WO2017170446A1 - 両面粘着シート - Google Patents

両面粘着シート Download PDF

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Publication number
WO2017170446A1
WO2017170446A1 PCT/JP2017/012471 JP2017012471W WO2017170446A1 WO 2017170446 A1 WO2017170446 A1 WO 2017170446A1 JP 2017012471 W JP2017012471 W JP 2017012471W WO 2017170446 A1 WO2017170446 A1 WO 2017170446A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
double
sided
adhesive layer
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Application number
PCT/JP2017/012471
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English (en)
French (fr)
Japanese (ja)
Inventor
迪 三浦
千春 平野
宮田　壮
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020187021222A priority Critical patent/KR20180088918A/ko
Priority to CN201780005806.1A priority patent/CN108473829B/zh
Priority to JP2017534751A priority patent/JP6204636B1/ja
Publication of WO2017170446A1 publication Critical patent/WO2017170446A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a double-sided pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet depends on the composition of the pressure-sensitive adhesive and the polarity, as well as the coating amount of the pressure-sensitive adhesive on the support, that is, the thickness of the pressure-sensitive adhesive layer to be formed. That is, as the pressure-sensitive adhesive sheet generally has a thicker pressure-sensitive adhesive layer, the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet becomes higher.
  • the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet such as a label or tape is appropriately set according to the application of the pressure-sensitive adhesive sheet. However, since there is a concern about a decrease in pressure-sensitive adhesive force, the thickness is less than 10 ⁇ m. Not. However, in recent years, it has been desired to reduce the thickness of electronic devices and optical devices, etc. For adhesive sheets used for bonding of members of such electronic devices and optical devices, or temporary bonding during processing, etc. Is required to have a high adhesive strength while being thinned.
  • Patent Document 1 has an adhesive layer on both surfaces of a support such as a polyethylene terephthalate (PET) film having a thickness of 0.002 to 0.012 mm, and the total thickness is 0.003 mm or more and 0.03 mm.
  • PET polyethylene terephthalate
  • a double-sided adhesive tape having a breaking strength of 2 to 26 MPa / 10 mm width is disclosed.
  • the thinning of the support is limited in terms of production and strength of the support.
  • a double-sided pressure-sensitive adhesive sheet having a structure in which the support layer (core material) is not provided and the pressure-sensitive adhesive layer is sandwiched between two release materials is used.
  • a method for reducing the thickness is also conceivable.
  • the support (core material) is omitted, when one of the two release materials is peeled off, the pressure-sensitive adhesive layer does not peel off at a predetermined interface where the release material should be peeled off, and the adhesive layer cohesively breaks down.
  • a “crying separation phenomenon” in which a part of the pressure-sensitive adhesive layer remains on both of the release materials tends to occur.
  • Patent Document 1 there is no examination for further reducing the film thickness while maintaining the adhesive force of the double-sided adhesive sheet and for avoiding the “crying separation phenomenon” associated with the thinner adhesive layer.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a double-sided pressure-sensitive adhesive sheet that can exhibit a sufficiently high adhesive force even if it is thinned, and is excellent in the effect of suppressing the tearing phenomenon.
  • the present inventors use the support containing polylactic acid and adjust the thickness of the support to a predetermined value or less, thereby I found that it could be solved. That is, the present invention provides the following [1] to [8].
  • [1] A double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on both sides of a support, The support comprises polylactic acid, and the support has a thickness of 1.5 ⁇ m or less; Double-sided adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet of the present invention can exhibit a sufficiently high adhesive force even if it is thinned, and is excellent in the effect of suppressing the tearing phenomenon.
  • the thickness of each layer constituting the double-sided pressure-sensitive adhesive sheet and the total thickness of the double-sided pressure-sensitive adhesive sheet are values measured by spectroscopic analysis of reflected light, specifically based on the method described in the examples. Means the measured value.
  • the value of the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically measured based on the method described in the examples. Means the value.
  • GPC gel permeation chromatography
  • the double-sided pressure-sensitive adhesive sheet of the present invention is particularly limited as long as it has a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer (hereinafter collectively referred to as “pressure-sensitive adhesive layer”) on both sides of the support, respectively.
  • FIG. 1 is a cross-sectional view of the double-sided pressure-sensitive adhesive sheet showing the configuration of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention.
  • a double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention for example, as shown in FIG. 1A, a first pressure-sensitive adhesive layer 12a and a second pressure-sensitive adhesive layer 12b are directly laminated on both surfaces of a support 11, respectively.
