WO2012105340A1 - Release agent, release material, and adhesive tape - Google Patents
Release agent, release material, and adhesive tape Download PDFInfo
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- WO2012105340A1 WO2012105340A1 PCT/JP2012/051215 JP2012051215W WO2012105340A1 WO 2012105340 A1 WO2012105340 A1 WO 2012105340A1 JP 2012051215 W JP2012051215 W JP 2012051215W WO 2012105340 A1 WO2012105340 A1 WO 2012105340A1
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- release agent
- release
- polyolefin
- solvent
- agent according
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Classifications
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/005—Presence of polyolefin in the release coating
Definitions
- the present invention relates to a release agent containing polyolefin (hereinafter sometimes abbreviated as “polyolefin release agent”), and a release material and an adhesive tape having a release agent layer formed from the release agent.
- polyolefin release agent a release agent containing polyolefin (hereinafter sometimes abbreviated as “polyolefin release agent”), and a release material and an adhesive tape having a release agent layer formed from the release agent.
- the release material is provided with a release agent layer on at least one surface of a substrate such as paper, plastic film and plastic laminated paper, and is intended to protect the adhesive surface of an adhesive tape, an adhesive sheet, a label, etc. It is used in manufacturing processes for green sheets.
- a silicone release agent As the release agent, a silicone release agent, a long-chain alkyl release agent, a polyolefin release agent, a fluorine release agent, and the like are known. However, in applications related to electronic parts and the like, there are cases in which silicone-based release agents cause problems, and therefore non-silicone release agents such as polyolefin-based release agents are used.
- an isocyanate crosslinking agent and a polyol may be used in the polyolefin release agent (for example, Patent Documents 1 to 3).
- a urethanization catalyst may be added to accelerate the urethanization reaction between the isocyanate-based crosslinking agent and the polyol.
- organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate have been widely used.
- the organotin compound has high catalytic activity in addition to having good solubility in an organic solvent, so that it can be used to form a release agent layer excellent in appearance and substrate adhesion. .
- JP 2004-346213 A Japanese Patent Laid-Open No. 2004-250681 JP 2004-230773 A
- the present invention has been made by paying attention to such circumstances, and the object thereof is to form a release agent layer having excellent adhesion to a substrate and having a good appearance without using an organic tin compound. It is to provide a release agent that can be used.
- a carboxylic acid metal salt that is a non-organotin compound is used as a urethanization catalyst, and a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent is used as an organic solvent.
- a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent is used as an organic solvent.
- the carboxylic acid metal salt is a non-organotin compound
- a release agent in which the organic solvent is a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent.
- the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene and xylene.
- An adhesive tape having a substrate, an adhesive layer and a release agent layer, A release agent layer formed from the release agent according to any one of the above [1] to [12] is provided on one side of the substrate, A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.
- the release agent of the present invention does not contain an organic tin compound, it can form a release agent layer having excellent adhesion to a substrate and having a good appearance.
- the release agent of the present invention contains polyolefin, isocyanate, polyolefin polyol, metal carboxylate and organic solvent. Hereinafter, each of these components will be described in order.
- polyolefin The release agent of the present invention contains one type or two or more types of polyolefin.
- polyolefin means a polyolefin that is solid at 38 ° C. Any polyolefin can be used as long as it can be dissolved in an organic solvent together with other components and applied to a substrate.
- the density of the polyolefin is preferably 0.885 g / cm 3 or less, more preferably 0.880 g / cm 3 or less.
- this density exceeds 0.885 g / cm 3 , solubility in an organic solvent tends to be lowered, and application to a substrate tends to be difficult, and peeling force tends to increase.
- the lower limit of the density of the polyolefin is not particularly limited, but this density is preferably 0.830 g / cm 3 or more, more preferably 0.857 g / cm 3 or more, and further preferably 0.858 g / cm 3 or more. is there.
- polystyrene resin examples include an ⁇ -olefin copolymer formed from at least two monomers selected from the group consisting of ethylene, propylene and an ⁇ -olefin having 4 to 20 carbon atoms.
- a copolymer having ethylene as a main monomer that is, an ethylene-based ⁇ -olefin copolymer
- a copolymer having propylene as a main monomer that is, a propylene-based ⁇ -olefin. Copolymer
- ⁇ -olefin having 4 to 20 carbon atoms 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1- Examples include pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like.
- the ⁇ -olefin copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
- the density of the ethylene-based ⁇ -olefin copolymer is preferably 0.857 g / cm 3 or more and 0.885 g / cm 3 or less (more preferably 0.880 g / cm 3 or less).
- the ethylene structural unit amount of the ethylene-based ⁇ -olefin copolymer is 50 mol% or more.
- the ethylene structural unit amount is preferably 60 to 95 mol%, more preferably 70 to 95 mol%.
- the ⁇ -olefin structural unit contained in the ethylene-based ⁇ -olefin copolymer is one formed from at least one monomer selected from the group consisting of 1-butene, propylene, 1-hexene and 1-octene. preferable.
- Particularly preferred ethylene-based ⁇ -olefin copolymers include ethylene-1-butene copolymers and ethylene-propylene copolymers.
- Such an ethylene-1-butene copolymer may contain a structural unit derived from ⁇ -olefin other than ethylene and 1-butene in an amount of 10 mol% or less.
- the ethylene-propylene copolymer may contain a structural unit derived from an ⁇ -olefin other than ethylene and propylene in an amount of 10 mol% or less.
- Such a copolymer is produced, for example, by copolymerizing ethylene and ⁇ -olefin using a catalyst comprising a transition metal catalyst component (for example, vanadium compound or zirconium compound) and an organoaluminum compound catalyst component.
- a transition metal catalyst component for example, vanadium compound or zirconium compound
- an organoaluminum compound catalyst component for example, vanadium compound or zirconium compound
- the density of the propylene-based ⁇ -olefin copolymer is preferably 0.858 g / cm 3 or more and 0.885 g / cm 3 or less (more preferably 0.880 g / cm 3 or less).
- the propylene structural unit amount of the propylene-based ⁇ -olefin copolymer is more than 50 mol%.
- the propylene structural unit amount is preferably 60 to 95 mol%, more preferably 70 to 95 mol%.
- the ⁇ -olefin structural unit contained in the propylene-based ⁇ -olefin copolymer is formed of at least one monomer selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene. Those are preferred.
- a particularly preferred propylene-based ⁇ -olefin copolymer is a propylene-ethylene random copolymer (propylene-based elastomer).
- the propylene-ethylene random copolymer may contain a constituent unit derived from ⁇ -olefin other than propylene and ethylene in an amount of 10 mol% or less.
- the propylene-based ⁇ -olefin copolymer can be produced using a metallocene-based catalyst as described in, for example, JP-A-2000-191862.
- ⁇ -olefin copolymer Commercially available products can be used as the ⁇ -olefin copolymer.
- Preferable commercial products of the ethylene-based ⁇ -olefin copolymer include, for example, Tuffmer P series, Tuffmer A series (all manufactured by Mitsui Chemicals), Engage (manufactured by Dow Chemical Company), and the like.
- Tuffmer XM series manufactured by Mitsui Chemicals
- Polymethylpentene can also be used as the polyolefin.
- polymethylpentene examples include a homopolymer of 4-methyl-1-pentene, and a copolymer of 4-methyl-1-pentene and other ⁇ -olefins.
- the amount of 4-methyl-1-pentene constituent unit in the polymethylpentene copolymer is preferably 50 to 95 mol%, more preferably 70 to 95 mol%.
- the polymethylpentene may be a crystalline polymer.
- the density of polymethylpentene is preferably 0.83 to 0.86 g / cm 3 .
- Examples of the ⁇ -olefin structural unit in the polymethylpentene copolymer include 2 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like. Those derived from .alpha.-olefins of .about.20 are preferred. Of these, 1-decene, 1-tetradecene and 1-octadecene, which exhibit good copolymerizability with 4-methyl-1-pentene, are more preferred.
- An example of a commercially available product of polymethylpentene is TPX-S (4-methylpentene-1- ⁇ -olefin copolymer, manufactured by Mitsui Chemicals).
- diolefin rubbers such as polyisoprene and polybutadiene can also be used as the polyolefin.
- polyisoprene has a cis-1,4 bond of 90% or more, a density of 0.90 to 0.92 g / cm 3 , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 40 to 70. Those are preferred.
- Mooney viscosity ML1 + 4 at 100 ° C.
- Examples of commercially available products of polyisoprene include IR-307 and IR-310 (manufactured by Kraton Polymer Co., Ltd.).
- polystyrene resin those having a cis-1,4 bond of 90% or more, a density of 0.88 to 0.91 g / cm 3 , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 25 to 50 are preferable.
- Mooney viscosity ML1 + 4 at 100 ° C.
- commercially available products of polybutadiene include Nipol BR1220, Nipol BR1220L (manufactured by Nippon Zeon), and BR01 (manufactured by JSR).
- the polyolefin in the present invention preferably does not react with the isocyanate described later.
- a modified polyolefin having a functional group such as a hydroxyl group (hydroxy group), an amino group, a carboxy group, or an isocyanate group (isocyanato group) may be used as long as the object of the present invention is not impaired.
- the number of functional groups (average value) per molecule of the modified polyolefin is preferably 1 or less.
- the release agent of the present invention when used in combination with an acrylic pressure-sensitive adhesive, the use of an ethylene-based ⁇ -olefin copolymer and / or a propylene-based ⁇ -olefin copolymer as an olefin may cause the release over time. It is preferable for preventing an increase in force.
- a propylene-based ⁇ -olefin copolymer and / or polymethylpentene is preferable.
- the MFR (melt flow rate) at 230 ° C. of the polyolefin is preferably 100 g / 10 min or less from the viewpoint of the strength (coating film strength) of the release agent layer to be formed. More preferably, it is 70 g / 10 minutes or less, More preferably, it is 50 g / 10 minutes or less, Most preferably, it is 10 g / 10 minutes or less.
- the MFR at 230 ° C. of at least one of the polyolefins is preferably 100 g / 10 min or less, more preferably 70 g / 10 min or less, and even more preferably 50 g / 10 Min. Or less, particularly preferably 10 g / 10 min or less.
- the content of polyolefin having such MFR is preferably 10% by weight, more preferably 50% by weight or more, still more preferably 90% by weight or more, and particularly preferably 100% by weight in the total polyolefin.
- the polyolefin has a tensile modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 8 MPa or less (A-1) Is preferably contained in the total polyolefin in an amount of 90% by weight or more.
- the content of the polyolefin (A-2) other than the polyolefin (A-1) is preferably limited to 10% by weight or less in the total polyolefin.
- the peeling speed dependency means that the peeling force of the release agent layer depends on the peeling speed, and more specifically, means that the peeling force at high speed peeling is larger than the peeling force at low speed peeling. .
- any of the above-described polyolefin (A-1) and polyolefin (A-2) may be used alone or in combination of two or more.
- the content of the polyolefin (A-1) is more preferably 95% by weight or more and still more preferably 100% by weight in the total polyolefin.
- polyolefin (A-1) reduces the release rate dependency because the tensile fracture stress is small under the assumption that fracture occurs near the interface between the adhesive layer and the release agent layer in the release process.
- the presence of the polyolefin (A-1) destroys the vicinity of the interface with a small force, and it is estimated that the increase in the peeling force can be suppressed even when the peeling speed is increased.
- the tensile modulus at 23 ° C. of the polyolefin (A-1) is 10 MPa or less, preferably 8 MPa or less, more preferably 7 MPa or less, and even more preferably 6 MPa or less.
- the tensile fracture stress of the polyolefin (A-1) at 23 ° C. Is 8 MPa or less, preferably 6 MPa or less, more preferably 4 MPa or less.
- Polyolefin (A-2) having a tensile modulus of elasticity exceeding 10 MPa at 23 ° C. tends to increase the peeling force of the release agent layer when peeled at a low speed and a high speed, and has a tensile fracture stress at 23 ° C. exceeding 8 MPa. (A-2) tends to increase the peeling force of the release agent layer when peeled at a high speed.
- the polyolefin (A-2) As the polyolefin (A-2), (i) a polyolefin having a tensile fracture stress at 23 ° C. of 8 MPa or less and a tensile elastic modulus at 23 ° C. of more than 10 MPa; (ii) a tensile elastic modulus at 23 ° C. of 10 MPa or less. And (iii) a polyolefin having a tensile modulus at 23 ° C. of greater than 10 MPa and a tensile fracture stress at 23 ° C. of greater than 8 MPa.
- the polyolefin (A-2) of the embodiment (ii) is preferable.
- the tensile modulus at 23 ° C. of the polyolefin (A-2) is preferably 100 MPa or less, and the tensile fracture stress at 23 ° C. of the polyolefin (A-2) is preferably 35 MPa or less.
- the tensile modulus of elasticity of the polyolefin (A-1) at 23 ° C. is preferably 2 MPa or more, more preferably 3 MPa or more.
- the fracture stress is preferably 1 MPa or more, more preferably 2 MPa or more.
- the “tensile modulus at 23 ° C.” and “tensile fracture stress at 23 ° C.” of the polyolefin are values measured by the following methods. Polyolefin is dissolved in toluene to make a 5 to 10% by weight solution, and this is applied onto a release film made of polyethylene terephthalate (PET) using a baker type applicator or a doctor blade type applicator. Heat-dry (100 ° C., 3 minutes), and immediately after the heat-dry, cool in a 23 ° C. atmosphere to produce a polyolefin film having a thickness of 20 ⁇ m after drying. If the solubility in toluene is poor, it may be dissolved by heating as necessary.
- PET polyethylene terephthalate
- the obtained polyolefin film was cut into strips of 30 mm in length and 100 mm in width, and while peeling off the polyolefin film from the release film, it was tightly wound in the longitudinal direction around one short side of the cut film as a length.
- a 30 mm rod-shaped sample is used.
- This rod-shaped sample was subjected to a tensile test with a tensile tester (manufactured by Shimadzu Corp., Autograph AG-IS type) in a 23 ° C atmosphere under conditions of a distance between chucks of 10 mm and a tensile speed of 50 mm / min. Obtain the stress-strain curve.
- the tensile modulus is calculated from the slope of the stress-strain curve immediately after the start of tension. Further, the stress when the rod-shaped sample is broken is determined as the tensile fracture stress.
- Examples of the polyolefin (A-1) having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 8 MPa or less include Toughmer P-0080K, Tuffmer P-0280, Tuffmer A-335070S, Tuffmer P-0680, Tuffmer P-0180, Tuffmer P-0480, Tuffmer P-0275, Tuffmer P-0775 (all are ethylene-based ⁇ -olefin copolymers, manufactured by Mitsui Chemicals, Inc.) and the like.
- the content of the polyolefin is preferably 80 to 99% by weight, more preferably 90 to 98% by weight in the solid content of the release agent.
- the solid content of the release agent means the total content of release agent components other than the organic solvent.
- the release agent of the present invention contains one or more isocyanates.
- the isocyanate may be either an aromatic isocyanate or an aliphatic isocyanate.
- the aliphatic isocyanate may be either a chain aliphatic isocyanate or an alicyclic isocyanate.
- aromatic isocyanate and alicyclic isocyanate are preferable. Since aromatic isocyanate and alicyclic isocyanate have low compatibility with polyolefin, even if they are used, the releasability of the release agent layer is not impaired.
- aromatic isocyanate and alicyclic isocyanate that are incompatible with polyolefin are unevenly distributed between the release agent layer to be formed and the base material, and greatly contribute to the improvement of adhesion.
- the isocyanate is preferably a polyisocyanate having three or more isocyanate groups in one molecule, more preferably an aromatic polyisocyanate and a fat. It is at least one selected from the group consisting of cyclic polyisocyanates, more preferably at least one selected from the group consisting of polyhydric alcohol adducts of aromatic diisocyanates and polyhydric alcohol adducts of alicyclic diisocyanates. .
- aromatic diisocyanate examples include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like. Of these, tolylene diisocyanate and xylylene diisocyanate are preferred.
- alicyclic diisocyanate examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, trans-cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, and the like. Of these, isophorone diisocyanate and hydrogenated xylylene diisocyanate are preferred.
- polyhydric alcohol examples include aliphatic polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Of these, trimethylolpropane is preferred.
- polyisocyanate examples include compounds having an isocyanate group at the terminal, obtained by reacting the polyhydric alcohol with an excess amount of the aromatic diisocyanate or the alicyclic diisocyanate.
- aromatic diisocyanates or alicyclic diisocyanates eg, isocyanurates
- polyhydric alcohol adduct of aromatic diisocyanate is preferably a polyhydric alcohol adduct of tolylene diisocyanate or xylylene diisocyanate, more preferably a polyhydric alcohol adduct of tolylene diisocyanate.
- the polyhydric alcohol adduct of tolylene diisocyanate is excellent in reactivity and can achieve excellent substrate adhesion.
- the polyhydric alcohol adduct of alicyclic diisocyanate is preferably a polyhydric alcohol adduct of hydrogenated xylylene diisocyanate or isophorone diisocyanate.
- the content of isocyanate in the release agent is preferably 0.5 to 20 parts by weight, more preferably 1.0 to 15 parts by weight, still more preferably 1.5 to 10 parts by weight with respect to 100 parts by weight of polyolefin. Part. If isocyanate is used at such a content, there is no adverse effect such as shortening the pot life of the release agent, and better substrate adhesion can be obtained.
- the release agent of the present invention contains one or more polyolefin polyols.
- Polyolefin polyol is used to react with isocyanate in the formation of a release agent layer.
- the polyolefin polyol those having good compatibility with the polyolefin are preferable.
- the number average molecular weight (Mn) of the polyolefin polyol is preferably 1500 to 50000, more preferably 1500 to 4000, and still more preferably 1500 to 3000.
- a polyolefin polyol having Mn in such a range has moderate solubility in both polyolefin and isocyanate. Therefore, such a polyolefin polyol can improve the release agent layer strength and heat resistance, while not impairing the appearance of the release agent layer.
- this Mn is outside the above range, a release agent layer having a whitish and cloudy appearance may be obtained.
- the release agent layer where the isocyanate on the side opposite to the substrate is not unevenly distributed does not have excessive hydroxyl groups due to the polyolefin polyol, and a release agent layer having a low release force is present. can get. Furthermore, if this Mn is within the above range, the isocyanate and the polyolefin polyol can be appropriately reacted in the release agent layer portion where the isocyanate on the substrate side is unevenly distributed, and more excellent substrate adhesion can be obtained.
- polyolefin polyol is not particularly limited.
- polyolefin polyols include polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, and hydrogenated polyisoprene polyols.
- hydrogenated polyisoprene polyol and polyisoprene polyol are preferable from the viewpoint of compatibility with polyolefin and influence on peeling force.
- the hydroxyl value (mgKOH / g) of the polyolefin polyol is preferably 20 or more from the viewpoint of the release agent layer strength and curability, and is preferably 75 or less from the viewpoint of the influence on the peeling force.
- a more preferred hydroxyl value (mgKOH / g) is 25-60.
