1 or 2 wherein the substrate layer comprises 100 parts by weight polyvinyl chloride; 30-60 parts by weight of a plasticizer, preferably 45-55 parts by weight of a plasticizer; 1.5-3 parts by weight of a heat stabilizer; 5-40 parts of a modifier, preferably 15-25 parts of the modifier; and 10 to 35 parts by weight of a filler.
4. The impact-protective tape according to claim 3, wherein the plasticizer is a plasticizer having a molecular weight of 1000 or less, preferably at least one of dinonyl phthalate, dioctyl phthalate, di (2-ethyl) hexyl phthalate; the modifier is at least one of MBS resin, chlorinated polyethylene, ethylene-vinyl acetate copolymer, natural rubber and acrylic resin; the filler is at least one of calcium carbonate, silicon dioxide, kaolin, titanium dioxide, carbon black and glass fiber.
5. The impact protection tape according to claim 4, wherein the chlorinated polyethylene has a chlorine content of 25 to 45% based on the total mass of the chlorinated polyethylene.
6. The impact protection tape of claim 1 or 2, wherein the pressure sensitive adhesive layer comprises a (meth) acrylic polymer.
7. The impact protection tape of claim 6 wherein the pressure sensitive adhesive layer further comprises a halogen-containing compound.
8. The impact-protective tape according to claim 7, wherein the halogen-containing compound is added in an amount of 4 to 45%, preferably 15 to 40%, based on the total mass of the pressure-sensitive adhesive layer.
9. The impact protection tape of claim 7 wherein the halogen-containing compound comprises one or more of a fluoroelastomer, a polyvinylidene fluoride, a fluororesin, a chlorinated rubber, a neoprene, a chlorobenzene rubber, a polyvinylidene chloride, a epichlorohydrin resin.
10. The impact-protective tape according to claim 1 or 2, wherein the pressure-sensitive adhesive layer optionally contains a tackifier resin, and the tackifier resin is added in an amount of 0 to 25%, preferably 0 to 15%, based on the total mass of the pressure-sensitive adhesive layer.
11. The impact protection tape according to claim 7, wherein the halogen-containing compound is dissolved with toluene at 25 ℃ to a 20% strength liquid viscosity of 5 to 330 mPas, preferably 5 to 170 mPas, more preferably 5 to 100 mPas.
12. The impact-protective tape according to claim 1 or 2, wherein the halogen content of the pressure-sensitive adhesive layer is 1500 to 90000ppm based on the total mass of the pressure-sensitive adhesive layer.
CN202010637026.2A 2020-07-03 2020-07-03 Impact protection adhesive tape Pending CN113881358A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010637026.2A CN113881358A (en) 2020-07-03 2020-07-03 Impact protection adhesive tape

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010637026.2A CN113881358A (en) 2020-07-03 2020-07-03 Impact protection adhesive tape

Publications (1)

Publication Number Publication Date
CN113881358A true CN113881358A (en) 2022-01-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010637026.2A Pending CN113881358A (en) 2020-07-03 2020-07-03 Impact protection adhesive tape

Country Status (1)

Country Link
CN (1) CN113881358A (en)

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