  • the double-sided pressure-sensitive adhesive sheet 1 having the above-described configuration is exemplified.
  • the sheet 2 may be used.
  • the peeling material by which the peeling process was given to both surfaces was laminated
  • the double-sided adhesive sheet which has the structure wound by roll shape may be sufficient. That is, the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention may have a configuration in which a release material is further laminated on one or both surfaces of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer.
  • the total thickness of the double-sided pressure-sensitive adhesive sheet when affixed to two adherends via the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 6.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, still more preferably 4.0 ⁇ m or less, still more preferably 3.5 ⁇ m or less, and particularly preferably 3.0 ⁇ m or less. Even if the double-sided pressure-sensitive adhesive sheet of the present invention is made as thin as 6.0 ⁇ m or less, the double-sided pressure-sensitive adhesive sheet can exhibit a sufficiently high adhesive force, and can effectively suppress the tearing phenomenon.
  • the double-sided pressure-sensitive adhesive when being applied to two adherends via the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the total thickness of the sheet is preferably 1.5 ⁇ m or more, more preferably 1.7 ⁇ m or more, and further preferably 2.0 ⁇ m or more.
  • the “thinned double-sided pressure-sensitive adhesive sheet” means that the total thickness of the double-sided pressure-sensitive adhesive sheet when adhered to two adherends via the double-sided pressure-sensitive adhesive sheet is adjusted to 6.0 ⁇ m or less. It means a double-sided pressure-sensitive adhesive sheet.
  • the total thickness of the double-sided pressure-sensitive adhesive sheet when affixed to two adherends via a double-sided pressure-sensitive adhesive sheet means the layer of a release material or the like removed when affixed to the adherend
  • the thickness of the double-sided pressure-sensitive adhesive sheet excluding the thickness means, for example, the thickness indicated by “Z1” in the double-sided pressure-sensitive adhesive sheet 1 shown in FIG. 1 and “Z2” in the double-sided pressure-sensitive adhesive sheet 2. That is, the “total thickness of the double-sided pressure-sensitive adhesive sheet when pasted on two adherends via a double-sided pressure-sensitive adhesive sheet” is the thickness of the release materials 13a and 13b of the double-sided pressure-sensitive adhesive sheet 2 shown in FIG.
  • the layers other than the support and the pressure-sensitive adhesive layer that are not removed even when being attached to the adherend include a primer layer, an antistatic layer, an ultraviolet absorbing layer, and the like. It is preferable to be provided between the first adhesive layer or the second adhesive layer.
  • the ratio of the thickness of the support to the total thickness 100 of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is preferably 5.0 to 70.0, More preferably, it is 5.2 to 50.0, still more preferably 5.5 to 40.0, still more preferably 6.0 to 30.0, and particularly preferably 6.2 to 20.0. If the said ratio is in the said range, while producing the outstanding adhesive force, it can be set as the double-sided adhesive sheet which can suppress a tearing phenomenon effectively. Moreover, the tearing of the double-sided adhesive sheet which is easy to occur at the time of sticking or peeling can be suppressed.
  • the support which the double-sided pressure-sensitive adhesive sheet of the present invention has includes a polylactic acid and has a thickness of 1.5 ⁇ m or less.
  • a general-purpose resin such as polyethylene terephthalate (PET) or polyurethane, which is a constituent resin of a support used for general pressure-sensitive adhesive sheets, is difficult to be molded as thin as 1.5 ⁇ m or less by a normal molding method. . Further, even if a support having a thickness of 1.5 ⁇ m or less is obtained by using a general-purpose resin such as PET or polyurethane by a special molding method, the effect of improving the adhesive strength is not exhibited by using the support. .
  • PET polyethylene terephthalate
  • polyurethane which is a constituent resin of a support used for general pressure-sensitive adhesive sheets
  • the support containing polylactic acid since the support containing polylactic acid has high self-supporting property, it can be molded as thin as 1.5 ⁇ m or less.
  • the present inventors have found that a double-sided pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on both sides of a support containing polylactic acid has a very high effect of improving the adhesive strength, and particularly exhibits high adhesive strength even when it is made thin.
  • the double-sided pressure-sensitive adhesive sheet according to the present invention has been completed based on the findings.
  • the support containing polylactic acid has high self-supporting property and moderate flexibility even when the thickness is reduced to 1.5 ⁇ m or less.