- a commercially available polyolefin polyol can be used.
- the content of the polyolefin polyol in the release agent is represented by the following formula (I):
- A hydroxyl value of polyolefin polyol (mgKOH / g) ⁇ number of parts by weight of polyolefin polyol with respect to 100 parts by weight of polyolefin (I)
- the value of A is preferably set to 30 to 250, more preferably 40 to 200, and still more preferably 50 to 150. If the value of A is less than 30, the release agent layer strength tends to be insufficient, and if it is greater than 250, the release force of the release agent layer tends to be too high.
- the release agent of the present invention contains a carboxylic acid metal salt that is a non-organotin compound as a urethanization catalyst.
- the “organotin compound” refers to a compound or salt having a tin-carbon (Sn—C) bond, and examples thereof include dibutyltin dilaurate and dioctyltin dilaurate.
- non-organotin compound refers to a compound or salt having no tin-carbon bond.
- the carboxylic acid of the carboxylic acid metal salt may be either an aliphatic carboxylic acid or an aromatic carboxylic acid.
- the carboxylic acid may be either a monobasic acid or a polybasic acid.
- the aliphatic carboxylic acid may be linear or branched, and may be either saturated or unsaturated.
- the aliphatic carboxylic acid may have an alicyclic alkyl group.
- Examples of the aliphatic carboxylic acid include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, oleic acid and linoleic acid.
- Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the carboxylic acid may be naphthenic acid or resin acid.
- naphthenic acid means carboxylic acid contained in petroleum
- resin acid means carboxylic acid contained in natural resin.
- Naphthenic acid and resin acid may be either one kind or a mixture of two or more kinds.
- naphthenic acid include those having a carboxy group at the end of the methylene side chain of the cyclopentane ring or cyclohexane ring.
- the resin acid include abietic acid, neoabietic acid, dehydroabietic acid, pultrinic acid, levopimaric acid, podocarpic acid, d-pimalic acid, and iso-d-pimalic acid.
- the metal of the carboxylic acid metal salt examples include bismuth, zirconium, zinc, titanium, and calcium. From the viewpoint of catalytic activity and solubility in an organic solvent, the carboxylic acid metal salt is preferably bismuth carboxylate.
- a mixture of carboxylic acid metal salts includes a mixture formed from a plurality of carboxylic acids and one metal base, a mixture formed from one carboxylic acid and a plurality of metal bases, and a plurality of carboxylic acids and a plurality of metal bases. Any of the mixtures formed from
- a commercially available carboxylic acid metal salt may be used.
- commercially available bismuth carboxylates include Puccat B7 and Puccat B25 (both manufactured by Nippon Kagaku Sangyo Co., Ltd.), Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.), and K-KAT XC-227 (manufactured by KING INDUSTRIES). Is mentioned.
- Examples of commercially available zirconium carboxylates include naphthex Zr and Nikka Octix Zr (both manufactured by Nippon Chemical Industry Co., Ltd.).
- Examples of commercially available zinc carboxylates include naphthex Zn and Nikka octix Zn (both manufactured by Nippon Chemical Industry Co., Ltd.).
- Examples of commercially available calcium carboxylates include naphthex Ca, Nikka octix Ca and PACCAT Ca-5B (all manufactured by Nippon Kagaku Sangyo Co., Ltd.).
- the content of the carboxylic acid metal salt in the release agent is preferably 0.1 to 2.5 parts by weight, more preferably 0.3 to 2.0 parts by weight, and still more preferably 0 to 100 parts by weight of the polyolefin. .4 to 1.5 parts by weight.
- the content is less than 0.1 parts by weight, the catalytic action may be insufficient.
- the content exceeds 2.5 parts by weight, the release force of the release agent layer is increased or the release is peeled off. It may cause problems such as shortening the pot life of the agent.
- content of carboxylic acid metal salt here refers to the quantity of only carboxylic acid metal salt, for example, the solution which dissolved carboxylic acid metal salt in the solvent like "Pucat B7" used in the below-mentioned Example. When used, it means the amount of carboxylic acid metal salt only, excluding the amount of solvent.
- the release agent of the present invention contains a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent as an organic solvent.
- a hydrocarbon solvent and the aprotic polar solvent only one type may be used, or two or more types may be used in combination.
- hydrocarbon solvent examples include aliphatic hydrocarbons such as normal hexane and normal heptane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as toluene and xylene. From the viewpoint of the solubility of the release agent component (particularly isocyanate), aromatic hydrocarbons are preferred, toluene and xylene are more preferred, and toluene is more preferred.
- aprotic polar solvent examples include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; ether solvents such as diethyl ether; ester solvents such as ethyl acetate; nitrile solvents such as acetonitrile; N, N— Examples thereof include amide solvents such as dimethylformamide (DMF) and N, N-dimethylacetamide (DMAC); and sulfoxide solvents such as dimethyl sulfoxide (DMSO).
- ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone
- ether solvents such as diethyl ether
- ester solvents such as ethyl acetate
- nitrile solvents such as acetonitrile
- N N— Examples thereof include amide solvents such as dimethylformamide (DMF) and N
- ketone solvents are preferred, methyl ethyl ketone, cyclohexanone and acetylacetone are more preferred, and acetylacetone is more preferred.
- an aromatic hydrocarbon solvent having a high boiling point as a hydrocarbon solvent, particularly xylene (boiling point 144 ° C.) or a mixed solvent thereof, if the boiling point of the aprotic polar solvent is too low, When the release agent layer is formed, only the aprotic polar solvent is removed first, which may adversely affect the appearance of the resulting release agent layer. Therefore, when using an aromatic hydrocarbon solvent having a high boiling point, it is preferable to use an aprotic polar solvent having a high boiling point as well.
- the hydrocarbon solvent is xylene or toluene and xylene (preferably toluene and xylene)
- the aprotic polar solvent is preferably cyclohexanone (boiling point 156 ° C.), acetylacetone (boiling point 140 ° C.) , N, N-dimethylformamide (boiling point 153 ° C.) and N, N-dimethylacetamide (boiling point 165 ° C.), more preferably at least one selected from the group consisting of acetylacetone and cyclohexanone. More preferred is acetylacetone.
- the weight ratio of hydrocarbon solvent to aprotic polar solvent is The ratio is preferably 99: 1 to 90:10, more preferably 99: 1 to 92: 8, and still more preferably 99: 1 to 95: 5. Further, the content of the organic solvent is adjusted in the release agent, preferably in the range of 95 to 99.9% by weight.
- the release agent of the present invention may contain one or more optional components.
- one or more liquid hydrocarbons may be used as an optional component of the release agent.
- the “liquid hydrocarbon” in the present invention is a carbonization having a viscosity at 38 ° C. (hereinafter sometimes referred to as “38 ° C. viscosity”) of 5 to 1500 Pa ⁇ s measured according to JIS K7117-1: 1990. Means hydrogen.
- the 38 ° C. viscosity of the liquid hydrocarbon is usually 5 to 1500 Pa ⁇ s, preferably 5 to 1300 Pa ⁇ s.
- this 38 degreeC viscosity is less than 5 Pa * s, the speed dependence of peeling force may not fully reduce.
- the amount of liquid hydrocarbon having a viscosity at 38 ° C. of less than 5 Pa ⁇ s is increased, the adhesive strength of the adhesive tapes is lowered.
- the viscosity at 38 ° C. exceeds 1500 Pa ⁇ s, the fluidity of the liquid hydrocarbon decreases near the expected use temperature of the release material and the adhesive tape of 10-30 ° C. It may not be reduced sufficiently.
- liquid hydrocarbons examples include polymers of unsaturated hydrocarbons.
- the “polymer of unsaturated hydrocarbon” in the present invention is used to mean not only a polymer but also an oligomer.
- the liquid hydrocarbon is preferably a liquid copolymer of ethylene and an unsaturated hydrocarbon having 3 to 5 carbon atoms, a liquid homopolymer of an unsaturated hydrocarbon having 3 to 5 carbon atoms, and a carbon number. It is at least one selected from the group consisting of 3 to 5 unsaturated hydrocarbon liquid copolymers.
- Examples of the unsaturated hydrocarbon having 3 to 5 carbon atoms include propylene, 1-butene, isobutene, 2-butene, butadiene, 1-pentene, 2-pentene, isopentene, isoprene and the like.
- the liquid hydrocarbon is more preferably at least one selected from the group consisting of a liquid ethylene-olefin copolymer, liquid polybutadiene, liquid polyisoprene, liquid hydrogenated polybutadiene, liquid hydrogenated polyisoprene, and liquid polyisobutene.
- the liquid hydrocarbon can be produced by a known method such as radical polymerization or cationic polymerization.
- the content of the release agent in the release agent is preferably 3 to 30 parts by weight, more preferably 4 to 20 parts by weight, even more preferably 100 parts by weight in total of the polyolefin and the liquid hydrocarbon. Is 5 to 15 parts by weight. When this content is less than 3 parts by weight, the release rate dependency may not be sufficiently reduced. Conversely, when it exceeds 30 parts by weight, the strength of the release agent layer may be reduced or the adhesive layer of the adhesive tape. Liquid hydrocarbons may migrate to the adhesive tape, which may reduce the adhesive strength of the adhesive tape.
- the release agent of the present invention may be a resin other than the polyolefin, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer or an antistatic agent, carbon black, calcium oxide, magnesium oxide, if necessary. It may contain a filler such as silica, zinc oxide and titanium oxide, a pigment and the like.
- the present invention also provides a release material having a substrate and a release agent layer.
- the release material of the present invention is characterized by having a release agent layer formed from the release agent of the present invention on at least one surface of a substrate.
- the substrate and the release agent layer will be described in order.
- the substrate is not particularly limited.
- the substrate is preferably a plastic film having a smooth surface.
- the plastic film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polyolefin films such as polyethylene film and polypropylene film.
- paper such as kraft paper, glassine paper, and high-quality paper may be used as the base material.
- the base material may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance as necessary.
- the thickness of the base material is not particularly limited and can be appropriately set according to the purpose of use.
- the thickness is usually about 12 to 250 ⁇ m, preferably 16 to 200 ⁇ m, more preferably 25 to 125 ⁇ m.
- light stabilizers such as antioxidants, ultraviolet absorbers, hindered amine light stabilizers and antistatic agents, carbon black, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide fillers, You may mix
- the release agent layer is obtained, for example, by applying the release agent of the present invention containing an organic solvent to a substrate and drying it.
- the application method of the release agent is not particularly limited, and any known method, for example, a method using a kiss roll coater, a bead coater, a rod coater, a Meyer bar coater, a die coater, a gravure coater or the like can be used.
- a drying method There is no particular limitation on the drying method, and any known method can be used.
- a common drying method is hot air drying. The temperature of hot air drying may vary depending on the heat resistance of the substrate, but is usually about 80 to 150 ° C.
- the thickness of the release agent layer after drying is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm. When this thickness is less than 30 nm, the release force of the release agent layer may be too high. Conversely, when it exceeds 500 nm, the substrate and the release agent layer that come into contact with each other when the release material is wound into a roll shape, May cause a problem that it becomes easy to block, and a problem that the peeling force of the release agent layer becomes high.
- release agent layer In the release material, another layer may exist between the release agent layer and the substrate as long as the release agent layer is present on the outermost surface.
- the release agent layer is preferably formed directly on the substrate.
- the present invention also provides a pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer and the mold release material of the present invention, wherein the pressure-sensitive adhesive layer and the release agent layer of the mold release material are in contact with each other.
- the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer there is no particular limitation on the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive include a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a polyester-based pressure-sensitive adhesive. Among these, acrylic adhesives and polyester adhesives are preferred.
- the pressure-sensitive adhesive tape with a release material having a pressure-sensitive adhesive layer formed using an acrylic pressure-sensitive adhesive and a polyester-based pressure-sensitive adhesive exhibits stable releasability.
- the acrylic pressure-sensitive adhesive is mainly composed of an acrylic polymer obtained by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a UV polymerization method, and, as necessary, a crosslinking agent, a tackifier, a softener, It can be prepared by adding various additives such as anti-aging agents and fillers.
- alkyl (meth) acrylate such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is used as a main component.
- -Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, carboxy group-containing monomers such as (meth) acrylic acid, styrene monomers such as styrene, vinyl esters such as vinyl acetate, etc. Examples thereof include a copolymer of a monomer mixture to which a monomer is added.
- polyester-based pressure-sensitive adhesive a polyester-based polymer having an aliphatic polyol diol (for example, a carbonate diol obtained by reaction of a diol component such as butanediol and a carbonate compound such as ethylene carbonate) as an essential polyol component is used.
- aliphatic polyol diol for example, a carbonate diol obtained by reaction of a diol component such as butanediol and a carbonate compound such as ethylene carbonate
- examples include a pressure-sensitive adhesive as a main ingredient.
- the pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive solution to the release agent layer of the release material and drying it.
- a pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive solution on a base material different from the base material of the release material and drying it, and then bonding this to the release agent layer of the release material.
- the thickness of the pressure-sensitive adhesive layer can be appropriately selected in consideration of adhesiveness and the like, and is preferably 3 to 100 ⁇ m, more preferably 5 to 90 ⁇ m, and still more preferably 10 to 80 ⁇ m.
- the present invention also provides an adhesive tape having a base material, an adhesive layer and a release agent layer.
- This pressure-sensitive adhesive tape of the present invention has a release agent layer formed from the release agent of the present invention on one side of the substrate, and has an adhesive layer on the other side of the substrate where the release agent layer is not formed. It is characterized by.
- the release agent layer of this aspect may be referred to as a “back treatment layer”, and the adhesive tape of this aspect may be referred to as “back treatment layer-attached adhesive tape”.
- the backside treatment layer-attached adhesive tape may be either rolled up or laminated. In any form, the pressure-sensitive adhesive layer is protected by the back treatment layer.
- the pressure-sensitive adhesive layer and the back treatment layer may both be formed directly on the substrate, and another layer is formed between these layers and the substrate. It may be. However, both the pressure-sensitive adhesive layer and the back treatment layer must be present on the outermost surface. By doing this, when the pressure-sensitive adhesive tape is wound in a roll shape or when the pressure-sensitive adhesive tape in the form of a sheet is laminated, the back treatment layer can be in contact with the pressure-sensitive adhesive layer to protect it. it can. In addition, it is preferable that both the pressure-sensitive adhesive layer and the back treatment layer are directly formed on the substrate.
- the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape with the back treatment layer is not particularly limited.
- an adhesive for this what was demonstrated with the adhesive tape with a mold release material etc. are mentioned, for example.
- the formation method of an adhesive layer can also employ
- the thickness of the back treatment layer is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm, from the viewpoint of peeling force.
- Physical properties, properties, etc. The physical properties, properties, etc. in this specification are measured values by the following methods. (1) Density This is a value measured according to ASTM D1505. (2) Melt flow rate (230 ° C) It is a value measured according to ASTM D1238. (3) Number average molecular weight It is the value measured based on ASTM D2503. (4) Hydroxyl value A value measured in accordance with JIS K1557: 1970.
- Release agent component The release agent components used in Examples and Comparative Examples are described below.
- Polyolefin Tuffmer P-0280 (ethylene-propylene copolymer (ethylene: 87 mol%, propylene: 13 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 5.4 g / 10 min, density: 0.00 (87 g / cm 3 , tensile elastic modulus at 23 ° C .: 5.1 MPa, tensile fracture stress at 23 ° C .: 3.3 MPa)
- TAFMER A-3570S (ethylene-1-butene copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 65 g / 10 min, density: 0.87 g / cm 3 , tensile elastic modulus at 23 ° C .: 3.5 MPa, tensile fracture stress at 23 ° C .: 2.1 MPa)
- Isocyanate Coronate L (75% ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups in one molecule: 3, manufactured by Nippon Polyurethane)
- Liquid hydrocarbon Lucant HC-2000 (ethylene- ⁇ -olefin co-oligomer, 38 ° C. viscosity: 34 Pa ⁇ s, manufactured by Mitsui Chemicals)
- Neostan U-600 (2-ethylhexanoic acid solution of bismuth tris (2-ethylhexanoate), carboxylic acid metal salt content: 55-58%, manufactured by Nitto Kasei Co., Ltd.
- Pucat B7 Mineral spirit solution of bismuth resinate, metal bismuth content: 7%, mineral spirit content: 42%, manufactured by Nippon Chemical Industry Co., Ltd.
- Dibutyltin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dilaurate)
- Organic solvent Hydrocarbon solvent toluene, xylene, normal hexane
- Aprotic polar solvent methyl ethyl ketone, acetylacetone, cyclohexanone
- a release agent having a solid content of 1.5% was prepared by dissolving polyolefin, polyolefin polyol, isocyanate, liquid hydrocarbon and urethanization catalyst in an organic solvent in the number of parts shown in Tables 1 and 2.
- the number of parts of the urethanization catalyst shown in Tables 1 and 2 is the number of parts of the obtained urethanization catalyst itself, and when the obtained urethanization catalyst is a solution, it is the number of parts of the whole solution.
- the weight ratio of each organic solvent used is also shown in Tables 1 and 2.
- release agent layer (preparation of release material)
- the prepared release agent was applied to a 38 ⁇ m thick polyester film using a Mayer bar # 6, and then heated with a hot air dryer at 130 ° C. for 1 minute to obtain a release material.
- the thickness of the release agent layer of the obtained release material was about 150 nm.
- Dissolving state of release agent The dissolution state of the obtained release agent was visually determined according to the following criteria. ⁇ : The release agent is transparent, and the release agent component is uniformly dissolved in the organic solvent. X: There are insolubles in the release agent, and the release agent component is not uniformly dissolved in the organic solvent.
- the release agent of the present invention can form a release agent layer having excellent characteristics without using an organic tin compound having a problem with the environment.
- the release material and the adhesive tape having the release agent layer can be suitably used for various applications such as those related to electronic components.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a release agent containing a polyolefin, an isocyanate, a polyolefin polyol, a carboxylic acid metal salt, and an organic solvent. The carboxylic acid metal salt is a non-organic tin compound and the organic solvent is a mixture of a hydrocarbon solvent and a non-proton polar solvent.
Description
本発明は、ポリオレフィンを含有する剥離剤(以下「ポリオレフィン系剥離剤」と略称することがある)、並びに該剥離剤から形成された剥離剤層を有する離型材および粘着テープに関する。
The present invention relates to a release agent containing polyolefin (hereinafter sometimes abbreviated as “polyolefin release agent”), and a release material and an adhesive tape having a release agent layer formed from the release agent.
離型材は、紙、プラスチックフィルムおよびプラスチックラミネート紙等の基材の少なくとも片面に剥離剤層を設けたものであって、粘着テープ、粘着シートおよびラベル等の粘着剤面を保護する目的や、セラミックグリーンシート等の製造工程に使用されている。
The release material is provided with a release agent layer on at least one surface of a substrate such as paper, plastic film and plastic laminated paper, and is intended to protect the adhesive surface of an adhesive tape, an adhesive sheet, a label, etc. It is used in manufacturing processes for green sheets.