  • the double-sided pressure-sensitive adhesive sheet provided with a thinned pressure-sensitive adhesive layer on both sides of the support has excellent followability with respect to the surface of the adherend when applied to the adherend, and the pressure-sensitive adhesive layer is made thin. However, it is considered that excellent adhesive strength is expressed.
  • the two pressure-sensitive adhesive layers are divided by the support, and depending on the flexibility of one pressure-sensitive adhesive layer, the other It is unlikely that the adhesive strength of the adhesive layer will change. That is, the adhesive strength of each pressure-sensitive adhesive layer basically depends only on the configuration and characteristics of each pressure-sensitive adhesive layer, and the influence received by the configuration and characteristics of the other pressure-sensitive adhesive layer is extremely small.
  • the support containing polylactic acid is thinned to 1.5 ⁇ m or less.
  • the double-sided PSA sheet of the present invention is considered to exhibit excellent adhesive strength on both sides even when it is thinned. Moreover, since the double-sided adhesive sheet of this invention has a support body as a structure, it can suppress a tearing phenomenon effectively.
  • the thickness of the support used in the present invention is 1.5 ⁇ m or less, preferably 1.2 ⁇ m or less, more preferably 1.0 ⁇ m or less, still more preferably 0.8 ⁇ m or less, and still more preferably 0.6 ⁇ m. Hereinafter, it is particularly preferably 0.4 ⁇ m or less. Since the double-sided PSA sheet using a support having a thickness exceeding 1.5 ⁇ m is hard, the followability with respect to the surface of the adherend is lowered, and as a result, the adhesive force is easily lowered.
  • the thickness of the support is not limited to a lower limit, but the viewpoint of making a double-sided pressure-sensitive adhesive sheet that can effectively suppress the tearing phenomenon, and the breakage of the double-sided pressure-sensitive adhesive sheet that can occur at the time of sticking or peeling are suppressed. From the viewpoint, it is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and still more preferably 0.10 ⁇ m or more.
  • polylactic acid refers to a polymer having a structural unit (1) represented by the following formula (I), and the polymer has a structural unit other than the structural unit (1). May be.
  • the structural unit (1) may be a structural unit derived from L-lactic acid or a structural unit derived from D-lactic acid. That is, the polylactic acid may be poly-L-lactic acid, which is a homopolymer of L-lactic acid, or poly-D-lactic acid, which is a homopolymer of D-lactic acid. It may be a copolymer with D-lactic acid. Among these, the polylactic acid is preferably a copolymer of L-lactic acid and D-lactic acid.
  • the molar ratio of the structural unit derived from L-lactic acid to the structural unit derived from D-lactic acid in the copolymer is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40.
  • the crystallinity can be appropriately maintained, and the support including the copolymer can be adjusted to have an appropriate hardness. .
  • the obtained pressure-sensitive adhesive sheet is affixed to the adherend, excellent followability with respect to the surface of the adherend is obtained, and excellent adhesive strength is easily exhibited.
  • the mass average molecular weight (Mw) of polylactic acid is preferably 20,000 to 500,000, more preferably 50,000 to 400,000, and still more preferably 70,000 to 300,000.
  • the support used in one embodiment of the present invention may contain a resin, an additive, or the like other than polylactic acid as long as the effects of the present invention are not impaired.
  • resins other than polylactic acid that can be included in the support include, for example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, urethane resins such as urethane acrylate, polyethylene resins, polypropylene resins, and polyvinyl chloride.
  • Resin polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer, polystyrene resin, polycarbonate resin, acrylic resin, norbornene resin, cycloolefin resin and the like.
  • additives that can be contained in the support include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and coloring agents.
  • the support used in one embodiment of the present invention only needs to contain polylactic acid.
  • a support formed by molding a resin composition containing polylactic acid but also a resin other than polylactic acid, papers, Or the support body etc. which laminated the support body which consists of metal foils, such as aluminum and copper, with the resin composition containing polylactic acid may be sufficient.
  • the support used in one embodiment of the present invention is a single-layer support formed by molding a resin composition containing polylactic acid.
  • the resin composition may contain resin components other than polylactic acid and various additives as long as the effects of the present invention are not impaired.
  • the content of polylactic acid contained in the support used in one embodiment of the present invention is such that the double-sided pressure-sensitive adhesive sheet can exhibit sufficiently high adhesive strength even if it is thinned, and the support is 1.5 ⁇ m or less in thickness. From the viewpoint of producing the above, it is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably based on the total mass (100% by mass) of the support. Is 95 to 100% by mass.
  • the content of the copolymer of L-lactic acid and D-lactic acid contained in the support used in one embodiment of the present invention is preferably 60% with respect to the total mass (100% by mass) of the support.
  • the content of the copolymer of L-lactic acid and D-lactic acid contained in the support used in one embodiment of the present invention is preferably 60% with respect to the total mass (100% by mass) of the support.
  • 100% by mass more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
  • the film strength of the support used in one embodiment of the present invention is preferably 1 to 300 mN, more preferably 3 to 250 mN, from the viewpoint of providing a double-sided PSA sheet that can exhibit sufficiently high adhesive strength even if it is thinned. It is preferably 5 to 200 mN, more preferably 10 to 130 mN, and particularly preferably 15 to 90 mN. If the film strength of the support is within the above range, even when the double-sided pressure-sensitive adhesive sheet is provided with a thinned pressure-sensitive adhesive layer on both sides of the support, Excellent followability, and excellent adhesive strength is easily expressed.
  • strength of a support body is the value measured based on JISZ1707 (1997), Comprising: Specifically, the value measured based on the method and conditions as described in an Example. Means.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on both sides of the support, respectively.
  • the thickness of each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is preferably independently 0.5 to 3.0 ⁇ m, more preferably 0.7 to 2.0 ⁇ m, and still more preferably 0. .8 to 1.8 ⁇ m, more preferably 0.9 to 1.6 ⁇ m. Since the double-sided pressure-sensitive adhesive sheet of the present invention contains polylactic acid and has a support having a thickness of 1.5 ⁇ m or less, it is sufficiently high even if the thickness of each pressure-sensitive adhesive layer is reduced to 3.0 ⁇ m or less. It can be set as the double-sided adhesive sheet which can express adhesive force.
  • the total thickness of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is preferably 1.0 to 6.0 ⁇ m, more preferably 1.4 to 4.0 ⁇ m, and still more preferably 1.6. It is ⁇ 3.6 ⁇ m, more preferably 1.8 to 3.2 ⁇ m.
  • the pressure-sensitive adhesive which is a material for forming the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is not particularly limited as long as it can exhibit sufficiently high adhesive force even if the pressure-sensitive adhesive layer is thinned.
  • an adhesive containing at least one adhesive resin selected from acrylic resins, urethane resins, rubber resins, silicone resins, vinyl ether resins, polyester resins, and polyolefin resins can be used.
  • the adhesive resin is preferably an ultraviolet non-curable resin.
  • the ultraviolet non-curable resin means a resin having no polymerizable functional group that can be polymerized by irradiation with ultraviolet rays.
  • the pressure-sensitive adhesive is within a range not impairing the effects of the present invention, for example, a crosslinking agent, a tackifier, an ultraviolet absorber, an antioxidant, an antiseptic, a fungicide, a plasticizer, an antifoaming agent, and a wettability.
  • a crosslinking agent for example, a crosslinking agent, a tackifier, an ultraviolet absorber, an antioxidant, an antiseptic, a fungicide, a plasticizer, an antifoaming agent, and a wettability.
  • You may contain additives for adhesives, such as a regulator.
  • the pressure-sensitive adhesive is preferably as low as possible in the content of the oligomer component having a polymerizable functional group.
  • the content of the oligomer component having a polymerizable functional group is preferably less than 5 parts by mass, more preferably less than 1 part by mass, and still more preferably 0.01 parts by mass with respect to 100 parts by mass of the adhesive resin contained in the adhesive. Less than 0.001, more preferably less than 0.001 parts by weight.
  • the pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive to a support or a release material.
  • the pressure-sensitive adhesive is diluted with an organic solvent, It is good also as a solution of.
  • the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and the like, but the organic solvent used in the synthesis of the resin contained in the pressure-sensitive adhesive layer may be used as it is.
  • the solid content concentration of the adhesive solution is preferably 5 to 60% by mass, more preferably 10 to 40% by mass.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are formed from the viewpoint of exhibiting sufficiently high adhesive force even if the pressure-sensitive adhesive layer to be formed is thinned. It is preferable that at least one is a layer formed from an acrylic pressure-sensitive adhesive containing an acrylic resin, and both the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are formed from the acrylic pressure-sensitive adhesive. More preferably, it is a layer.