剥離剤としては、シリコーン系剥離剤、長鎖アルキル系剥離剤、ポリオレフィン系剥離剤およびフッ素系剥離剤等が知られている。しかし、電子部品関連等の用途では、シリコーン系剥離剤では問題を生ずるケースがあるため、非シリコーン系剥離剤、例えばポリオレフィン系剥離剤が使用されている。
As the release agent, a silicone release agent, a long-chain alkyl release agent, a polyolefin release agent, a fluorine release agent, and the like are known. However, in applications related to electronic parts and the like, there are cases in which silicone-based release agents cause problems, and therefore non-silicone release agents such as polyolefin-based release agents are used.
基材に対するポリオレフィン系剥離剤の密着性を向上させるために、ポリオレフィン系剥離剤中で、イソシアネート系架橋剤およびポリオールが使用されることがある(例えば、特許文献1~3)。さらに、イソシアネート系架橋剤とポリオールとのウレタン化反応を促進するために、ウレタン化触媒も添加される場合がある。ウレタン化触媒としては、これまで、ジブチル錫ジラウレート、ジオクチル錫ジラウレートなどの有機錫化合物が多用されてきた。有機錫化合物は、有機溶媒への良好な溶解性を有することに加えて、高い触媒活性を有するため、これを用いれば、外観および基材密着性に優れた剥離剤層を形成することができる。
In order to improve the adhesion of the polyolefin release agent to the substrate, an isocyanate crosslinking agent and a polyol may be used in the polyolefin release agent (for example, Patent Documents 1 to 3). Furthermore, a urethanization catalyst may be added to accelerate the urethanization reaction between the isocyanate-based crosslinking agent and the polyol. As the urethanization catalyst, organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate have been widely used. The organotin compound has high catalytic activity in addition to having good solubility in an organic solvent, so that it can be used to form a release agent layer excellent in appearance and substrate adhesion. .
しかし、近年、環境問題への意識が高まるにつれて、有機錫化合物の使用が制限される傾向にある。そこで、有機錫化合物を含有しない剥離剤が求められている。本発明はこのような事情に着目してなされたものであって、その目的は、有機錫化合物を用いずに、基材への密着性に優れ、且つ良好な外観の剥離剤層を形成することができる剥離剤を提供することにある。
However, in recent years, the use of organotin compounds tends to be restricted as the awareness of environmental issues increases. Therefore, there is a demand for a release agent that does not contain an organic tin compound. The present invention has been made by paying attention to such circumstances, and the object thereof is to form a release agent layer having excellent adhesion to a substrate and having a good appearance without using an organic tin compound. It is to provide a release agent that can be used.
本発明者らが鋭意検討を重ねた結果、ウレタン化触媒として非有機錫化合物であるカルボン酸金属塩を使用し、且つ有機溶媒として炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒を使用すれば、上記目的を達成し得ることを見出し、本発明を完成した。本発明は以下の通りである。
As a result of intensive studies by the present inventors, a carboxylic acid metal salt that is a non-organotin compound is used as a urethanization catalyst, and a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent is used as an organic solvent. Thus, the inventors have found that the above object can be achieved and completed the present invention. The present invention is as follows.
[1] ポリオレフィン、イソシアネート、ポリオレフィンポリオール、カルボン酸金属塩および有機溶媒を含有する剥離剤であり、
カルボン酸金属塩が、非有機錫化合物であり、
有機溶媒が、炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒である剥離剤。
[2] 炭化水素系溶媒が、芳香族炭化水素系溶媒である上記[1]に記載の剥離剤。
[3] 芳香族炭化水素系溶媒が、トルエンおよびキシレンからなる群から選ばれる少なくとも一つである上記[2]に記載の剥離剤。
[4] 非プロトン性極性溶媒が、ケトン系溶媒である上記[1]~[3]のいずれか一つに記載の剥離剤。
[5] ケトン系溶媒が、メチルエチルケトン、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つである上記[4]に記載の剥離剤。
[6] 炭化水素系溶媒が、キシレン、またはトルエンおよびキシレンであり、非プロトン性極性溶媒が、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つである上記[1]に記載の剥離剤。
[7] 炭化水素系溶媒と非プロトン性極性溶媒との重量比が、99:1~90:10である上記[1]~[6]のいずれか一つに記載の剥離剤。
[8] カルボン酸金属塩が、カルボン酸ビスマスである上記[1]~[7]のいずれか一つに記載の剥離剤。
[9] イソシアネートが、1分子中にイソシアネート基を3個以上有するポリイソシアネートである上記[1]~[8]のいずれか一つに記載の剥離剤。
[10] ポリイソシアネートが、芳香族ポリイソシアネートおよび脂環式ポリイソシアネートからなる群から選ばれる少なくとも一つである上記[9]に記載の剥離剤。
[11] ポリイソシアネートが、芳香族ジイソシアネートの多価アルコール付加体および脂環式ジイソシアネートの多価アルコール付加体からなる群から選ばれる少なくとも一つである上記[10]に記載の剥離剤。
[12] ポリオレフィンポリオールの数平均分子量が、1500~50000である上記[1]~[11]のいずれか一つに記載の剥離剤。
[13] 基材および剥離剤層を有する離型材であり、
上記[1]~[12]のいずれか一つに記載の剥離剤から形成された剥離剤層を、基材の少なくとも片面に有する離型材。
[14] 粘着剤層および上記[13]に記載の離型材を有する粘着テープであり、
粘着剤層と離型材の剥離剤層とが接触している粘着テープ。
[15] 基材、粘着剤層および剥離剤層を有する粘着テープであり、
上記[1]~[12]のいずれか一つに記載の剥離剤から形成された剥離剤層を、基材の片面に有し、
剥離剤層が形成されていない基材の他方の面に、粘着剤層を有する粘着テープ。 [1] A release agent containing polyolefin, isocyanate, polyolefin polyol, metal carboxylate and an organic solvent,
The carboxylic acid metal salt is a non-organotin compound,
A release agent in which the organic solvent is a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent.
[2] The stripping agent according to [1], wherein the hydrocarbon solvent is an aromatic hydrocarbon solvent.
[3] The stripping agent according to [2], wherein the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene and xylene.
[4] The release agent according to any one of [1] to [3], wherein the aprotic polar solvent is a ketone solvent.
[5] The release agent according to [4], wherein the ketone solvent is at least one selected from the group consisting of methyl ethyl ketone, acetylacetone, and cyclohexanone.
[6] The stripping agent according to the above [1], wherein the hydrocarbon solvent is xylene or toluene and xylene, and the aprotic polar solvent is at least one selected from the group consisting of acetylacetone and cyclohexanone.
[7] The stripping agent according to any one of the above [1] to [6], wherein the weight ratio of the hydrocarbon solvent to the aprotic polar solvent is 99: 1 to 90:10.
[8] The stripping agent according to any one of [1] to [7], wherein the metal carboxylate is bismuth carboxylate.
[9] The release agent according to any one of [1] to [8], wherein the isocyanate is a polyisocyanate having 3 or more isocyanate groups in one molecule.
[10] The release agent according to [9], wherein the polyisocyanate is at least one selected from the group consisting of aromatic polyisocyanates and alicyclic polyisocyanates.
[11] The release agent according to [10], wherein the polyisocyanate is at least one selected from the group consisting of a polyhydric alcohol adduct of an aromatic diisocyanate and a polyhydric alcohol adduct of an alicyclic diisocyanate.
[12] The release agent according to any one of [1] to [11], wherein the polyolefin polyol has a number average molecular weight of 1500 to 50000.
[13] A release material having a base material and a release agent layer,
A release material having a release agent layer formed from the release agent according to any one of [1] to [12] above on at least one surface of a substrate.
[14] A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer and the release material according to [13] above,
An adhesive tape in which the adhesive layer and the release agent layer of the release material are in contact.
[15] An adhesive tape having a substrate, an adhesive layer and a release agent layer,
A release agent layer formed from the release agent according to any one of the above [1] to [12] is provided on one side of the substrate,
A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.
カルボン酸金属塩が、非有機錫化合物であり、
有機溶媒が、炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒である剥離剤。
[2] 炭化水素系溶媒が、芳香族炭化水素系溶媒である上記[1]に記載の剥離剤。
[3] 芳香族炭化水素系溶媒が、トルエンおよびキシレンからなる群から選ばれる少なくとも一つである上記[2]に記載の剥離剤。
[4] 非プロトン性極性溶媒が、ケトン系溶媒である上記[1]~[3]のいずれか一つに記載の剥離剤。
[5] ケトン系溶媒が、メチルエチルケトン、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つである上記[4]に記載の剥離剤。
[6] 炭化水素系溶媒が、キシレン、またはトルエンおよびキシレンであり、非プロトン性極性溶媒が、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つである上記[1]に記載の剥離剤。
[7] 炭化水素系溶媒と非プロトン性極性溶媒との重量比が、99:1~90:10である上記[1]~[6]のいずれか一つに記載の剥離剤。
[8] カルボン酸金属塩が、カルボン酸ビスマスである上記[1]~[7]のいずれか一つに記載の剥離剤。
[9] イソシアネートが、1分子中にイソシアネート基を3個以上有するポリイソシアネートである上記[1]~[8]のいずれか一つに記載の剥離剤。
[10] ポリイソシアネートが、芳香族ポリイソシアネートおよび脂環式ポリイソシアネートからなる群から選ばれる少なくとも一つである上記[9]に記載の剥離剤。
[11] ポリイソシアネートが、芳香族ジイソシアネートの多価アルコール付加体および脂環式ジイソシアネートの多価アルコール付加体からなる群から選ばれる少なくとも一つである上記[10]に記載の剥離剤。
[12] ポリオレフィンポリオールの数平均分子量が、1500~50000である上記[1]~[11]のいずれか一つに記載の剥離剤。
[13] 基材および剥離剤層を有する離型材であり、
上記[1]~[12]のいずれか一つに記載の剥離剤から形成された剥離剤層を、基材の少なくとも片面に有する離型材。
[14] 粘着剤層および上記[13]に記載の離型材を有する粘着テープであり、
粘着剤層と離型材の剥離剤層とが接触している粘着テープ。
[15] 基材、粘着剤層および剥離剤層を有する粘着テープであり、
上記[1]~[12]のいずれか一つに記載の剥離剤から形成された剥離剤層を、基材の片面に有し、
剥離剤層が形成されていない基材の他方の面に、粘着剤層を有する粘着テープ。 [1] A release agent containing polyolefin, isocyanate, polyolefin polyol, metal carboxylate and an organic solvent,
The carboxylic acid metal salt is a non-organotin compound,
A release agent in which the organic solvent is a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent.
[2] The stripping agent according to [1], wherein the hydrocarbon solvent is an aromatic hydrocarbon solvent.
[3] The stripping agent according to [2], wherein the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene and xylene.
[4] The release agent according to any one of [1] to [3], wherein the aprotic polar solvent is a ketone solvent.
[5] The release agent according to [4], wherein the ketone solvent is at least one selected from the group consisting of methyl ethyl ketone, acetylacetone, and cyclohexanone.
[6] The stripping agent according to the above [1], wherein the hydrocarbon solvent is xylene or toluene and xylene, and the aprotic polar solvent is at least one selected from the group consisting of acetylacetone and cyclohexanone.
[7] The stripping agent according to any one of the above [1] to [6], wherein the weight ratio of the hydrocarbon solvent to the aprotic polar solvent is 99: 1 to 90:10.
[8] The stripping agent according to any one of [1] to [7], wherein the metal carboxylate is bismuth carboxylate.
[9] The release agent according to any one of [1] to [8], wherein the isocyanate is a polyisocyanate having 3 or more isocyanate groups in one molecule.
[10] The release agent according to [9], wherein the polyisocyanate is at least one selected from the group consisting of aromatic polyisocyanates and alicyclic polyisocyanates.
[11] The release agent according to [10], wherein the polyisocyanate is at least one selected from the group consisting of a polyhydric alcohol adduct of an aromatic diisocyanate and a polyhydric alcohol adduct of an alicyclic diisocyanate.
[12] The release agent according to any one of [1] to [11], wherein the polyolefin polyol has a number average molecular weight of 1500 to 50000.
[13] A release material having a base material and a release agent layer,
A release material having a release agent layer formed from the release agent according to any one of [1] to [12] above on at least one surface of a substrate.
[14] A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer and the release material according to [13] above,
An adhesive tape in which the adhesive layer and the release agent layer of the release material are in contact.
[15] An adhesive tape having a substrate, an adhesive layer and a release agent layer,
A release agent layer formed from the release agent according to any one of the above [1] to [12] is provided on one side of the substrate,
A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.
本発明の剥離剤は、有機錫化合物を含有しないにもかかわらず、基材への密着に優れ、且つ良好な外観の剥離剤層を形成することができる。
Although the release agent of the present invention does not contain an organic tin compound, it can form a release agent layer having excellent adhesion to a substrate and having a good appearance.
1.剥離剤
本発明の剥離剤は、ポリオレフィン、イソシアネート、ポリオレフィンポリオール、カルボン酸金属塩および有機溶媒を含有する。以下、これらの各成分を順に説明する。 1. Release Agent The release agent of the present invention contains polyolefin, isocyanate, polyolefin polyol, metal carboxylate and organic solvent. Hereinafter, each of these components will be described in order.
本発明の剥離剤は、ポリオレフィン、イソシアネート、ポリオレフィンポリオール、カルボン酸金属塩および有機溶媒を含有する。以下、これらの各成分を順に説明する。 1. Release Agent The release agent of the present invention contains polyolefin, isocyanate, polyolefin polyol, metal carboxylate and organic solvent. Hereinafter, each of these components will be described in order.
[ポリオレフィン]
本発明の剥離剤は、1種または2種以上のポリオレフィンを含有する。なお、本発明において「ポリオレフィン」とは、38℃において固体であるポリオレフィンを意味する。ポリオレフィンとしては、他の成分とともに有機溶媒に溶解して基材に塗布できる限り、あらゆるものを使用することができる。 [Polyolefin]
The release agent of the present invention contains one type or two or more types of polyolefin. In the present invention, “polyolefin” means a polyolefin that is solid at 38 ° C. Any polyolefin can be used as long as it can be dissolved in an organic solvent together with other components and applied to a substrate.
本発明の剥離剤は、1種または2種以上のポリオレフィンを含有する。なお、本発明において「ポリオレフィン」とは、38℃において固体であるポリオレフィンを意味する。ポリオレフィンとしては、他の成分とともに有機溶媒に溶解して基材に塗布できる限り、あらゆるものを使用することができる。 [Polyolefin]
The release agent of the present invention contains one type or two or more types of polyolefin. In the present invention, “polyolefin” means a polyolefin that is solid at 38 ° C. Any polyolefin can be used as long as it can be dissolved in an organic solvent together with other components and applied to a substrate.
有機溶媒への溶解性の観点から、ポリオレフィンの密度は、好ましくは0.885g/cm3以下、より好ましくは0.880g/cm3以下である。この密度が0.885g/cm3を超えると、有機溶媒への溶解性が低下して、基材への塗布が困難になる傾向があり、また剥離力も増大する傾向がある。一方、ポリオレフィンの密度の下限に特に限定は無いが、この密度は、好ましくは0.830g/cm3以上、より好ましくは0.857g/cm3以上、さらに好ましくは0.858g/cm3以上である。
From the viewpoint of solubility in an organic solvent, the density of the polyolefin is preferably 0.885 g / cm 3 or less, more preferably 0.880 g / cm 3 or less. When this density exceeds 0.885 g / cm 3 , solubility in an organic solvent tends to be lowered, and application to a substrate tends to be difficult, and peeling force tends to increase. On the other hand, the lower limit of the density of the polyolefin is not particularly limited, but this density is preferably 0.830 g / cm 3 or more, more preferably 0.857 g / cm 3 or more, and further preferably 0.858 g / cm 3 or more. is there.
ポリオレフィンとしては、例えば、エチレン、プロピレンおよび炭素数が4~20のα-オレフィンからなる群から選ばれる少なくとも二つの単量体から形成されるα-オレフィン共重合体が挙げられる。これらの中でも、エチレンを主たる単量体とする共重合体(即ち、エチレン系α-オレフィン共重合体)、および/またはプロピレンを主たる単量体とする共重合体(即ち、プロピレン系α-オレフィン共重合体)が好ましい。ここで、炭素数が4~20のα-オレフィンとしては、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン等が挙げられる。また、α-オレフィン共重合体は、ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれでもよい。
Examples of the polyolefin include an α-olefin copolymer formed from at least two monomers selected from the group consisting of ethylene, propylene and an α-olefin having 4 to 20 carbon atoms. Among these, a copolymer having ethylene as a main monomer (that is, an ethylene-based α-olefin copolymer) and / or a copolymer having propylene as a main monomer (that is, a propylene-based α-olefin). Copolymer) is preferred. Here, as the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1- Examples include pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like. The α-olefin copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
エチレン系α-オレフィン共重合体の密度は、好ましくは0.857g/cm3以上0.885g/cm3以下(より好ましくは0.880g/cm3以下)である。エチレン系α-オレフィン共重合体のエチレン構成単位量は、50モル%以上である。このエチレン構成単位量は、好ましくは60~95モル%、より好ましくは70~95モル%である。エチレン系α-オレフィン共重合体に含まれるα-オレフィン構成単位としては、1-ブテン、プロピレン、1-ヘキセン、1-オクテンからなる群から選ばれる少なくとも一つの単量体から形成されるものが好ましい。特に好ましいエチレン系α-オレフィン共重合体として、エチレン-1-ブテン共重合体およびエチレン-プロピレン共重合体が挙げられる。なお、このようなエチレン-1-ブテン共重合体は、エチレンおよび1-ブテン以外のα-オレフィンに由来する構成単位を10モル%以下の量で含んでいてもよい。同様に、エチレン-プロピレン共重合体は、エチレンおよびプロピレン以外のα-オレフィンに由来する構成単位を10モル%以下の量で含んでいてもよい。このような共重合体は、例えば、遷移金属触媒成分(例えばバナジウム化合物やジルコニウム化合物)と有機アルミニウム化合物触媒成分とからなる触媒を用いて、エチレンとα-オレフィンとを共重合することによって製造することができる。
The density of the ethylene-based α-olefin copolymer is preferably 0.857 g / cm 3 or more and 0.885 g / cm 3 or less (more preferably 0.880 g / cm 3 or less). The ethylene structural unit amount of the ethylene-based α-olefin copolymer is 50 mol% or more. The ethylene structural unit amount is preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit contained in the ethylene-based α-olefin copolymer is one formed from at least one monomer selected from the group consisting of 1-butene, propylene, 1-hexene and 1-octene. preferable. Particularly preferred ethylene-based α-olefin copolymers include ethylene-1-butene copolymers and ethylene-propylene copolymers. Such an ethylene-1-butene copolymer may contain a structural unit derived from α-olefin other than ethylene and 1-butene in an amount of 10 mol% or less. Similarly, the ethylene-propylene copolymer may contain a structural unit derived from an α-olefin other than ethylene and propylene in an amount of 10 mol% or less. Such a copolymer is produced, for example, by copolymerizing ethylene and α-olefin using a catalyst comprising a transition metal catalyst component (for example, vanadium compound or zirconium compound) and an organoaluminum compound catalyst component. be able to.