  • the acrylic pressure-sensitive adhesive is an ultraviolet non-curable acrylic pressure-sensitive adhesive from the viewpoint of maintaining a sufficiently high adhesive force regardless of the environment even if the pressure-sensitive adhesive layer to be formed is thinned.
  • the acrylic resin contained in the adhesive is preferably an ultraviolet non-curable acrylic resin.
  • the acrylic pressure-sensitive adhesive used in one embodiment of the present invention is an acrylic resin having 1 to 20 carbon atoms from the viewpoint of exhibiting sufficiently high adhesive strength even when the pressure-sensitive adhesive layer to be formed is thinned. It is preferable to include an acrylic copolymer (A) having a structural unit (a1) derived from an alkyl (meth) acrylate having an alkyl group and a structural unit (a2) derived from a functional group-containing monomer.
  • the acrylic pressure-sensitive adhesive preferably contains the crosslinking agent (B) together with the acrylic copolymer (A), and contains the above-mentioned pressure-sensitive adhesive additive as long as the effects of the present invention are not impaired. May be.
  • acrylic copolymer (A) and the crosslinking agent (B) contained in an acrylic pressure-sensitive adhesive suitable as a pressure-sensitive adhesive that is a material for forming the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer will be described.
  • the acrylic copolymer (A) contains a structural unit (a1) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “monomer (a1 ′)”) and a functional group. It has a structural unit (a2) derived from a monomer (hereinafter also referred to as “monomer (a2 ′)”).
  • the acrylic copolymer (A) includes the structural units (a3) derived from the monomer (a3 ′) other than the monomers (a1 ′) and (a1 ′) together with the structural units (a1) and (a2). You may have.
  • the form of copolymerization of the acrylic copolymer (A1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • An acrylic copolymer (A) may be used independently and may use 2 or more types together.
  • the acrylic copolymer (A1) is preferably an ultraviolet non-curable acrylic copolymer having no polymerizable functional group.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 16, more preferably 1 to 12, still more preferably 4 to 8, and still more preferably 4 to 6.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Examples include acrylate and stearyl (meth) acryl
  • the monomer (a1 ′) is preferably n-butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate, and more preferably n-butyl (meth) acrylate.
  • the content of the structural unit (a1) is preferably 50 to 98 mol%, more preferably 60 to 97 mol%, still more preferably based on the total structural units (100 mol%) of the acrylic copolymer (A). Is 70 to 96 mol%, more preferably 80 to 93 mol%.
  • Examples of the monomer (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. . These monomers (a2 ′) may be used alone or in combination of two or more.
  • the monomer (a2 ′) is preferably a carboxy group-containing monomer.
  • the carboxy group-containing monomer include (meth) acrylic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, and derivatives thereof, but (meth) acrylic acid, succinic acid, and derivatives thereof are preferable. More preferred are mono (2-acryloyloxyethyl) succinate and 2-carboxyethyl acrylate.
  • the content of the structural unit (a2) is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, still more preferably based on all structural units (100 mol%) of the acrylic copolymer (A). Is 4 to 30 mol%, more preferably 7 to 20 mol%.
  • the acrylic copolymer (A) includes, as the structural unit (a2), a structural unit derived from any of mono (2-acryloyloxyethyl) succinate and 2-carboxyethyl acrylate ( a2-1).
  • the content of the structural unit (a2-1) in the structural unit (a2) is preferably 60 to 100 mol%, more preferably 70 to 100 mol, based on the total amount (100 mol%) of the structural unit (a2). %, More preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, particularly preferably 100 mol%.
  • the content of the structural unit (a2-1) is preferably 2 to 45 mol%, more preferably 3 to 35 mol, based on all structural units (100 mol%) of the acrylic copolymer (A). %, More preferably 4 to 25 mol%, still more preferably 7 to 20 mol%.
  • Examples of the monomer (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl.
  • Examples include (meth) acrylates having a cyclic structure such as (meth) acrylates and imide (meth) acrylates, vinyl acetate, acrylonitrile, and styrene. These monomers (a3 ′) may be used alone or in combination of two or more.
  • the content of the structural unit (a3) is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably based on the total structural units (100 mass%) of the acrylic copolymer (A). Is from 0 to 5 mol%, more preferably from 0 to 1 mol%.
  • the mass average molecular weight (Mw) of the acrylic copolymer (A) is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,300,000, still more preferably 250,000 to 1,100,000, still more preferably 350,000. ⁇ 900,000.
  • the content of the acrylic copolymer (A) in the acrylic pressure-sensitive adhesive used in one aspect of the present invention is preferably 50 to 100% with respect to the total amount (100% by mass) of the active ingredients of the acrylic pressure-sensitive adhesive. It is 100% by mass, more preferably 60 to 99.99% by mass, still more preferably 70 to 99.90% by mass, still more preferably 80 to 99.00% by mass, and particularly preferably 90 to 98% by mass.
  • the acrylic pressure-sensitive adhesive used in one embodiment of the present invention may contain a pressure-sensitive adhesive resin other than the acrylic copolymer (A).
  • the content of the adhesive resin other than the acrylic copolymer (A) is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A) contained in the acrylic adhesive.
  • the amount is more preferably 0 to 60 parts by mass, still more preferably 0 to 30 parts by mass, still more preferably 0 to 15 parts by mass, and particularly preferably 0 to 10 parts by mass.
  • the acrylic pressure-sensitive adhesive used in one embodiment of the present invention preferably contains a crosslinking agent (B) together with the acrylic copolymer (A).
  • the crosslinking agent (B) include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These crosslinking agents (B) may be used independently and may use 2 or more types together.
  • the crosslinking agent (B) preferably contains an isocyanate-based crosslinking agent from the viewpoint of exhibiting sufficiently high adhesive force even in the thinned adhesive layer.
  • the content of the crosslinking agent (B) in the acrylic pressure-sensitive adhesive used in one embodiment of the present invention is preferably 0.01 to 8 parts by mass, more preferably 100 parts by mass of the acrylic copolymer (A). Is 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention preferably has a configuration in which a release material is further laminated on at least one surface of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has a support containing polylactic acid, when the double-sided pressure-sensitive adhesive sheet 2 shown in FIG. The acquired crying phenomenon can be effectively suppressed.
  • the release material to be used is not particularly limited, but a release sheet obtained by applying a release agent on a substrate is preferable from the viewpoint of ease of handling.
  • the release sheet may be one in which a release agent is applied to both surfaces of the substrate and subjected to a release treatment, or may be one in which the release agent is applied to only one surface of the substrate and subjected to the release treatment.
  • the base material for the release material examples include paper base materials such as glassine paper, coated paper and cast coated paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; and polyethylene terephthalate and polybutylene terephthalate. And polyester films such as polyethylene naphthalate, and plastic films such as polyolefin films such as polypropylene and polyethylene.
  • the release agent include release agents containing a resin such as an olefin resin, an isoprene resin, a rubber elastomer such as a butadiene resin, a long-chain alkyl resin, an alkyd resin, a fluorine resin, or a silicone resin. It is done.
  • the mutually same peeling material 13a, 13b may be used, and different things are used. Also good.
  • the release material 13a and the release material 13b are adjusted so that the difference in the release force is different, and the release material (heavy release material) having a higher release force and the release material (lighter release force) than the heavy release material. It is preferable to use two types of release materials.
  • coated to both surfaces and the peeling process was used it is preferable that it was adjusted so that the difference of the peeling force of each surface of the said peeling material may differ.
  • the thickness of the release sheet is not particularly limited and is appropriately selected, but is usually 10 to 200 ⁇ m, preferably 25 to 150 ⁇ m, more preferably 35 to 80 ⁇ m.
  • the manufacturing method of the double-sided adhesive sheet of this invention is not specifically limited.
  • a pressure-sensitive adhesive is applied on one surface of the support 11 and dried to form the first pressure-sensitive adhesive layer 12a.
  • an adhesive can be applied on the other surface of the substrate and dried to form the second adhesive layer 12b.
  • the double-sided pressure-sensitive adhesive sheet 2 shown in FIG. 1B can be produced by the following procedures (ia) to (iiia).
  • An adhesive is applied in the same manner on the surface of the release material 13b prepared separately, and the second adhesive layer 12b is formed by drying.
  • Double-sided adhesive by bonding the surface of the support 11 of the single-sided pressure-sensitive adhesive sheet prepared in (ia) above to the surface of the second pressure-sensitive adhesive layer 12b formed in (iia) above. Sheet 2 is obtained.
  • the double-sided pressure-sensitive adhesive sheet 2 in FIG. 1B it can also be produced by the following procedures (ib) to (iiib).
  • a pressure-sensitive adhesive is applied to the surface of the release material 13a on which the release treatment has been performed, and dried to form the first pressure-sensitive adhesive layer 12a.