プロピレン系α-オレフィン共重合体の密度は、好ましくは0.858g/cm3以上0.885g/cm3以下(より好ましくは0.880g/cm3以下)である。プロピレン系α-オレフィン共重合体のプロピレン構成単位量は、50モル%超である。このプロピレン構成単位量は、好ましくは60~95モル%、より好ましくは70~95モル%である。また、プロピレン系α-オレフィン共重合体に含まれるα-オレフィン構成単位としては、エチレン、1-ブテン、1-ヘキセン、1-オクテンからなる群から選ばれる少なくとも一つの単量体から形成されるものが好ましい。特に好ましいプロピレン系α-オレフィン共重合体は、プロピレン-エチレンランダム共重合体(プロピレン系エラストマー)である。なお、このプロピレン-エチレンランダム共重合体は、プロピレンおよびエチレン以外のα-オレフィンに由来する構成単位を10モル%以下の量で含んでいてもよい。プロピレン系α-オレフィン共重合体は、例えば特開2000-191862に記載されているように、メタロセン系触媒を用いて製造することができる。
The density of the propylene-based α-olefin copolymer is preferably 0.858 g / cm 3 or more and 0.885 g / cm 3 or less (more preferably 0.880 g / cm 3 or less). The propylene structural unit amount of the propylene-based α-olefin copolymer is more than 50 mol%. The propylene structural unit amount is preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit contained in the propylene-based α-olefin copolymer is formed of at least one monomer selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene. Those are preferred. A particularly preferred propylene-based α-olefin copolymer is a propylene-ethylene random copolymer (propylene-based elastomer). The propylene-ethylene random copolymer may contain a constituent unit derived from α-olefin other than propylene and ethylene in an amount of 10 mol% or less. The propylene-based α-olefin copolymer can be produced using a metallocene-based catalyst as described in, for example, JP-A-2000-191862.
α-オレフィン共重合体として、市販品を使用することができる。エチレン系α-オレフィン共重合体の好ましい市販品としては、例えば、タフマーPシリーズ、タフマーAシリーズ(いずれも、三井化学社製)、エンゲージ(ダウ・ケミカル社製)等が挙げられる。また、プロピレン系α-オレフィン共重合体の好ましい市販品としては、例えば、タフマーXMシリーズ(三井化学社製)等が挙げられる。
Commercially available products can be used as the α-olefin copolymer. Preferable commercial products of the ethylene-based α-olefin copolymer include, for example, Tuffmer P series, Tuffmer A series (all manufactured by Mitsui Chemicals), Engage (manufactured by Dow Chemical Company), and the like. In addition, as a preferable commercial product of the propylene-based α-olefin copolymer, for example, Tuffmer XM series (manufactured by Mitsui Chemicals) and the like can be mentioned.
ポリオレフィンとして、ポリメチルペンテンも使用することができる。ポリメチルペンテンとしては、4-メチル-1-ペンテンの単独重合体、および4-メチル-1-ペンテンとそれ以外のα-オレフィンとの共重合体が挙げられる。ポリメチルペンテン共重合体の4-メチル-1-ペンテン構成単位量は、好ましくは50~95モル%、より好ましくは70~95モル%である。ポリメチルペンテンは、結晶性重合体であってもよい。ポリメチルペンテンの密度は、好ましくは0.83~0.86g/cm3である。ポリメチルペンテン共重合体中のα-オレフィン構成単位としては、例えば、エチレン、プロピレン、1-ブテン、1-ヘキセン、1-オクテン、1-デセン、1-テトラデセン、1-オクタデセンなどの炭素数2~20のα-オレフィンに由来するものが好ましい。これらの中でも、4-メチル-1-ペンテンと良好な共重合性を示す1-デセン、1-テトラデセンおよび1-オクタデセンがより好ましい。なお、ポリメチルペンテンの市販品としては、TPX-S(4-メチルペンテン-1-α-オレフィン共重合体、三井化学社製)が挙げられる。
Polymethylpentene can also be used as the polyolefin. Examples of polymethylpentene include a homopolymer of 4-methyl-1-pentene, and a copolymer of 4-methyl-1-pentene and other α-olefins. The amount of 4-methyl-1-pentene constituent unit in the polymethylpentene copolymer is preferably 50 to 95 mol%, more preferably 70 to 95 mol%. The polymethylpentene may be a crystalline polymer. The density of polymethylpentene is preferably 0.83 to 0.86 g / cm 3 . Examples of the α-olefin structural unit in the polymethylpentene copolymer include 2 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like. Those derived from .alpha.-olefins of .about.20 are preferred. Of these, 1-decene, 1-tetradecene and 1-octadecene, which exhibit good copolymerizability with 4-methyl-1-pentene, are more preferred. An example of a commercially available product of polymethylpentene is TPX-S (4-methylpentene-1-α-olefin copolymer, manufactured by Mitsui Chemicals).
有機溶媒に溶解する限り、ポリオレフィンとして、ポリイソプレン、ポリブタジエン等のジエン系ゴムも使用することができる。このようなポリイソプレンとしては、シス-1,4結合が90%以上であり、密度が0.90~0.92g/cm3であり、ムーニー粘度(100℃におけるML1+4)が40~70であるものが好ましい。ポリイソプレンの市販品としては、IR-307、IR-310(クレイトンポリマー社製)が挙げられる。ポリブタジエンとしては、シス-1,4結合が90%以上であり、密度が0.88~0.91g/cm3であり、ムーニー粘度(100℃におけるML1+4)が25~50であるものが好ましい。ポリブタジエンの市販品としては、Nipol BR1220、Nipol BR1220L(日本ゼオン社製)、BR01(JSR社製)が挙げられる。
As long as it dissolves in an organic solvent, diolefin rubbers such as polyisoprene and polybutadiene can also be used as the polyolefin. Such polyisoprene has a cis-1,4 bond of 90% or more, a density of 0.90 to 0.92 g / cm 3 , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 40 to 70. Those are preferred. Examples of commercially available products of polyisoprene include IR-307 and IR-310 (manufactured by Kraton Polymer Co., Ltd.). As the polybutadiene, those having a cis-1,4 bond of 90% or more, a density of 0.88 to 0.91 g / cm 3 , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 25 to 50 are preferable. Examples of commercially available products of polybutadiene include Nipol BR1220, Nipol BR1220L (manufactured by Nippon Zeon), and BR01 (manufactured by JSR).
本発明におけるポリオレフィンは、後述するイソシアネートと反応しないことが好ましい。但し、本発明の目的を阻害しない範囲内において、水酸基(ヒドロキシ基)、アミノ基、カルボキシ基、イソシアネート基(イソシアナト基)等の官能基を有する変性ポリオレフィンを使用してもよい。変性ポリオレフィンの1分子あたりの官能基数(平均値)は、好ましくは1以下である。
The polyolefin in the present invention preferably does not react with the isocyanate described later. However, a modified polyolefin having a functional group such as a hydroxyl group (hydroxy group), an amino group, a carboxy group, or an isocyanate group (isocyanato group) may be used as long as the object of the present invention is not impaired. The number of functional groups (average value) per molecule of the modified polyolefin is preferably 1 or less.
本発明の剥離剤をアクリル系粘着剤と組み合わせて使用する場合は特に、オレフィンとしてエチレン系α-オレフィン共重合体および/またはプロピレン系α-オレフィン共重合体を使用することが、経時的な剥離力の上昇を防止するために好ましい。一方、本発明の剥離剤を、比較的大きな剥離力が必要とされる用途に使用する場合、プロピレン系α-オレフィン共重合体および/またはポリメチルペンテンが好ましい。
In particular, when the release agent of the present invention is used in combination with an acrylic pressure-sensitive adhesive, the use of an ethylene-based α-olefin copolymer and / or a propylene-based α-olefin copolymer as an olefin may cause the release over time. It is preferable for preventing an increase in force. On the other hand, when the release agent of the present invention is used for an application requiring a relatively large release force, a propylene-based α-olefin copolymer and / or polymethylpentene is preferable.
本発明において、一つのポリオレフィンだけを使用する場合、形成する剥離剤層の強度(塗膜強度)等の観点から、ポリオレフィンの230℃におけるMFR(メルトフローレート)は、好ましくは100g/10分以下、より好ましくは70g/10分以下、さらに好ましくは50g/10分以下、特に好ましくは10g/10分以下である。
In the present invention, when only one polyolefin is used, the MFR (melt flow rate) at 230 ° C. of the polyolefin is preferably 100 g / 10 min or less from the viewpoint of the strength (coating film strength) of the release agent layer to be formed. More preferably, it is 70 g / 10 minutes or less, More preferably, it is 50 g / 10 minutes or less, Most preferably, it is 10 g / 10 minutes or less.
本発明において、二つ以上のポリオレフィンを使用する場合、そのうちの少なくとも一つのポリオレフィンの230℃におけるMFRは、好ましくは100g/10分以下、より好ましくは70g/10分以下、さらに好ましくは50g/10分以下、特に好ましくは10g/10分以下である。このようなMFRを有するポリオレフィンの含有量は、全ポリオレフィン中、好ましくは10重量%、より好ましくは50重量%以上、さらに好ましくは90重量%以上、特に好ましくは100重量%である。
In the present invention, when two or more polyolefins are used, the MFR at 230 ° C. of at least one of the polyolefins is preferably 100 g / 10 min or less, more preferably 70 g / 10 min or less, and even more preferably 50 g / 10 Min. Or less, particularly preferably 10 g / 10 min or less. The content of polyolefin having such MFR is preferably 10% by weight, more preferably 50% by weight or more, still more preferably 90% by weight or more, and particularly preferably 100% by weight in the total polyolefin.
剥離剤層の剥離力および剥離速度依存性を低減させるために、ポリオレフィンは、23℃における引張弾性率が10MPa以下であり、且つ23℃における引張破壊応力が8MPa以下であるポリオレフィン(A-1)を、全ポリオレフィン中に90重量%以上の量で含有することが好ましい。言い換えると、前記ポリオレフィン(A-1)以外のポリオレフィン(A-2)の含有量が、全ポリオレフィン中、10重量%以下に制限されていることが好ましい。ここで、剥離速度依存性とは、剥離剤層の剥離力が剥離速度に依存することをいい、より詳しくは、低速剥離での剥離力に比べて高速剥離での剥離力が大きいことをいう。
In order to reduce the dependency of the release agent layer on the peeling force and the peeling rate, the polyolefin has a tensile modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 8 MPa or less (A-1) Is preferably contained in the total polyolefin in an amount of 90% by weight or more. In other words, the content of the polyolefin (A-2) other than the polyolefin (A-1) is preferably limited to 10% by weight or less in the total polyolefin. Here, the peeling speed dependency means that the peeling force of the release agent layer depends on the peeling speed, and more specifically, means that the peeling force at high speed peeling is larger than the peeling force at low speed peeling. .
上述したポリオレフィン(A-1)およびポリオレフィン(A-2)のいずれも、1種のみを使用してもよく、2種以上を併用してもよい。ポリオレフィン(A-1)の含有量は、全ポリオレフィン中、より好ましくは95重量%以上、さらに好ましくは100重量%である。
Any of the above-described polyolefin (A-1) and polyolefin (A-2) may be used alone or in combination of two or more. The content of the polyolefin (A-1) is more preferably 95% by weight or more and still more preferably 100% by weight in the total polyolefin.
ポリオレフィン(A-1)を使用することによって剥離速度依存性が低減されるのは、剥離過程では粘着剤層と剥離剤層との界面付近で破壊が起こるという仮定の下、引張破壊応力が小さいポリオレフィン(A-1)が存在することによって界面付近が小さな力で破壊されるので、剥離速度が速くなっても剥離力の増大を抑制し得るためであると推定される。
The use of polyolefin (A-1) reduces the release rate dependency because the tensile fracture stress is small under the assumption that fracture occurs near the interface between the adhesive layer and the release agent layer in the release process. The presence of the polyolefin (A-1) destroys the vicinity of the interface with a small force, and it is estimated that the increase in the peeling force can be suppressed even when the peeling speed is increased.
ポリオレフィン(A-1)の23℃における引張弾性率は、10MPa以下、好ましくは8MPa以下、より好ましくは7MPa以下、さらに好ましくは6MPa以下であり、ポリオレフィン(A-1)の23℃における引張破壊応力は、8MPa以下、好ましくは6MPa以下、より好ましくは4MPa以下である。23℃における引張弾性率が10MPaを超えるポリオレフィン(A-2)は、低速および高速で剥離した時の剥離剤層の剥離力を増大させる傾向があり、23℃における引張破壊応力が8MPaを超えるポリオレフィン(A-2)は、高速で剥離した時の剥離剤層の剥離力を増大させる傾向がある。
The tensile modulus at 23 ° C. of the polyolefin (A-1) is 10 MPa or less, preferably 8 MPa or less, more preferably 7 MPa or less, and even more preferably 6 MPa or less. The tensile fracture stress of the polyolefin (A-1) at 23 ° C. Is 8 MPa or less, preferably 6 MPa or less, more preferably 4 MPa or less. Polyolefin (A-2) having a tensile modulus of elasticity exceeding 10 MPa at 23 ° C. tends to increase the peeling force of the release agent layer when peeled at a low speed and a high speed, and has a tensile fracture stress at 23 ° C. exceeding 8 MPa. (A-2) tends to increase the peeling force of the release agent layer when peeled at a high speed.
ポリオレフィン(A-2)としては、(i)23℃における引張破壊応力が8MPa以下であり、23℃における引張弾性率が10MPaを超えるポリオレフィン;(ii)23℃における引張弾性率が10MPa以下であり、23℃における引張破壊応力が8MPaを超えるポリオレフィン;および(iii)23℃における引張弾性率が10MPaを超え、23℃における引張破壊応力が8MPaを超えるポリオレフィン;がある。これらの中では、前記(ii)の態様のポリオレフィン(A-2)が好ましい。また、ポリオレフィン(A-2)の23℃における引張弾性率は、好ましくは100MPa以下であり、ポリオレフィン(A-2)の23℃における引張破壊応力は、好ましくは35MPa以下である。
As the polyolefin (A-2), (i) a polyolefin having a tensile fracture stress at 23 ° C. of 8 MPa or less and a tensile elastic modulus at 23 ° C. of more than 10 MPa; (ii) a tensile elastic modulus at 23 ° C. of 10 MPa or less. And (iii) a polyolefin having a tensile modulus at 23 ° C. of greater than 10 MPa and a tensile fracture stress at 23 ° C. of greater than 8 MPa. Among these, the polyolefin (A-2) of the embodiment (ii) is preferable. The tensile modulus at 23 ° C. of the polyolefin (A-2) is preferably 100 MPa or less, and the tensile fracture stress at 23 ° C. of the polyolefin (A-2) is preferably 35 MPa or less.
本発明において、ポリオレフィン(A-1)の23℃における引張弾性率および23℃における引張破壊応力の下限値のいずれにも限定は無い。但し、充分な剥離剤層強度(塗膜強度)を得るために、ポリオレフィン(A-1)の23℃における引張弾性率は、好ましくは2MPa以上、より好ましくは3MPa以上であり、23℃における引張破壊応力は、好ましくは1MPa以上、より好ましくは2MPa以上である。
In the present invention, there is no limitation on the lower limit of the tensile modulus at 23 ° C. and the tensile fracture stress at 23 ° C. of polyolefin (A-1). However, in order to obtain sufficient release agent layer strength (coating film strength), the tensile modulus of elasticity of the polyolefin (A-1) at 23 ° C. is preferably 2 MPa or more, more preferably 3 MPa or more. The fracture stress is preferably 1 MPa or more, more preferably 2 MPa or more.
ポリオレフィンの「23℃における引張弾性率」および「23℃における引張破壊応力」とは、以下の方法で測定した値である。
ポリオレフィンをトルエンに溶かして5~10重量%の溶液とし、ベーカー式アプリケーターまたはドクターブレード型アプリケーターを使用して、これをポリエチレンテレフタレート(PET)製の離型フィルム上に塗布した後、熱風乾燥機で加熱乾燥し(100℃、3分間)、加熱乾燥後は直ちに23℃雰囲気下で冷却することによって、乾燥後の厚さが20μmのポリオレフィンフィルムを作製する。トルエンへの溶解性が悪い場合は、必要に応じて加温して溶解させても良い。得られたポリオレフィンフィルムを縦30mm×横100mmの短冊状に切り出し、ポリオレフィンフィルムを離型フィルムから剥がしながら、切り出したフィルムの一方の短辺を軸にして長手方向に密に巻回して、長さ30mmの棒状サンプルとする。
この棒状サンプルについて、23℃雰囲気下で、チャック間距離10mm、引張速度50mm/minの条件で引張試験機(島津製作所(株)製、オートグラフ AG-IS型)にて引張試験を行い、その時の応力-ひずみ曲線を得る。その応力-ひずみ曲線における引張開始直後の曲線の傾きから引張弾性率を算出する。また、棒状サンプルが破断したときの応力を引張破壊応力として求める。 The “tensile modulus at 23 ° C.” and “tensile fracture stress at 23 ° C.” of the polyolefin are values measured by the following methods.
Polyolefin is dissolved in toluene to make a 5 to 10% by weight solution, and this is applied onto a release film made of polyethylene terephthalate (PET) using a baker type applicator or a doctor blade type applicator. Heat-dry (100 ° C., 3 minutes), and immediately after the heat-dry, cool in a 23 ° C. atmosphere to produce a polyolefin film having a thickness of 20 μm after drying. If the solubility in toluene is poor, it may be dissolved by heating as necessary. The obtained polyolefin film was cut into strips of 30 mm in length and 100 mm in width, and while peeling off the polyolefin film from the release film, it was tightly wound in the longitudinal direction around one short side of the cut film as a length. A 30 mm rod-shaped sample is used.
This rod-shaped sample was subjected to a tensile test with a tensile tester (manufactured by Shimadzu Corp., Autograph AG-IS type) in a 23 ° C atmosphere under conditions of a distance between chucks of 10 mm and a tensile speed of 50 mm / min. Obtain the stress-strain curve. The tensile modulus is calculated from the slope of the stress-strain curve immediately after the start of tension. Further, the stress when the rod-shaped sample is broken is determined as the tensile fracture stress.