  • An adhesive is applied in the same manner on the surface of the release material 13b prepared separately, and the second adhesive layer 12b is formed by drying.
  • the double-sided pressure-sensitive adhesive sheet 2 is bonded to both surfaces of the support 11 by bonding the surface of the first pressure-sensitive adhesive layer 12a and the surface of the second pressure-sensitive adhesive layer 12b, respectively. obtain.
  • an application sheet may be used in order to improve the handleability of the support 11.
  • the “application sheet” is affixed to support the core material or the pressure-sensitive adhesive sheet in order to improve the handling of the core material or pressure-sensitive adhesive sheet that is so thin that it is difficult to convey or affix. This means the sheet.
  • the application sheet is bonded to the support 11 while being laminated, and then the application sheet is peeled off.
  • a double-sided PSA sheet may be produced by laminating one PSA layer.
  • the adhesive When applying the adhesive to the support or release material, in order to facilitate the formation of a thin adhesive layer, as described above, the adhesive is diluted with an organic solvent to form a solution of the adhesive. It is preferable that
  • Examples of the method for applying the pressure-sensitive adhesive on the support or the release material include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating. There are known methods. In order to prevent residual solvents and low-boiling components, and when a cross-linking agent is blended, apply a pressure-sensitive adhesive on the support or release material in order to develop cross-linking (reaction) and develop tackiness. It is preferable to heat-treat after forming the coating film.
  • the temperature condition for the heat treatment is preferably 70 to 150 ° C., more preferably 80 to 120 ° C.
  • the treatment time for the heat treatment is preferably 30 seconds to 5 minutes, more preferably 40 to 180 seconds.
  • the double-sided pressure-sensitive adhesive sheet of the present invention can exhibit a sufficiently high adhesive force and is excellent in the effect of suppressing the tearing phenomenon.
  • RH relative humidity
  • JIS Z0237 2000
  • the adhesive strength measured according to the above is preferably 1.5 N / 25 mm or more, more preferably 2.0 N / 25 mm or more, still more preferably 2.5 N / 25 mm or more, still more preferably 3.0 N / 25 mm or more, Particularly preferably, it is 4.5 N / 25 mm or more.
  • the said adhesive force points out the value measured based on JISZ0237: 2000, and specifically means the value measured by the method and conditions as described in the below-mentioned Example. To do.
  • Mass average molecular weight It is a value determined by standard polystyrene conversion, measured with the following equipment and conditions.
  • Device name “HLC-8220GPC” (manufactured by Tosoh Corporation) Column: “TSKgelGMHXL”, “TSKgelGMMHXL”, and “TSKgel2000HXL” (all manufactured by Tosoh Corporation) connected in sequence
  • Developing solvent Tetrahydrofuran Injection volume: 80 ⁇ l
  • Flow rate 1.0 mL / min
  • Detector Differential refractometer
  • the thickness and total thickness of each layer of the double-sided PSA sheet were measured with a reflective film thickness meter (manufactured by Filmetrics, product name “F20”). Specifically, using the reflective film thickness meter, the film thickness at any seven locations of the double-sided PSA sheet cut to 10 mm ⁇ 100 mm was measured, and the maximum value among the measured film thickness values at the seven locations and The average value of the film thickness values at five locations excluding the minimum value was calculated, and the average value was defined as the thickness or total thickness of each layer of the double-sided pressure-sensitive adhesive sheet to be measured.
  • a reflective film thickness meter manufactured by Filmetrics, product name “F20”.
  • PET film (0.5): Polyethylene terephthalate (PET) film having a thickness of 0.5 ⁇ m (membrane strength 180 mN).
  • PET film (6.0): PET film having a thickness of 6.0 ⁇ m (membrane strength 2040 mN).
  • -Polyurethane film (6.0): A polyurethane film having a thickness of 6.0 ⁇ m (film strength 1540 mN) produced based on the description of Production Example 4 in paragraph [0073] of Patent Document 2 except that the thickness was changed from 2 ⁇ m to 6.0 ⁇ m.
  • the solid content which mixed 0.45 mass part (solid content mass part) of the mass part (solid content mass part) and isocyanate type crosslinking agent (the Tosoh Corporation make, product name "Coronate L”), and diluted with ethyl acetate.
  • a solution of acrylic adhesive having a concentration of 13% by mass.