ポリオレフィンをトルエンに溶かして5~10重量%の溶液とし、ベーカー式アプリケーターまたはドクターブレード型アプリケーターを使用して、これをポリエチレンテレフタレート(PET)製の離型フィルム上に塗布した後、熱風乾燥機で加熱乾燥し(100℃、3分間)、加熱乾燥後は直ちに23℃雰囲気下で冷却することによって、乾燥後の厚さが20μmのポリオレフィンフィルムを作製する。トルエンへの溶解性が悪い場合は、必要に応じて加温して溶解させても良い。得られたポリオレフィンフィルムを縦30mm×横100mmの短冊状に切り出し、ポリオレフィンフィルムを離型フィルムから剥がしながら、切り出したフィルムの一方の短辺を軸にして長手方向に密に巻回して、長さ30mmの棒状サンプルとする。
この棒状サンプルについて、23℃雰囲気下で、チャック間距離10mm、引張速度50mm/minの条件で引張試験機(島津製作所(株)製、オートグラフ AG-IS型)にて引張試験を行い、その時の応力-ひずみ曲線を得る。その応力-ひずみ曲線における引張開始直後の曲線の傾きから引張弾性率を算出する。また、棒状サンプルが破断したときの応力を引張破壊応力として求める。 The “tensile modulus at 23 ° C.” and “tensile fracture stress at 23 ° C.” of the polyolefin are values measured by the following methods.
Polyolefin is dissolved in toluene to make a 5 to 10% by weight solution, and this is applied onto a release film made of polyethylene terephthalate (PET) using a baker type applicator or a doctor blade type applicator. Heat-dry (100 ° C., 3 minutes), and immediately after the heat-dry, cool in a 23 ° C. atmosphere to produce a polyolefin film having a thickness of 20 μm after drying. If the solubility in toluene is poor, it may be dissolved by heating as necessary. The obtained polyolefin film was cut into strips of 30 mm in length and 100 mm in width, and while peeling off the polyolefin film from the release film, it was tightly wound in the longitudinal direction around one short side of the cut film as a length. A 30 mm rod-shaped sample is used.
This rod-shaped sample was subjected to a tensile test with a tensile tester (manufactured by Shimadzu Corp., Autograph AG-IS type) in a 23 ° C atmosphere under conditions of a distance between chucks of 10 mm and a tensile speed of 50 mm / min. Obtain the stress-strain curve. The tensile modulus is calculated from the slope of the stress-strain curve immediately after the start of tension. Further, the stress when the rod-shaped sample is broken is determined as the tensile fracture stress.
23℃における引張弾性率が10MPa以下であり、且つ23℃における引張破壊応力が8MPa以下であるポリオレフィン(A-1)としては、例えば、タフマーP-0080K、タフマーP-0280、タフマーA-35070S、タフマーP-0680、タフマーP-0180、タフマーP-0480、タフマーP-0275、タフマーP-0775(いずれもエチレン系α-オレフィン共重合体、三井化学社製)等が挙げられる。
Examples of the polyolefin (A-1) having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 8 MPa or less include Toughmer P-0080K, Tuffmer P-0280, Tuffmer A-335070S, Tuffmer P-0680, Tuffmer P-0180, Tuffmer P-0480, Tuffmer P-0275, Tuffmer P-0775 (all are ethylene-based α-olefin copolymers, manufactured by Mitsui Chemicals, Inc.) and the like.
ポリオレフィンの含有量は、剥離剤の固形分中、好ましくは80~99重量%、より好ましくは90~98重量%である。この含有量が80重量%未満の場合、剥離力が大きくなる傾向が強く、一方、99重量%を超える場合は、架橋成分が少なすぎるために、充分な剥離剤層強度が得られにくくなる。なお、剥離剤の固形分とは、有機溶媒以外の剥離剤成分の含有量合計を意味する。
The content of the polyolefin is preferably 80 to 99% by weight, more preferably 90 to 98% by weight in the solid content of the release agent. When this content is less than 80% by weight, the peeling force tends to increase. On the other hand, when it exceeds 99% by weight, there are too few crosslinking components, so that it is difficult to obtain sufficient release agent layer strength. The solid content of the release agent means the total content of release agent components other than the organic solvent.
[イソシアネート]
本発明の剥離剤は、1種または2種以上のイソシアネートを含有する。イソシアネートは、芳香族イソシアネートおよび脂肪族イソシアネートのいずれでもよい。脂肪族イソシアネートは、鎖状脂肪族イソシアネートおよび脂環式イソシアネートのいずれでもよい。これらの中でも、芳香族イソシアネートおよび脂環式イソシアネートが好ましい。芳香族イソシアネートおよび脂環式イソシアネートは、ポリオレフィンとの相溶性が低いため、これらを使用しても、剥離剤層の剥離性は損なわれない。一方、ポリオレフィンと相溶しない芳香族イソシアネートおよび脂環式イソシアネートは、形成される剥離剤層と基材との間に偏在し、これらの密着性向上に大きく寄与する。 [Isocyanate]
The release agent of the present invention contains one or more isocyanates. The isocyanate may be either an aromatic isocyanate or an aliphatic isocyanate. The aliphatic isocyanate may be either a chain aliphatic isocyanate or an alicyclic isocyanate. Among these, aromatic isocyanate and alicyclic isocyanate are preferable. Since aromatic isocyanate and alicyclic isocyanate have low compatibility with polyolefin, even if they are used, the releasability of the release agent layer is not impaired. On the other hand, aromatic isocyanate and alicyclic isocyanate that are incompatible with polyolefin are unevenly distributed between the release agent layer to be formed and the base material, and greatly contribute to the improvement of adhesion.
本発明の剥離剤は、1種または2種以上のイソシアネートを含有する。イソシアネートは、芳香族イソシアネートおよび脂肪族イソシアネートのいずれでもよい。脂肪族イソシアネートは、鎖状脂肪族イソシアネートおよび脂環式イソシアネートのいずれでもよい。これらの中でも、芳香族イソシアネートおよび脂環式イソシアネートが好ましい。芳香族イソシアネートおよび脂環式イソシアネートは、ポリオレフィンとの相溶性が低いため、これらを使用しても、剥離剤層の剥離性は損なわれない。一方、ポリオレフィンと相溶しない芳香族イソシアネートおよび脂環式イソシアネートは、形成される剥離剤層と基材との間に偏在し、これらの密着性向上に大きく寄与する。 [Isocyanate]
The release agent of the present invention contains one or more isocyanates. The isocyanate may be either an aromatic isocyanate or an aliphatic isocyanate. The aliphatic isocyanate may be either a chain aliphatic isocyanate or an alicyclic isocyanate. Among these, aromatic isocyanate and alicyclic isocyanate are preferable. Since aromatic isocyanate and alicyclic isocyanate have low compatibility with polyolefin, even if they are used, the releasability of the release agent layer is not impaired. On the other hand, aromatic isocyanate and alicyclic isocyanate that are incompatible with polyolefin are unevenly distributed between the release agent layer to be formed and the base material, and greatly contribute to the improvement of adhesion.
基材密着性および耐熱性に優れた剥離剤層を形成するためには、イソシアネートは、好ましくは1分子中にイソシアネート基を3個以上有するポリイソシアネートであり、より好ましくは芳香族ポリイソシアネートおよび脂環式ポリイソシアネートからなる群から選ばれる少なくとも一つであり、さらに好ましくは芳香族ジイソシアネートの多価アルコール付加体および脂環式ジイソシアネートの多価アルコール付加体からなる群から選ばれる少なくとも一つである。
In order to form a release agent layer excellent in substrate adhesion and heat resistance, the isocyanate is preferably a polyisocyanate having three or more isocyanate groups in one molecule, more preferably an aromatic polyisocyanate and a fat. It is at least one selected from the group consisting of cyclic polyisocyanates, more preferably at least one selected from the group consisting of polyhydric alcohol adducts of aromatic diisocyanates and polyhydric alcohol adducts of alicyclic diisocyanates. .
芳香族ジイソシアネートとしては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、1,5-ナフチレンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。これらの中で、トリレンジイソシアネートおよびキシリレンジイソシアネートが好ましい。
Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like. Of these, tolylene diisocyanate and xylylene diisocyanate are preferred.
脂環式ジイソシアネートとしては、例えば、イソホロンジイソシアネート、水素化キシリレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、ダイマー酸ジイソシアネート、ノルボルネンジイソシアネート、トランス-シクロヘキサンジイソシアネート、水素化トリレンジイソシアネート等が挙げられる。これらの中で、イソホロンジイソシアネートおよび水素化キシリレンジイソシアネートが好ましい。
Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, trans-cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, and the like. Of these, isophorone diisocyanate and hydrogenated xylylene diisocyanate are preferred.
多価アルコールとしては、例えば、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトールなどの脂肪族多価アルコール等が挙げられる。これらの中で、トリメチロールプロパンが好ましい。
Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Of these, trimethylolpropane is preferred.
ポリイソシアネートとしては、例えば、前記多価アルコールと、過剰量の前記芳香族ジイソシアネートまたは前記脂環式ジイソシアネートとを反応させて得られる、イソシアネート基を末端に含有する化合物が挙げられる。また、芳香族ジイソシアネートまたは脂環式ジイソシアネートの多量体(例えば、イソシアヌレート体)も、ポリイソシアネートとして好適である。芳香族ジイソシアネートの多価アルコール付加体は、好ましくはトリレンジイソシアネートまたはキシリレンジイソシアネートの多価アルコール付加体であり、より好ましくはトリレンジイソシアネートの多価アルコール付加体である。トリレンジイソシアネートの多価アルコール付加体は、反応性に優れ、優れた基材密着性を達成できる。また、脂環式ジイソシアネートの多価アルコール付加体は、好ましくは水素化キシリレンジイソシアネートまたはイソホロンジイソシアネートの多価アルコール付加体である。
Examples of the polyisocyanate include compounds having an isocyanate group at the terminal, obtained by reacting the polyhydric alcohol with an excess amount of the aromatic diisocyanate or the alicyclic diisocyanate. In addition, aromatic diisocyanates or alicyclic diisocyanates (eg, isocyanurates) are also suitable as polyisocyanates. The polyhydric alcohol adduct of aromatic diisocyanate is preferably a polyhydric alcohol adduct of tolylene diisocyanate or xylylene diisocyanate, more preferably a polyhydric alcohol adduct of tolylene diisocyanate. The polyhydric alcohol adduct of tolylene diisocyanate is excellent in reactivity and can achieve excellent substrate adhesion. The polyhydric alcohol adduct of alicyclic diisocyanate is preferably a polyhydric alcohol adduct of hydrogenated xylylene diisocyanate or isophorone diisocyanate.
剥離剤中のイソシアネートの含有量は、ポリオレフィン100重量部に対して、好ましくは0.5~20重量部であり、より好ましくは1.0~15重量部、さらに好ましくは1.5~10重量部である。このような含有量でイソシアネートを使用すれば、剥離剤のポットライフが短くなるなどの悪影響もなく、より優れた基材密着性が得られる。
The content of isocyanate in the release agent is preferably 0.5 to 20 parts by weight, more preferably 1.0 to 15 parts by weight, still more preferably 1.5 to 10 parts by weight with respect to 100 parts by weight of polyolefin. Part. If isocyanate is used at such a content, there is no adverse effect such as shortening the pot life of the release agent, and better substrate adhesion can be obtained.
[ポリオレフィンポリオール]
本発明の剥離剤は、1種または2種以上のポリオレフィンポリオールを含有する。ポリオレフィンポリオールは、剥離剤層の形成でイソシアネートと反応させるために用いられる。ポリオレフィンポリオールとしては、ポリオレフィンとの相溶性が良いものが好ましい。 [Polyolefin polyol]
The release agent of the present invention contains one or more polyolefin polyols. Polyolefin polyol is used to react with isocyanate in the formation of a release agent layer. As the polyolefin polyol, those having good compatibility with the polyolefin are preferable.
本発明の剥離剤は、1種または2種以上のポリオレフィンポリオールを含有する。ポリオレフィンポリオールは、剥離剤層の形成でイソシアネートと反応させるために用いられる。ポリオレフィンポリオールとしては、ポリオレフィンとの相溶性が良いものが好ましい。 [Polyolefin polyol]
The release agent of the present invention contains one or more polyolefin polyols. Polyolefin polyol is used to react with isocyanate in the formation of a release agent layer. As the polyolefin polyol, those having good compatibility with the polyolefin are preferable.
ポリオレフィンポリオールの数平均分子量(Mn)は、好ましくは1500~50000、より好ましくは1500~4000、さらに好ましくは1500~3000である。このような範囲のMnを有するポリオレフィンポリオールは、ポリオレフィンおよびイソシアネートの両方に対して適度な溶解性を有する。そのため、このようなポリオレフィンポリオールは、剥離剤層強度や耐熱性を向上させることができ、一方で、剥離剤層の外観を損なわない。なお、このMnが前記範囲外であると、白っぽく曇った外観の剥離剤層が得られることがある。さらに、このMnが前記範囲内であれば、基材とは反対側のイソシアネートが偏在していない剥離剤層部分においてポリオレフィンポリオールに起因する水酸基が過剰にならず、剥離力の低い剥離剤層が得られる。さらに、このMnが前記範囲内であれば、基材側のイソシアネートが偏在する剥離剤層部分においてイソシアネートとポリオレフィンポリオールとが適度に反応することができ、より優れた基材密着性が得られる。
The number average molecular weight (Mn) of the polyolefin polyol is preferably 1500 to 50000, more preferably 1500 to 4000, and still more preferably 1500 to 3000. A polyolefin polyol having Mn in such a range has moderate solubility in both polyolefin and isocyanate. Therefore, such a polyolefin polyol can improve the release agent layer strength and heat resistance, while not impairing the appearance of the release agent layer. In addition, when this Mn is outside the above range, a release agent layer having a whitish and cloudy appearance may be obtained. Furthermore, if this Mn is within the above range, the release agent layer where the isocyanate on the side opposite to the substrate is not unevenly distributed does not have excessive hydroxyl groups due to the polyolefin polyol, and a release agent layer having a low release force is present. can get. Furthermore, if this Mn is within the above range, the isocyanate and the polyolefin polyol can be appropriately reacted in the release agent layer portion where the isocyanate on the substrate side is unevenly distributed, and more excellent substrate adhesion can be obtained.
本発明において、ポリオレフィンポリオールの種類に特に限定はない。ポリオレフィンポリオールとしては、例えば、ポリエチレン系ポリオール、ポリプロピレン系ポリオール、ポリブタジエンポリオール、水素添加ポリブタジエンポリオール、ポリイソプレンポリオールおよび水素添加ポリイソプレンポリオール等が挙げられる。これらの中でも、ポリオレフィンとの相溶性や剥離力への影響の観点から、水素添加ポリイソプレンポリオールおよびポリイソプレンポリオールが好ましい。
In the present invention, the type of polyolefin polyol is not particularly limited. Examples of polyolefin polyols include polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, and hydrogenated polyisoprene polyols. Among these, hydrogenated polyisoprene polyol and polyisoprene polyol are preferable from the viewpoint of compatibility with polyolefin and influence on peeling force.
また、ポリオレフィンポリオールの水酸基価(mgKOH/g)は、剥離剤層強度および硬化性の観点から20以上が好ましく、一方、剥離力への影響の観点から75以下が好ましい。より好ましい水酸基価(mgKOH/g)は、25~60である。
In addition, the hydroxyl value (mgKOH / g) of the polyolefin polyol is preferably 20 or more from the viewpoint of the release agent layer strength and curability, and is preferably 75 or less from the viewpoint of the influence on the peeling force. A more preferred hydroxyl value (mgKOH / g) is 25-60.
本発明において、市販のポリオレフィンポリオールを使用することができる。そのような市販品としては、例えば、Poly bdR-45HT(水酸基末端液状ポリブタジエン:Mn=2800、水酸基価=46.6mgKOH/g、出光興産社製)、Poly ip(水酸基末端液状ポリイソプレン:Mn=2500、水酸基価=46.6mgKOH/g、出光興産社製)、エポール(水酸基末端液状水添ポリイソプレン:Mn=2500、水酸基価=50.5mgKOH/g、出光興産社製)、GI-1000(水酸基含有液状水添ポリブタジエン:Mn=1500、水酸基価=60~75mgKOH/g、日本曹達社製)、GI-2000(水酸基含有液状水添ポリブタジエン:Mn=2100、水酸基価=40~55mgKOH/g、日本曹達社製)、GI-3000(水酸基含有液状水添ポリブタジエン:Mn=3000、水酸基価=25~35mgKOH/g、日本曹達社製)などが挙げられる。これらのポリオレフィンポリオールは、いずれも常温で液状である。また、ユニストールP-801(水酸基含有ポリオレフィンの16重量%トルエン溶液、トルエン除去物は固体、水酸基価40mgKOH/g、三井化学社製)を使用することもできる。
In the present invention, a commercially available polyolefin polyol can be used. Examples of such commercially available products include Poly bdR-45HT (hydroxyl-terminated liquid polybutadiene: Mn = 2800, hydroxyl value = 46.6 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Poly ip (hydroxyl-terminated liquid polyisoprene: Mn = 2500, hydroxyl value = 46.6 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Epol (hydroxyl-terminated liquid hydrogenated polyisoprene: Mn = 2500, hydroxyl value = 50.5 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), GI-1000 ( Hydroxyl group-containing liquid hydrogenated polybutadiene: Mn = 1500, hydroxyl value = 60 to 75 mgKOH / g, manufactured by Nippon Soda Co., Ltd., GI-2000 (hydroxyl group-containing liquid hydrogenated polybutadiene: Mn = 2100, hydroxyl value = 40 to 55 mgKOH / g, Nippon Soda Co., Ltd.), GI-3000 (Hydroxyl-containing liquid hydrogenated polybutadiene: n = 3000, hydroxyl value = 25 ~ 35mgKOH / g, manufactured by Nippon Soda Co., Ltd.) and the like. These polyolefin polyols are all liquid at room temperature. Unistor P-801 (16% by weight toluene solution of hydroxyl group-containing polyolefin, toluene removed product is solid, hydroxyl value 40 mg KOH / g, manufactured by Mitsui Chemicals, Inc.) can also be used.
剥離剤中のポリオレフィンポリオールの含有量は、次式(I):
A=ポリオレフィンポリオールの水酸基価(mgKOH/g)×ポリオレフィン100重量部に対するポリオレフィンポリオールの重量部数 ・・・ (I)
におけるAの値が、好ましくは30~250、より好ましくは40~200、さらに好ましくは50~150となるように設定される。Aの値が30より小さいと、剥離剤層強度が充分ではなくなる傾向があり、250より大きいと、剥離剤層の剥離力が高くなりすぎる傾向がある。 The content of the polyolefin polyol in the release agent is represented by the following formula (I):
A = hydroxyl value of polyolefin polyol (mgKOH / g) × number of parts by weight of polyolefin polyol with respect to 100 parts by weight of polyolefin (I)
The value of A is preferably set to 30 to 250, more preferably 40 to 200, and still more preferably 50 to 150. If the value of A is less than 30, the release agent layer strength tends to be insufficient, and if it is greater than 250, the release force of the release agent layer tends to be too high.
A=ポリオレフィンポリオールの水酸基価(mgKOH/g)×ポリオレフィン100重量部に対するポリオレフィンポリオールの重量部数 ・・・ (I)
におけるAの値が、好ましくは30~250、より好ましくは40~200、さらに好ましくは50~150となるように設定される。Aの値が30より小さいと、剥離剤層強度が充分ではなくなる傾向があり、250より大きいと、剥離剤層の剥離力が高くなりすぎる傾向がある。 The content of the polyolefin polyol in the release agent is represented by the following formula (I):
A = hydroxyl value of polyolefin polyol (mgKOH / g) × number of parts by weight of polyolefin polyol with respect to 100 parts by weight of polyolefin (I)
The value of A is preferably set to 30 to 250, more preferably 40 to 200, and still more preferably 50 to 150. If the value of A is less than 30, the release agent layer strength tends to be insufficient, and if it is greater than 250, the release force of the release agent layer tends to be too high.
[カルボン酸金属塩]
本発明の剥離剤は、ウレタン化触媒として、非有機錫化合物であるカルボン酸金属塩を含有する。本発明において「有機錫化合物」とは、錫-炭素(Sn-C)結合を有する化合物または塩をいい、例えば、ジブチル錫ジラウレート、ジオクチル錫ジラウレートなどが挙げられる。これに対して、「非有機錫化合物」とは、錫-炭素結合を有さない化合物または塩をいう。 [Carboxylic acid metal salt]
The release agent of the present invention contains a carboxylic acid metal salt that is a non-organotin compound as a urethanization catalyst. In the present invention, the “organotin compound” refers to a compound or salt having a tin-carbon (Sn—C) bond, and examples thereof include dibutyltin dilaurate and dioctyltin dilaurate. In contrast, “non-organotin compound” refers to a compound or salt having no tin-carbon bond.
本発明の剥離剤は、ウレタン化触媒として、非有機錫化合物であるカルボン酸金属塩を含有する。本発明において「有機錫化合物」とは、錫-炭素(Sn-C)結合を有する化合物または塩をいい、例えば、ジブチル錫ジラウレート、ジオクチル錫ジラウレートなどが挙げられる。これに対して、「非有機錫化合物」とは、錫-炭素結合を有さない化合物または塩をいう。 [Carboxylic acid metal salt]
The release agent of the present invention contains a carboxylic acid metal salt that is a non-organotin compound as a urethanization catalyst. In the present invention, the “organotin compound” refers to a compound or salt having a tin-carbon (Sn—C) bond, and examples thereof include dibutyltin dilaurate and dioctyltin dilaurate. In contrast, “non-organotin compound” refers to a compound or salt having no tin-carbon bond.
カルボン酸金属塩のカルボン酸は、脂肪族カルボン酸および芳香族カルボン酸のいずれでもよい。また、カルボン酸は、一塩基酸および多塩基酸のいずれでもよい。脂肪族カルボン酸は、直鎖状および分枝鎖状のいずれでもよく、また飽和および不飽和のいずれでもよい。また、脂肪族カルボン酸は、脂環式アルキル基を有していてもよい。
The carboxylic acid of the carboxylic acid metal salt may be either an aliphatic carboxylic acid or an aromatic carboxylic acid. The carboxylic acid may be either a monobasic acid or a polybasic acid. The aliphatic carboxylic acid may be linear or branched, and may be either saturated or unsaturated. The aliphatic carboxylic acid may have an alicyclic alkyl group.
脂肪族カルボン酸としては、例えば、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、2-エチルヘキサン酸、ノナン酸、デカン酸、ネオデカン酸、オレイン酸およびリノール酸などが挙げられる。芳香族カルボン酸としては、例えば、安息香酸、フタル酸、イソフタル酸およびテレフタル酸などが挙げられる。
Examples of the aliphatic carboxylic acid include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, oleic acid and linoleic acid. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid.
カルボン酸は、ナフテン酸または樹脂酸であってもよい。本発明において、ナフテン酸とは、石油中に含まれるカルボン酸を意味し、樹脂酸とは、天然樹脂に含まれるカルボン酸を意味する。ナフテン酸および樹脂酸は、いずれも、1種のみでもよく、2種以上の混合物でもよい。ナフテン酸としては、例えば、シクロペンタン環またはシクロヘキサン環のメチレン側鎖の末端にカルボキシ基を有するものなどが挙げられる。樹脂酸としては、例えば、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、パルストリン酸、レボピマル酸、ポドカルプ酸、d-ピマル酸およびイソ-d-ピマル酸などが挙げられる。
The carboxylic acid may be naphthenic acid or resin acid. In the present invention, naphthenic acid means carboxylic acid contained in petroleum, and resin acid means carboxylic acid contained in natural resin. Naphthenic acid and resin acid may be either one kind or a mixture of two or more kinds. Examples of naphthenic acid include those having a carboxy group at the end of the methylene side chain of the cyclopentane ring or cyclohexane ring. Examples of the resin acid include abietic acid, neoabietic acid, dehydroabietic acid, pultrinic acid, levopimaric acid, podocarpic acid, d-pimalic acid, and iso-d-pimalic acid.
カルボン酸金属塩の金属としては、例えば、ビスマス、ジルコニウム、亜鉛、チタンおよびカルシウムなどが挙げられる。触媒活性や有機溶媒への溶解性などの観点から、カルボン酸金属塩は、好ましくはカルボン酸ビスマスである。
Examples of the metal of the carboxylic acid metal salt include bismuth, zirconium, zinc, titanium, and calcium. From the viewpoint of catalytic activity and solubility in an organic solvent, the carboxylic acid metal salt is preferably bismuth carboxylate.
カルボン酸金属塩としては、1種のみを使用してもよく、2種以上の混合物を使用してもよい。カルボン酸金属塩の混合物は、複数のカルボン酸と一つの金属塩基とから形成される混合物、一つのカルボン酸と複数の金属塩基とから形成される混合物、および複数のカルボン酸と複数の金属塩基とから形成される混合物のいずれでもよい。
As the carboxylic acid metal salt, only one kind may be used, or a mixture of two or more kinds may be used. A mixture of carboxylic acid metal salts includes a mixture formed from a plurality of carboxylic acids and one metal base, a mixture formed from one carboxylic acid and a plurality of metal bases, and a plurality of carboxylic acids and a plurality of metal bases. Any of the mixtures formed from
本発明において、市販のカルボン酸金属塩を使用してもよい。市販のカルボン酸ビスマスとしては、例えば、プキャットB7およびプキャットB25(いずれも日本化学産業社製)、ネオスタンU-600(日東化成社製)、並びにK-KAT XC-227(KING INDUSTRIES社製)などが挙げられる。市販のカルボン酸ジルコニウムとしては、例えば、ナフテックスZrおよびニッカオクチックスZr(いずれも日本化学産業社製)などが挙げられる。市販のカルボン酸亜鉛としては、例えば、ナフテックスZnおよびニッカオクチックスZn(いずれも日本化学産業社製)などが挙げられる。市販のカルボン酸カルシウムとしては、例えば、ナフテックスCa、ニッカオクチックスCaおよびプキャットCa-5B(いずれも日本化学産業社製)などが挙げられる。
In the present invention, a commercially available carboxylic acid metal salt may be used. Examples of commercially available bismuth carboxylates include Puccat B7 and Puccat B25 (both manufactured by Nippon Kagaku Sangyo Co., Ltd.), Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.), and K-KAT XC-227 (manufactured by KING INDUSTRIES). Is mentioned. Examples of commercially available zirconium carboxylates include naphthex Zr and Nikka Octix Zr (both manufactured by Nippon Chemical Industry Co., Ltd.). Examples of commercially available zinc carboxylates include naphthex Zn and Nikka octix Zn (both manufactured by Nippon Chemical Industry Co., Ltd.). Examples of commercially available calcium carboxylates include naphthex Ca, Nikka octix Ca and PACCAT Ca-5B (all manufactured by Nippon Kagaku Sangyo Co., Ltd.).
剥離剤中のカルボン酸金属塩の含有量は、ポリオレフィン100重量部に対して、好ましくは0.1~2.5重量部、より好ましくは0.3~2.0重量部、さらに好ましくは0.4~1.5重量部である。この含有量が0.1重量部未満では、触媒作用が不充分となることがあり、一方、この含有量が2.5重量部を超えると、剥離剤層の剥離力が高くなったり、剥離剤のポットライフが短くなるなどの不具合の原因となることがある。
The content of the carboxylic acid metal salt in the release agent is preferably 0.1 to 2.5 parts by weight, more preferably 0.3 to 2.0 parts by weight, and still more preferably 0 to 100 parts by weight of the polyolefin. .4 to 1.5 parts by weight. When the content is less than 0.1 parts by weight, the catalytic action may be insufficient. On the other hand, when the content exceeds 2.5 parts by weight, the release force of the release agent layer is increased or the release is peeled off. It may cause problems such as shortening the pot life of the agent.
なお、ここでいうカルボン酸金属塩の含有量は、カルボン酸金属塩のみの量を指し、例えば後述の実施例で使用する「プキャットB7」のようにカルボン酸金属塩を溶媒に溶かした溶液を使用する場合、溶媒量を除いたカルボン酸金属塩のみの量を意味する。
In addition, content of carboxylic acid metal salt here refers to the quantity of only carboxylic acid metal salt, for example, the solution which dissolved carboxylic acid metal salt in the solvent like "Pucat B7" used in the below-mentioned Example. When used, it means the amount of carboxylic acid metal salt only, excluding the amount of solvent.
[有機溶媒]
本発明の剥離剤は、有機溶媒として、炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒を含有する。炭化水素系溶媒および非プロトン性極性溶媒は、それぞれ、1種のみを使用してもよく、2種以上を併用してもよい。 [Organic solvent]
The release agent of the present invention contains a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent as an organic solvent. As the hydrocarbon solvent and the aprotic polar solvent, only one type may be used, or two or more types may be used in combination.
本発明の剥離剤は、有機溶媒として、炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒を含有する。炭化水素系溶媒および非プロトン性極性溶媒は、それぞれ、1種のみを使用してもよく、2種以上を併用してもよい。 [Organic solvent]
The release agent of the present invention contains a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent as an organic solvent. As the hydrocarbon solvent and the aprotic polar solvent, only one type may be used, or two or more types may be used in combination.
炭化水素系溶媒としては、例えば、ノルマルヘキサンおよびノルマルヘプタン等の脂肪族炭化水素;シクロヘキサン等の脂環式炭化水素;並びにトルエンおよびキシレン等の芳香族系炭化水素が挙げられる。剥離剤成分(特にイソシアネート)の溶解性などの観点から、芳香族炭化水素が好ましく、トルエンおよびキシレンがより好ましく、トルエンがさらに好ましい。
Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as normal hexane and normal heptane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as toluene and xylene. From the viewpoint of the solubility of the release agent component (particularly isocyanate), aromatic hydrocarbons are preferred, toluene and xylene are more preferred, and toluene is more preferred.
非プロトン性極性溶媒としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノンおよびアセチルアセトン等のケトン系溶媒;ジエチルエーテル等のエーテル系溶媒;酢酸エチル等のエステル系溶媒;アセトニトリル等のニトリル系溶媒;N,N-ジメチルホルムアミド(DMF)およびN,N-ジメチルアセトアミド(DMAC)等のアミド系溶媒;並びにジメチルスルホキシド(DMSO)等のスルホキシド系溶媒などが挙げられる。剥離剤成分(特にカルボン酸金属塩)の溶解性などの観点から、ケトン系溶媒が好ましく、メチルエチルケトン、シクロヘキサノンおよびアセチルアセトンがより好ましく、アセチルアセトンがさらに好ましい。
Examples of the aprotic polar solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; ether solvents such as diethyl ether; ester solvents such as ethyl acetate; nitrile solvents such as acetonitrile; N, N— Examples thereof include amide solvents such as dimethylformamide (DMF) and N, N-dimethylacetamide (DMAC); and sulfoxide solvents such as dimethyl sulfoxide (DMSO). From the viewpoint of the solubility of the release agent component (particularly metal carboxylate), ketone solvents are preferred, methyl ethyl ketone, cyclohexanone and acetylacetone are more preferred, and acetylacetone is more preferred.
炭化水素系溶媒として沸点が高い芳香族炭化水素系溶媒、特にキシレン(沸点144℃)またはその混合溶媒を使用する場合、これに比べて非プロトン性極性溶媒の沸点が低すぎると、溶媒除去による剥離剤層の形成時に非プロトン性極性溶媒のみが先に除去されてしまい、得られる剥離剤層の外観に悪影響を及ぼす場合がある。そこで、沸点が高い芳香族炭化水素系溶媒を使用する場合には、同様に沸点が高い非プロトン性極性溶媒を使用することが好ましい。例えば、炭化水素系溶媒が、キシレン、またはトルエンおよびキシレンである場合(好ましくはトルエンおよびキシレンである場合)、非プロトン性極性溶媒は、好ましくはシクロヘキサノン(沸点156℃)、アセチルアセトン(沸点140℃)、N,N-ジメチルホルムアミド(沸点153℃)およびN,N-ジメチルアセトアミド(沸点165℃)からなる群から選ばれる少なくとも一つであり、より好ましくはアセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つであり、さらに好ましくはアセチルアセトンである。
When using an aromatic hydrocarbon solvent having a high boiling point as a hydrocarbon solvent, particularly xylene (boiling point 144 ° C.) or a mixed solvent thereof, if the boiling point of the aprotic polar solvent is too low, When the release agent layer is formed, only the aprotic polar solvent is removed first, which may adversely affect the appearance of the resulting release agent layer. Therefore, when using an aromatic hydrocarbon solvent having a high boiling point, it is preferable to use an aprotic polar solvent having a high boiling point as well. For example, when the hydrocarbon solvent is xylene or toluene and xylene (preferably toluene and xylene), the aprotic polar solvent is preferably cyclohexanone (boiling point 156 ° C.), acetylacetone (boiling point 140 ° C.) , N, N-dimethylformamide (boiling point 153 ° C.) and N, N-dimethylacetamide (boiling point 165 ° C.), more preferably at least one selected from the group consisting of acetylacetone and cyclohexanone. More preferred is acetylacetone.
剥離剤成分の溶解性のバランス、特にイソシアネートおよびカルボン酸金属塩の溶解性のバランスから、炭化水素系溶媒と非プロトン性極性溶媒との重量比(炭化水素系溶媒:非プロトン性極性溶媒)は、好ましくは99:1~90:10、より好ましくは99:1~92:8、さらに好ましくは99:1~95:5である。また、有機溶媒の含有量は、剥離剤中、好ましくは95~99.9重量%の範囲内で調整される。
From the balance of solubility of the release agent component, especially the balance of solubility of isocyanate and carboxylic acid metal salt, the weight ratio of hydrocarbon solvent to aprotic polar solvent (hydrocarbon solvent: aprotic polar solvent) is The ratio is preferably 99: 1 to 90:10, more preferably 99: 1 to 92: 8, and still more preferably 99: 1 to 95: 5. Further, the content of the organic solvent is adjusted in the release agent, preferably in the range of 95 to 99.9% by weight.
[任意成分]
本発明の剥離剤は、1種または2種以上の任意成分を含有していてもよい。例えば、低剥離力を有する剥離剤層が求められる場合には、剥離剤の任意成分として1種または2種以上の液状炭化水素を使用してもよい。ここで、本発明における「液状炭化水素」とは、JIS K7117-1:1990に従って測定した38℃における粘度(以下「38℃粘度」と略称することがある)が5~1500Pa・sである炭化水素を意味する。このような液状炭化水素を使用することによって、粘着テープ類の粘着力を低下させることなく、剥離剤層の剥離力の速度依存性を低減し得る。 [Optional ingredients]
The release agent of the present invention may contain one or more optional components. For example, when a release agent layer having a low release force is required, one or more liquid hydrocarbons may be used as an optional component of the release agent. Here, the “liquid hydrocarbon” in the present invention is a carbonization having a viscosity at 38 ° C. (hereinafter sometimes referred to as “38 ° C. viscosity”) of 5 to 1500 Pa · s measured according to JIS K7117-1: 1990. Means hydrogen. By using such a liquid hydrocarbon, the speed dependency of the release force of the release agent layer can be reduced without reducing the adhesive force of the adhesive tapes.
本発明の剥離剤は、1種または2種以上の任意成分を含有していてもよい。例えば、低剥離力を有する剥離剤層が求められる場合には、剥離剤の任意成分として1種または2種以上の液状炭化水素を使用してもよい。ここで、本発明における「液状炭化水素」とは、JIS K7117-1:1990に従って測定した38℃における粘度(以下「38℃粘度」と略称することがある)が5~1500Pa・sである炭化水素を意味する。このような液状炭化水素を使用することによって、粘着テープ類の粘着力を低下させることなく、剥離剤層の剥離力の速度依存性を低減し得る。 [Optional ingredients]
The release agent of the present invention may contain one or more optional components. For example, when a release agent layer having a low release force is required, one or more liquid hydrocarbons may be used as an optional component of the release agent. Here, the “liquid hydrocarbon” in the present invention is a carbonization having a viscosity at 38 ° C. (hereinafter sometimes referred to as “38 ° C. viscosity”) of 5 to 1500 Pa · s measured according to JIS K7117-1: 1990. Means hydrogen. By using such a liquid hydrocarbon, the speed dependency of the release force of the release agent layer can be reduced without reducing the adhesive force of the adhesive tapes.
液状炭化水素の38℃粘度は、通常5~1500Pa・sであり、好ましくは5~1300Pa・sである。この38℃粘度が5Pa・s未満である場合、剥離力の速度依存性が充分に低減しないことがある。剥離力の速度依存性を充分に低減するために、38℃粘度が5Pa・s未満である液状炭化水素の使用量を多くすると、粘着テープ類の粘着力が低下する。一方で、38℃粘度が1500Pa・sを超える場合、離型材および粘着テープの想定使用温度である10~30℃付近で、液状炭化水素の流動性が低くなるため、剥離力の速度依存性が充分に低減しないことがある。
The 38 ° C. viscosity of the liquid hydrocarbon is usually 5 to 1500 Pa · s, preferably 5 to 1300 Pa · s. When this 38 degreeC viscosity is less than 5 Pa * s, the speed dependence of peeling force may not fully reduce. In order to sufficiently reduce the speed dependency of the peeling force, when the amount of liquid hydrocarbon having a viscosity at 38 ° C. of less than 5 Pa · s is increased, the adhesive strength of the adhesive tapes is lowered. On the other hand, when the viscosity at 38 ° C. exceeds 1500 Pa · s, the fluidity of the liquid hydrocarbon decreases near the expected use temperature of the release material and the adhesive tape of 10-30 ° C. It may not be reduced sufficiently.