  • Examples 1-6, Comparative Examples 2-5 On the release-treated surface of a heavy release sheet (product name “SP-PET 381031”, manufactured by Lintec Co., Ltd., PET film with a thickness of 38 ⁇ m peeled with a silicone-based release agent), the type of adhesive shown in Table 1 was applied. And dried at 100 ° C. for 1 minute to form a first pressure-sensitive adhesive layer having a thickness shown in Table 1. And the support body of the kind shown in Table 1 was bonded together on the surface of the exposed 1st adhesive layer, and the single-sided adhesive sheet was obtained.
  • SP-PET 381031 manufactured by Lintec Co., Ltd., PET film with a thickness of 38 ⁇ m peeled with a silicone-based release agent
  • the surface of the PLA film on which the application sheet is not laminated is left in a state in which the application sheet laminated on the PLA film is left in order to maintain handling properties.
  • the first pressure-sensitive adhesive layer were bonded together, and then the application sheet was removed to obtain a single-sided pressure-sensitive adhesive sheet.
  • the first pressure-sensitive adhesive is provided on the release-treated surface of a separately prepared light release sheet (product name “SP-PET381130” manufactured by Lintec Corporation, 38 ⁇ m thick PET film peel-treated with a silicone-based release agent).
  • SP-PET381130 manufactured by Lintec Corporation
  • a second pressure-sensitive adhesive layer having the thickness shown in Table 1.
  • the surface on the support side of the above-mentioned single-sided pressure-sensitive adhesive sheet and the surface of the second pressure-sensitive adhesive layer are bonded, respectively, a heavy release sheet, a first pressure-sensitive adhesive layer, a support, a second pressure-sensitive adhesive layer, A double-sided PSA sheet (P) having a structure in which light release sheets were laminated in this order was produced.
  • a double-sided pressure-sensitive adhesive sheet (Q) having a structure in which a light release sheet, a first pressure-sensitive adhesive layer, a support, a second pressure-sensitive adhesive layer, and a light release sheet were laminated in this order was also produced.
  • a double-sided pressure-sensitive adhesive sheet (Q) having a structure in which a light release sheet, a first pressure-sensitive adhesive layer, a support, a second pressure-sensitive adhesive layer, and a light release sheet were laminated in this order was also produced.
  • the double-sided PSA sheets prepared in Examples 1 to 6 are less susceptible to tearing despite having a thin PSA layer and have excellent adhesive strength.
  • the double-sided pressure-sensitive adhesive sheet produced in Comparative Example 1 resulted in a high frequency of occurrence of the tearing phenomenon.
  • the double-sided PSA sheets prepared in Comparative Examples 2 to 5 were able to suppress the occurrence of the tearing-off phenomenon, but as the PSA layer was made thinner, the double-sided PSA sheets were sufficient compared to the double-sided PSA sheets prepared in Examples. Adhesive strength was not obtained.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is used for, for example, bonding of two members at a location where the clearance is narrow, or temporary bonding at the time of processing, in portable electronic devices and optical devices that are required to be thinned. It is suitable for.

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  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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PCT/JP2017/012471 2016-03-29 2017-03-27 両面粘着シート WO2017170446A1 (ja)

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JP2013075999A (ja) * 2011-09-30 2013-04-25 Lintec Corp 両面粘着シート
JP2014198411A (ja) * 2013-03-29 2014-10-23 リンテック株式会社 粘着シート
WO2015056499A1 (ja) * 2013-10-15 2015-04-23 日東電工株式会社 粘着シート

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JP4646508B2 (ja) 2003-10-01 2011-03-09 日東電工株式会社 両面接着テープ又はシートおよびその製造方法
TWI455966B (zh) * 2007-09-10 2014-10-11 Teijin Ltd 薄膜
US8748543B2 (en) * 2008-09-29 2014-06-10 Teijin Limited Polylactic acid film
CN103228713A (zh) * 2010-11-26 2013-07-31 日东电工株式会社 聚乳酸系薄膜或片
CN104263272A (zh) * 2014-09-25 2015-01-07 无锡市天聚科技有限公司 一种蔬菜和水果用捆绑胶带

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Publication number Priority date Publication date Assignee Title
JP2013075999A (ja) * 2011-09-30 2013-04-25 Lintec Corp 両面粘着シート
JP2014198411A (ja) * 2013-03-29 2014-10-23 リンテック株式会社 粘着シート
WO2015056499A1 (ja) * 2013-10-15 2015-04-23 日東電工株式会社 粘着シート

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