液状炭化水素としては、例えば、不飽和炭化水素の重合体等が挙げられる。ここで、本発明における「不飽和炭化水素の重合体」は、ポリマーだけでなく、オリゴマーも含む意味で用いられる。相溶性の観点から、液状炭化水素は、好ましくはエチレンと炭素数3~5の不飽和炭化水素との液状共重合体、炭素数3~5の不飽和炭化水素の液状単独重合体および炭素数3~5の不飽和炭化水素の液状共重合体からなる群から選ばれる少なくとも一つである。炭素数3~5の不飽和炭化水素としては、例えば、プロピレン、1-ブテン、イソブテン、2-ブテン、ブタジエン、1-ペンテン、2-ペンテン、イソペンテン、イソプレン等が挙げられる。液状炭化水素は、より好ましくは液状エチレン-オレフィン共重合体、液状ポリブタジエン、液状ポリイソプレン、液状水素化ポリブタジエン、液状水素化ポリイソプレンおよび液状ポリイソブテンからなる群から選ばれる少なくとも一つである。液状炭化水素は、公知の方法、例えばラジカル重合またはカチオン重合等によって製造できる。
Examples of liquid hydrocarbons include polymers of unsaturated hydrocarbons. Here, the “polymer of unsaturated hydrocarbon” in the present invention is used to mean not only a polymer but also an oligomer. From the viewpoint of compatibility, the liquid hydrocarbon is preferably a liquid copolymer of ethylene and an unsaturated hydrocarbon having 3 to 5 carbon atoms, a liquid homopolymer of an unsaturated hydrocarbon having 3 to 5 carbon atoms, and a carbon number. It is at least one selected from the group consisting of 3 to 5 unsaturated hydrocarbon liquid copolymers. Examples of the unsaturated hydrocarbon having 3 to 5 carbon atoms include propylene, 1-butene, isobutene, 2-butene, butadiene, 1-pentene, 2-pentene, isopentene, isoprene and the like. The liquid hydrocarbon is more preferably at least one selected from the group consisting of a liquid ethylene-olefin copolymer, liquid polybutadiene, liquid polyisoprene, liquid hydrogenated polybutadiene, liquid hydrogenated polyisoprene, and liquid polyisobutene. The liquid hydrocarbon can be produced by a known method such as radical polymerization or cationic polymerization.
液状炭化水素として、市販品を用いてもよい。市販の液状炭化水素としては、例えば、ルーカント HC-600(38℃粘度=8.5Pa・s)、HC-2000(38℃粘度=34Pa・s)(以上、三井化学社製)、クラプレンLIR-30(38℃粘度=74Pa・s)、LIR-50(38℃粘度=480Pa・s)、LIR-290(38℃粘度=1000Pa・s)、LBR-300(38℃粘度=280Pa・s)(以上、クラレ社製)、日石ポリブテンHV-100、HV-300、HV-1900(以上、新日本石油社製)、ニッサンポリブテン10N、30N、200N(以上、日油社製)等が挙げられる。
Commercial products may be used as liquid hydrocarbons. Examples of commercially available liquid hydrocarbons include Lucant HC-600 (38 ° C. viscosity = 8.5 Pa · s), HC-2000 (38 ° C. viscosity = 34 Pa · s) (Mitsui Chemicals, Inc.), Claprene LIR- 30 (38 ° C. viscosity = 74 Pa · s), LIR-50 (38 ° C. viscosity = 480 Pa · s), LIR-290 (38 ° C. viscosity = 1000 Pa · s), LBR-300 (38 ° C. viscosity = 280 Pa · s) ( As mentioned above, Kuraray Co., Ltd.), Nisseki Polybutene HV-100, HV-300, HV-1900 (above, manufactured by Nippon Oil Corporation), Nissan Polybutene 10N, 30N, 200N (above, made by NOF Corporation), etc. .
液状炭化水素を使用する場合、剥離剤中のその含有量は、ポリオレフィンおよび液状炭化水素の合計100重量部に対して、好ましくは3~30重量部、より好ましくは4~20重量部、さらに好ましくは5~15重量部である。この含有量が、3重量部未満である場合、剥離速度依存性が充分に低減しないことがあり、逆に30重量部を超える場合、剥離剤層強度が低くなったり、粘着テープの粘着剤層に液状炭化水素が移行して、粘着テープの粘着力が低下することがある。
When liquid hydrocarbon is used, the content of the release agent in the release agent is preferably 3 to 30 parts by weight, more preferably 4 to 20 parts by weight, even more preferably 100 parts by weight in total of the polyolefin and the liquid hydrocarbon. Is 5 to 15 parts by weight. When this content is less than 3 parts by weight, the release rate dependency may not be sufficiently reduced. Conversely, when it exceeds 30 parts by weight, the strength of the release agent layer may be reduced or the adhesive layer of the adhesive tape. Liquid hydrocarbons may migrate to the adhesive tape, which may reduce the adhesive strength of the adhesive tape.
本発明の剥離剤は、その他必要に応じて、前記ポリオレフィン以外の樹脂、酸化防止剤、紫外線吸収剤、ヒンダードアミン光安定剤等の光安定剤や帯電防止剤、カーボンブラック、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタン等の充填剤、顔料等を含有していてもよい。
The release agent of the present invention may be a resin other than the polyolefin, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer or an antistatic agent, carbon black, calcium oxide, magnesium oxide, if necessary. It may contain a filler such as silica, zinc oxide and titanium oxide, a pigment and the like.
2.離型材
本発明は、基材および剥離剤層を有する離型材も提供する。本発明の離型材は、本発明の剥離剤から形成された剥離剤層を、基材の少なくとも片面に有することを特徴とする。以下、基材および剥離剤層について順に説明する。 2. Release material The present invention also provides a release material having a substrate and a release agent layer. The release material of the present invention is characterized by having a release agent layer formed from the release agent of the present invention on at least one surface of a substrate. Hereinafter, the substrate and the release agent layer will be described in order.
本発明は、基材および剥離剤層を有する離型材も提供する。本発明の離型材は、本発明の剥離剤から形成された剥離剤層を、基材の少なくとも片面に有することを特徴とする。以下、基材および剥離剤層について順に説明する。 2. Release material The present invention also provides a release material having a substrate and a release agent layer. The release material of the present invention is characterized by having a release agent layer formed from the release agent of the present invention on at least one surface of a substrate. Hereinafter, the substrate and the release agent layer will be described in order.
[基材]
本発明において、基材に特に限定は無い。但し、基材は、表面が平滑であるプラスチックフィルムであることが好ましい。プラスチックフィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルム;ポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルム;が挙げられる。また、クラフト紙、グラシン紙、上質紙等の紙を基材として用いてもよい。紙基材としては、剥離剤の基材への過度の含浸を防ぐために、ポリエチレン等のプラスチックがラミネートされたもの、または目止め処理されたものが好ましい。基材には、必要に応じて、予めコロナ処理、プラズマ処理、火炎処理等の処理を施しておいても良い。 [Base material]
In the present invention, the substrate is not particularly limited. However, the substrate is preferably a plastic film having a smooth surface. Examples of the plastic film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polyolefin films such as polyethylene film and polypropylene film. Further, paper such as kraft paper, glassine paper, and high-quality paper may be used as the base material. As the paper base material, in order to prevent excessive impregnation of the release agent into the base material, one laminated with a plastic such as polyethylene, or one subjected to sealing treatment is preferable. The base material may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance as necessary.
本発明において、基材に特に限定は無い。但し、基材は、表面が平滑であるプラスチックフィルムであることが好ましい。プラスチックフィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルム;ポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルム;が挙げられる。また、クラフト紙、グラシン紙、上質紙等の紙を基材として用いてもよい。紙基材としては、剥離剤の基材への過度の含浸を防ぐために、ポリエチレン等のプラスチックがラミネートされたもの、または目止め処理されたものが好ましい。基材には、必要に応じて、予めコロナ処理、プラズマ処理、火炎処理等の処理を施しておいても良い。 [Base material]
In the present invention, the substrate is not particularly limited. However, the substrate is preferably a plastic film having a smooth surface. Examples of the plastic film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polyolefin films such as polyethylene film and polypropylene film. Further, paper such as kraft paper, glassine paper, and high-quality paper may be used as the base material. As the paper base material, in order to prevent excessive impregnation of the release agent into the base material, one laminated with a plastic such as polyethylene, or one subjected to sealing treatment is preferable. The base material may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance as necessary.
基材の厚さは、特に制限されず、使用目的に応じて適宜設定することができる。基材としてプラスチックフィルムを使用する場合、その厚さは、通常12~250μm程度、好ましくは16~200μm、より好ましくは25~125μmである。
The thickness of the base material is not particularly limited and can be appropriately set according to the purpose of use. When a plastic film is used as the substrate, the thickness is usually about 12 to 250 μm, preferably 16 to 200 μm, more preferably 25 to 125 μm.
また、必要に応じて、酸化防止剤、紫外線吸収剤、ヒンダードアミン光安定剤等の光安定剤や帯電防止剤、カーボンブラック、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタン等の充填剤、顔料等を、基材に配合してもよい。
In addition, if necessary, light stabilizers such as antioxidants, ultraviolet absorbers, hindered amine light stabilizers and antistatic agents, carbon black, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide fillers, You may mix | blend a pigment etc. with a base material.
[剥離剤層]
剥離剤層は、例えば、有機溶媒を含有する本発明の剥離剤を基材に塗布し、乾燥させることによって得られる。 [Release layer]
The release agent layer is obtained, for example, by applying the release agent of the present invention containing an organic solvent to a substrate and drying it.
剥離剤層は、例えば、有機溶媒を含有する本発明の剥離剤を基材に塗布し、乾燥させることによって得られる。 [Release layer]
The release agent layer is obtained, for example, by applying the release agent of the present invention containing an organic solvent to a substrate and drying it.
剥離剤の塗布方法としては特に限定は無く、あらゆる公知の方法、例えばキスロールコーター、ビードコーター、ロッドコーター、マイヤーバーコーター、ダイコーター、グラビアコーター等を用いる方法を使用できる。乾燥方法についても特に限定は無く、あらゆる公知の方法を使用できる。一般的な乾燥方法として、熱風乾燥が挙げられる。熱風乾燥の温度は、基材の耐熱性によっても変わり得るが、通常80~150℃程度である。
The application method of the release agent is not particularly limited, and any known method, for example, a method using a kiss roll coater, a bead coater, a rod coater, a Meyer bar coater, a die coater, a gravure coater or the like can be used. There is no particular limitation on the drying method, and any known method can be used. A common drying method is hot air drying. The temperature of hot air drying may vary depending on the heat resistance of the substrate, but is usually about 80 to 150 ° C.
乾燥後の剥離剤層の厚さは、好ましくは30~500nm、より好ましくは45~400nm、さらに好ましくは60~300nmである。この厚さが30nm未満である場合、剥離剤層の剥離力が高くなりすぎる場合があり、逆に500nmを超える場合、離型材をロール状に巻き取った時に接触する基材と剥離剤層とがブロッキングしやすくなるという問題や、剥離剤層の剥離力が高くなるという問題が生じる場合がある。
The thickness of the release agent layer after drying is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm. When this thickness is less than 30 nm, the release force of the release agent layer may be too high. Conversely, when it exceeds 500 nm, the substrate and the release agent layer that come into contact with each other when the release material is wound into a roll shape, May cause a problem that it becomes easy to block, and a problem that the peeling force of the release agent layer becomes high.
離型材において、剥離剤層が最表面に存在する限り、剥離剤層と基材との間に別の層が存在していてもよい。但し、剥離剤層は、基材の上に直接形成されていることが好ましい。
In the release material, another layer may exist between the release agent layer and the substrate as long as the release agent layer is present on the outermost surface. However, the release agent layer is preferably formed directly on the substrate.
3.離型材付き粘着テープ
本発明は、粘着剤層および本発明の離型材を有し、粘着剤層と離型材の剥離剤層とが接触している粘着テープも提供する。 3. The present invention also provides a pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer and the mold release material of the present invention, wherein the pressure-sensitive adhesive layer and the release agent layer of the mold release material are in contact with each other.
本発明は、粘着剤層および本発明の離型材を有し、粘着剤層と離型材の剥離剤層とが接触している粘着テープも提供する。 3. The present invention also provides a pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer and the mold release material of the present invention, wherein the pressure-sensitive adhesive layer and the release agent layer of the mold release material are in contact with each other.
粘着剤層を形成するために用いられる粘着剤に、特に限定は無い。粘着剤としては、例えばゴム系粘着剤、アクリル系粘着剤、ポリエステル系粘着剤等が挙げられる。これらの中で、アクリル系粘着剤およびポリエステル系粘着剤が好ましい。アクリル系粘着剤およびポリエステル系粘着剤を用いて粘着剤層を形成した離型材付き粘着テープは、安定した剥離性を示す。
There is no particular limitation on the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer. Examples of the pressure-sensitive adhesive include a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a polyester-based pressure-sensitive adhesive. Among these, acrylic adhesives and polyester adhesives are preferred. The pressure-sensitive adhesive tape with a release material having a pressure-sensitive adhesive layer formed using an acrylic pressure-sensitive adhesive and a polyester-based pressure-sensitive adhesive exhibits stable releasability.
アクリル系粘着剤は、溶液重合法、エマルション重合法、UV重合法などの慣用の重合法により得られるアクリル系ポリマーを主剤とし、これに必要に応じて、架橋剤、粘着付与剤、軟化剤、老化防止剤、充填剤などの各種添加剤を加えることによって調製できる。
The acrylic pressure-sensitive adhesive is mainly composed of an acrylic polymer obtained by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a UV polymerization method, and, as necessary, a crosslinking agent, a tackifier, a softener, It can be prepared by adding various additives such as anti-aging agents and fillers.
アクリル系ポリマーとしては、例えばブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレートなどのアルキル(メタ)アクリレートを主成分とし、これに必要に応じて共重合可能な改質用単量体として2-ヒドロキシエチル(メタ)アクリレートなどのヒドロキシ基含有単量体、(メタ)アクリル酸などのカルボキシ基含有単量体、スチレンなどのスチレン系単量体、酢酸ビニルなどのビニルエステル類等の他の単量体を加えた単量体混合物の共重合体などが挙げられる。
As the acrylic polymer, for example, alkyl (meth) acrylate such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is used as a main component. -Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, carboxy group-containing monomers such as (meth) acrylic acid, styrene monomers such as styrene, vinyl esters such as vinyl acetate, etc. Examples thereof include a copolymer of a monomer mixture to which a monomer is added.
ポリエステル系粘着剤としては、脂肪族系カーボネートジオール(例えば、ブタンジオール等のジオール成分とエチレンカーボネートなどのカーボネート化合物との反応により得られるカーボネートジオールなど)を必須のポリオール成分としたポリエステル系重合体を主剤とする粘着剤が挙げられる。
As the polyester-based pressure-sensitive adhesive, a polyester-based polymer having an aliphatic polyol diol (for example, a carbonate diol obtained by reaction of a diol component such as butanediol and a carbonate compound such as ethylene carbonate) as an essential polyol component is used. Examples include a pressure-sensitive adhesive as a main ingredient.
粘着剤層は、例えば、粘着剤溶液を離型材の剥離剤層に塗布し、乾燥させることによって形成することができる。また、離型材の基材とは別の基材上に粘着剤溶液を塗布し、乾燥させることによって粘着剤層を形成し、これを離型材の剥離剤層に貼り合わせてもよい。さらに、市販の粘着テープを離型材の剥離剤層に貼り合わせることによって、離型材の粘着剤層を形成してもよい。粘着剤層の厚さは、粘着性などを考慮して適宜選択することができ、好ましくは3~100μm、より好ましくは5~90μm、さらに好ましくは10~80μmである。
The pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive solution to the release agent layer of the release material and drying it. Alternatively, a pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive solution on a base material different from the base material of the release material and drying it, and then bonding this to the release agent layer of the release material. Furthermore, you may form the adhesive layer of a mold release material by bonding a commercially available adhesive tape to the release agent layer of a mold release material. The thickness of the pressure-sensitive adhesive layer can be appropriately selected in consideration of adhesiveness and the like, and is preferably 3 to 100 μm, more preferably 5 to 90 μm, and still more preferably 10 to 80 μm.
4.剥離剤層付き粘着テープ
本発明は、基材、粘着剤層および剥離剤層を有する粘着テープも提供する。この本発明の粘着テープは、本発明の剥離剤から形成された剥離剤層を基材の片面に有し、剥離剤層が形成されていない基材の他方の面に粘着剤層を有することを特徴とする。なお以下では、この態様の剥離剤層を「背面処理層」と呼ぶことがあり、この態様の粘着テープを「背面処理層付き粘着テープ」と呼ぶことがある。 4). TECHNICAL FIELD The present invention also provides an adhesive tape having a base material, an adhesive layer and a release agent layer. This pressure-sensitive adhesive tape of the present invention has a release agent layer formed from the release agent of the present invention on one side of the substrate, and has an adhesive layer on the other side of the substrate where the release agent layer is not formed. It is characterized by. Hereinafter, the release agent layer of this aspect may be referred to as a “back treatment layer”, and the adhesive tape of this aspect may be referred to as “back treatment layer-attached adhesive tape”.
本発明は、基材、粘着剤層および剥離剤層を有する粘着テープも提供する。この本発明の粘着テープは、本発明の剥離剤から形成された剥離剤層を基材の片面に有し、剥離剤層が形成されていない基材の他方の面に粘着剤層を有することを特徴とする。なお以下では、この態様の剥離剤層を「背面処理層」と呼ぶことがあり、この態様の粘着テープを「背面処理層付き粘着テープ」と呼ぶことがある。 4). TECHNICAL FIELD The present invention also provides an adhesive tape having a base material, an adhesive layer and a release agent layer. This pressure-sensitive adhesive tape of the present invention has a release agent layer formed from the release agent of the present invention on one side of the substrate, and has an adhesive layer on the other side of the substrate where the release agent layer is not formed. It is characterized by. Hereinafter, the release agent layer of this aspect may be referred to as a “back treatment layer”, and the adhesive tape of this aspect may be referred to as “back treatment layer-attached adhesive tape”.
背面処理層付き粘着テープは、ロール状に巻回された形態またはシートが積層された形態のいずれでもよい。いずれの形態においても、粘着剤層が背面処理層によって保護される。
The backside treatment layer-attached adhesive tape may be either rolled up or laminated. In any form, the pressure-sensitive adhesive layer is protected by the back treatment layer.
背面処理層付き粘着テープにおいて、粘着剤層および背面処理層は、いずれも基材の上に直接形成されていてもよく、また、これらの層と基材との間に別の層が形成されていてもよい。但し、粘着剤層および背面処理層はいずれも最表面に存在することが必要である。こうすることによって、該粘着テープがロール状に巻回された場合、またはシート形態の該粘着テープが積層された場合に、背面処理層が、粘着剤層と接触してこれを保護することができる。なお、粘着剤層および背面処理層は、いずれも基材の上に直接形成されていることが好ましい。
In the pressure-sensitive adhesive tape with a back treatment layer, the pressure-sensitive adhesive layer and the back treatment layer may both be formed directly on the substrate, and another layer is formed between these layers and the substrate. It may be. However, both the pressure-sensitive adhesive layer and the back treatment layer must be present on the outermost surface. By doing this, when the pressure-sensitive adhesive tape is wound in a roll shape or when the pressure-sensitive adhesive tape in the form of a sheet is laminated, the back treatment layer can be in contact with the pressure-sensitive adhesive layer to protect it. it can. In addition, it is preferable that both the pressure-sensitive adhesive layer and the back treatment layer are directly formed on the substrate.
背面処理層付き粘着テープの粘着剤層を形成するために用いられる粘着剤に、特に限定は無い。このための粘着剤としては、例えば、離型材付き粘着テープで説明したものなどが挙げられる。また、粘着剤層の形成方法も、離型材付き粘着テープで説明したものと同様の方法を採用することができる。
The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape with the back treatment layer is not particularly limited. As an adhesive for this, what was demonstrated with the adhesive tape with a mold release material etc. are mentioned, for example. Moreover, the formation method of an adhesive layer can also employ | adopt the method similar to what was demonstrated with the adhesive tape with a mold release material.
背面処理層の形成方法は、離型材付き粘着テープで説明したものと同様の方法を採用することができる。背面処理層の厚さは、剥離力の観点から、好ましくは30~500nm、より好ましくは45~400nm、さらに好ましくは60~300nmである。
As the method for forming the back treatment layer, the same method as described for the pressure-sensitive adhesive tape with a release material can be employed. The thickness of the back treatment layer is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm, from the viewpoint of peeling force.
5.物性、特性等
本明細書中の物性および特性等は、以下の方法での測定値である。
(1)密度
ASTM D1505に準拠して測定した値である。
(2)メルトフローレート(230℃)
ASTM D1238に準拠して測定した値である。
(3)数平均分子量
ASTM D2503に準拠して測定した値である。
(4)水酸基価
JIS K1557:1970に準拠して測定した値である。 5. Physical properties, properties, etc. The physical properties, properties, etc. in this specification are measured values by the following methods.
(1) Density This is a value measured according to ASTM D1505.
(2) Melt flow rate (230 ° C)
It is a value measured according to ASTM D1238.
(3) Number average molecular weight It is the value measured based on ASTM D2503.
(4) Hydroxyl value A value measured in accordance with JIS K1557: 1970.
本明細書中の物性および特性等は、以下の方法での測定値である。
(1)密度
ASTM D1505に準拠して測定した値である。
(2)メルトフローレート(230℃)
ASTM D1238に準拠して測定した値である。
(3)数平均分子量
ASTM D2503に準拠して測定した値である。
(4)水酸基価
JIS K1557:1970に準拠して測定した値である。 5. Physical properties, properties, etc. The physical properties, properties, etc. in this specification are measured values by the following methods.
(1) Density This is a value measured according to ASTM D1505.
(2) Melt flow rate (230 ° C)
It is a value measured according to ASTM D1238.
(3) Number average molecular weight It is the value measured based on ASTM D2503.
(4) Hydroxyl value A value measured in accordance with JIS K1557: 1970.
以下に、実施例および比較例を挙げて本発明を具体的に説明するが、これらは本発明を限定するものではない。なお、以下において「部」および「%」は、別の記載が無い限り、それぞれ「重量部」および「重量%」を示す。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but these do not limit the present invention. In the following, “part” and “%” represent “part by weight” and “% by weight”, respectively, unless otherwise specified.
1.剥離剤成分
実施例および比較例で用いた剥離剤成分を、以下に記載する。 1. Release agent component The release agent components used in Examples and Comparative Examples are described below.
実施例および比較例で用いた剥離剤成分を、以下に記載する。 1. Release agent component The release agent components used in Examples and Comparative Examples are described below.
(1)ポリオレフィン
タフマーP-0280(エチレン-プロピレン共重合体(エチレン:87モル%、プロピレン:13モル%)、三井化学社製、MFR(230℃):5.4g/10min、密度:0.87g/cm3、23℃における引張弾性率:5.1MPa、23℃における引張破壊応力:3.3MPa)
タフマーA-35070S(エチレン-1-ブテン共重合体(エチレン:85モル%、1-ブテン:15モル%)、三井化学社製、MFR(230℃):65g/10min、密度:0.87g/cm3、23℃における引張弾性率:3.5MPa、23℃における引張破壊応力:2.1MPa) (1) Polyolefin Tuffmer P-0280 (ethylene-propylene copolymer (ethylene: 87 mol%, propylene: 13 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 5.4 g / 10 min, density: 0.00 (87 g / cm 3 , tensile elastic modulus at 23 ° C .: 5.1 MPa, tensile fracture stress at 23 ° C .: 3.3 MPa)
TAFMER A-3570S (ethylene-1-butene copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 65 g / 10 min, density: 0.87 g / cm 3 , tensile elastic modulus at 23 ° C .: 3.5 MPa, tensile fracture stress at 23 ° C .: 2.1 MPa)
タフマーP-0280(エチレン-プロピレン共重合体(エチレン:87モル%、プロピレン:13モル%)、三井化学社製、MFR(230℃):5.4g/10min、密度:0.87g/cm3、23℃における引張弾性率:5.1MPa、23℃における引張破壊応力:3.3MPa)
タフマーA-35070S(エチレン-1-ブテン共重合体(エチレン:85モル%、1-ブテン:15モル%)、三井化学社製、MFR(230℃):65g/10min、密度:0.87g/cm3、23℃における引張弾性率:3.5MPa、23℃における引張破壊応力:2.1MPa) (1) Polyolefin Tuffmer P-0280 (ethylene-propylene copolymer (ethylene: 87 mol%, propylene: 13 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 5.4 g / 10 min, density: 0.00 (87 g / cm 3 , tensile elastic modulus at 23 ° C .: 5.1 MPa, tensile fracture stress at 23 ° C .: 3.3 MPa)
TAFMER A-3570S (ethylene-1-butene copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 65 g / 10 min, density: 0.87 g / cm 3 , tensile elastic modulus at 23 ° C .: 3.5 MPa, tensile fracture stress at 23 ° C .: 2.1 MPa)
(2)ポリオレフィンポリオール
エポール(水酸基末端液状水添ポリイソプレン、Mn:2500、水酸基価:50.5mgKOH/g、出光興産社製) (2) Polyolefin polyol Epol (hydroxyl-terminated liquid hydrogenated polyisoprene, Mn: 2500, hydroxyl value: 50.5 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.)
エポール(水酸基末端液状水添ポリイソプレン、Mn:2500、水酸基価:50.5mgKOH/g、出光興産社製) (2) Polyolefin polyol Epol (hydroxyl-terminated liquid hydrogenated polyisoprene, Mn: 2500, hydroxyl value: 50.5 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.)
(3)イソシアネート
コロネートL(トリレンジイソシアネートのトリメチロールプロパン付加物の75%酢酸エチル溶液、1分子中のイソシアネート基数:3個、日本ポリウレタン社製) (3) Isocyanate Coronate L (75% ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups in one molecule: 3, manufactured by Nippon Polyurethane)
コロネートL(トリレンジイソシアネートのトリメチロールプロパン付加物の75%酢酸エチル溶液、1分子中のイソシアネート基数:3個、日本ポリウレタン社製) (3) Isocyanate Coronate L (75% ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups in one molecule: 3, manufactured by Nippon Polyurethane)
(4)液状炭化水素
ルーカント HC-2000(エチレン-α-オレフィンコオリゴマー、38℃粘度:34Pa・s、三井化学社製) (4) Liquid hydrocarbon Lucant HC-2000 (ethylene-α-olefin co-oligomer, 38 ° C. viscosity: 34 Pa · s, manufactured by Mitsui Chemicals)
ルーカント HC-2000(エチレン-α-オレフィンコオリゴマー、38℃粘度:34Pa・s、三井化学社製) (4) Liquid hydrocarbon Lucant HC-2000 (ethylene-α-olefin co-oligomer, 38 ° C. viscosity: 34 Pa · s, manufactured by Mitsui Chemicals)
(5)ウレタン化触媒
ネオスタンU-600(トリス(2-エチルヘキサン酸)ビスマスの2-エチルヘキサン酸溶液、カルボン酸金属塩の含有量:55~58%、日東化成社製)
プキャットB7(樹脂酸ビスマスのミネラルスピリット溶液、金属ビスマスの含有量:7%、ミネラルスピリットの含有量:42%、日本化学産業社製)
ジラウリン酸ジブチルすず(IV)(和光純薬工業社製、ジブチル錫ジラウレート) (5) Urethane catalyst Neostan U-600 (2-ethylhexanoic acid solution of bismuth tris (2-ethylhexanoate), carboxylic acid metal salt content: 55-58%, manufactured by Nitto Kasei Co., Ltd.)
Pucat B7 (Mineral spirit solution of bismuth resinate, metal bismuth content: 7%, mineral spirit content: 42%, manufactured by Nippon Chemical Industry Co., Ltd.)
Dibutyltin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dilaurate)
ネオスタンU-600(トリス(2-エチルヘキサン酸)ビスマスの2-エチルヘキサン酸溶液、カルボン酸金属塩の含有量:55~58%、日東化成社製)
プキャットB7(樹脂酸ビスマスのミネラルスピリット溶液、金属ビスマスの含有量:7%、ミネラルスピリットの含有量:42%、日本化学産業社製)
ジラウリン酸ジブチルすず(IV)(和光純薬工業社製、ジブチル錫ジラウレート) (5) Urethane catalyst Neostan U-600 (2-ethylhexanoic acid solution of bismuth tris (2-ethylhexanoate), carboxylic acid metal salt content: 55-58%, manufactured by Nitto Kasei Co., Ltd.)
Pucat B7 (Mineral spirit solution of bismuth resinate, metal bismuth content: 7%, mineral spirit content: 42%, manufactured by Nippon Chemical Industry Co., Ltd.)
Dibutyltin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dilaurate)
(6)有機溶媒
炭化水素系溶媒:トルエン、キシレン、ノルマルヘキサン
非プロトン性極性溶媒:メチルエチルケトン、アセチルアセトン、シクロヘキサノン (6) Organic solvent Hydrocarbon solvent: toluene, xylene, normal hexane Aprotic polar solvent: methyl ethyl ketone, acetylacetone, cyclohexanone
炭化水素系溶媒:トルエン、キシレン、ノルマルヘキサン
非プロトン性極性溶媒:メチルエチルケトン、アセチルアセトン、シクロヘキサノン (6) Organic solvent Hydrocarbon solvent: toluene, xylene, normal hexane Aprotic polar solvent: methyl ethyl ketone, acetylacetone, cyclohexanone
2.剥離剤の調製
表1および2に示す部数で、ポリオレフィン、ポリオレフィンポリオール、イソシアネート、液状炭化水素およびウレタン化触媒を有機溶媒に溶解させて、固形分が1.5%である剥離剤を調製した。なお、表1および2に示すウレタン化触媒の部数は、入手したウレタン化触媒そのものの部数であり、入手したウレタン化触媒が溶液である場合、溶液全体の部数である。また、使用した各有機溶媒の重量比も、表1および2に示す。 2. Preparation of Release Agent A release agent having a solid content of 1.5% was prepared by dissolving polyolefin, polyolefin polyol, isocyanate, liquid hydrocarbon and urethanization catalyst in an organic solvent in the number of parts shown in Tables 1 and 2. In addition, the number of parts of the urethanization catalyst shown in Tables 1 and 2 is the number of parts of the obtained urethanization catalyst itself, and when the obtained urethanization catalyst is a solution, it is the number of parts of the whole solution. The weight ratio of each organic solvent used is also shown in Tables 1 and 2.
表1および2に示す部数で、ポリオレフィン、ポリオレフィンポリオール、イソシアネート、液状炭化水素およびウレタン化触媒を有機溶媒に溶解させて、固形分が1.5%である剥離剤を調製した。なお、表1および2に示すウレタン化触媒の部数は、入手したウレタン化触媒そのものの部数であり、入手したウレタン化触媒が溶液である場合、溶液全体の部数である。また、使用した各有機溶媒の重量比も、表1および2に示す。 2. Preparation of Release Agent A release agent having a solid content of 1.5% was prepared by dissolving polyolefin, polyolefin polyol, isocyanate, liquid hydrocarbon and urethanization catalyst in an organic solvent in the number of parts shown in Tables 1 and 2. In addition, the number of parts of the urethanization catalyst shown in Tables 1 and 2 is the number of parts of the obtained urethanization catalyst itself, and when the obtained urethanization catalyst is a solution, it is the number of parts of the whole solution. The weight ratio of each organic solvent used is also shown in Tables 1 and 2.
3.剥離剤層の形成(離型材の調製)
マイヤーバー#6を用いて、調製した剥離剤を厚さ38μmのポリエステルフィルムに塗布した後、熱風乾燥機で130℃×1分間加熱し、離型材を得た。得られた離型材の剥離剤層の厚さは約150nmであった。 3. Formation of release agent layer (preparation of release material)
The prepared release agent was applied to a 38 μm thick polyester film using a Mayer bar # 6, and then heated with a hot air dryer at 130 ° C. for 1 minute to obtain a release material. The thickness of the release agent layer of the obtained release material was about 150 nm.
マイヤーバー#6を用いて、調製した剥離剤を厚さ38μmのポリエステルフィルムに塗布した後、熱風乾燥機で130℃×1分間加熱し、離型材を得た。得られた離型材の剥離剤層の厚さは約150nmであった。 3. Formation of release agent layer (preparation of release material)
The prepared release agent was applied to a 38 μm thick polyester film using a Mayer bar # 6, and then heated with a hot air dryer at 130 ° C. for 1 minute to obtain a release material. The thickness of the release agent layer of the obtained release material was about 150 nm.
4.特性評価
使用した触媒の特性(即ち、非有機錫化合物であるか否か)、剥離剤の溶解状態、得られた剥離剤層の特性(即ち、外観、基材密着性および常態剥離力)を、表3および4に記載する。剥離剤の溶解状態および剥離剤層の特性の評価方法を以下に記載する。 4). Characteristic evaluation The characteristics of the catalyst used (that is, whether it is a non-organotin compound), the dissolution state of the release agent, and the characteristics of the resulting release agent layer (that is, appearance, substrate adhesion and normal release force) In Tables 3 and 4. The method for evaluating the dissolved state of the release agent and the properties of the release agent layer are described below.
使用した触媒の特性(即ち、非有機錫化合物であるか否か)、剥離剤の溶解状態、得られた剥離剤層の特性(即ち、外観、基材密着性および常態剥離力)を、表3および4に記載する。剥離剤の溶解状態および剥離剤層の特性の評価方法を以下に記載する。 4). Characteristic evaluation The characteristics of the catalyst used (that is, whether it is a non-organotin compound), the dissolution state of the release agent, and the characteristics of the resulting release agent layer (that is, appearance, substrate adhesion and normal release force) In Tables 3 and 4. The method for evaluating the dissolved state of the release agent and the properties of the release agent layer are described below.
(1)剥離剤の溶解状態
得られた剥離剤の溶解状態を、下記基準に従い、目視で判定した。
○:剥離剤が透明であり、剥離剤成分が有機溶媒に均一に溶解している。
×:剥離剤中に不溶物があり、剥離剤成分が有機溶媒に均一に溶解していない。 (1) Dissolving state of release agent The dissolution state of the obtained release agent was visually determined according to the following criteria.
○: The release agent is transparent, and the release agent component is uniformly dissolved in the organic solvent.
X: There are insolubles in the release agent, and the release agent component is not uniformly dissolved in the organic solvent.
得られた剥離剤の溶解状態を、下記基準に従い、目視で判定した。
○:剥離剤が透明であり、剥離剤成分が有機溶媒に均一に溶解している。
×:剥離剤中に不溶物があり、剥離剤成分が有機溶媒に均一に溶解していない。 (1) Dissolving state of release agent The dissolution state of the obtained release agent was visually determined according to the following criteria.
○: The release agent is transparent, and the release agent component is uniformly dissolved in the organic solvent.
X: There are insolubles in the release agent, and the release agent component is not uniformly dissolved in the organic solvent.
(2)剥離剤層の外観
形成した剥離剤層の外観を、下記基準に従い、目視で判定した。
○:ムラやハジキがなく、剥離剤層が均一。
×:すじ状、点状または不定形状のムラやハジキがあり、剥離剤層が不均一。 (2) Appearance of release agent layer The appearance of the formed release agent layer was visually determined according to the following criteria.
○: There is no unevenness or repellency, and the release agent layer is uniform.
X: There are stripes, dots, irregular shapes, repelling, and the release agent layer is uneven.
形成した剥離剤層の外観を、下記基準に従い、目視で判定した。
○:ムラやハジキがなく、剥離剤層が均一。
×:すじ状、点状または不定形状のムラやハジキがあり、剥離剤層が不均一。 (2) Appearance of release agent layer The appearance of the formed release agent layer was visually determined according to the following criteria.
○: There is no unevenness or repellency, and the release agent layer is uniform.
X: There are stripes, dots, irregular shapes, repelling, and the release agent layer is uneven.
(3)剥離剤層の基材密着性
剥離剤層表面を指で3往復こすった時の状態を、下記基準で判定した。
○:変化がないか、または表面が白っぽく曇った状態になるが、剥離剤層の脱落はない。
×:剥離剤層がボロボロと脱落して、消しゴムをこすった時に出るようなカスが発生し、基材が露出する。 (3) Base material adhesion of release agent layer The state when the release agent layer surface was rubbed 3 times with a finger was determined according to the following criteria.
◯: There is no change or the surface becomes whitish and cloudy, but the release agent layer does not fall off.
X: The release agent layer falls off and scraps are generated when the eraser is rubbed, and the substrate is exposed.
剥離剤層表面を指で3往復こすった時の状態を、下記基準で判定した。
○:変化がないか、または表面が白っぽく曇った状態になるが、剥離剤層の脱落はない。
×:剥離剤層がボロボロと脱落して、消しゴムをこすった時に出るようなカスが発生し、基材が露出する。 (3) Base material adhesion of release agent layer The state when the release agent layer surface was rubbed 3 times with a finger was determined according to the following criteria.
◯: There is no change or the surface becomes whitish and cloudy, but the release agent layer does not fall off.
X: The release agent layer falls off and scraps are generated when the eraser is rubbed, and the substrate is exposed.
(4)剥離剤層の常態剥離力
25mm幅のアクリル系粘着テープNo.31B(日東電工社製)を剥離剤層表面にハンドローラーを用いて貼り合わせ、23℃で24時間保存した後、引張試験機にて離型材を180°方向に3.0m/minの速さで引っ張り、23℃雰囲気下で常態剥離力を測定した。 (4) Normal peel strength of release agent layer Acrylic adhesive tape No. 25 mm wide 31B (manufactured by Nitto Denko Corporation) was bonded to the surface of the release agent layer using a hand roller and stored at 23 ° C. for 24 hours, and then the mold release material was 3.0 m / min in the 180 ° direction with a tensile tester. The normal peel strength was measured in an atmosphere at 23 ° C.
25mm幅のアクリル系粘着テープNo.31B(日東電工社製)を剥離剤層表面にハンドローラーを用いて貼り合わせ、23℃で24時間保存した後、引張試験機にて離型材を180°方向に3.0m/minの速さで引っ張り、23℃雰囲気下で常態剥離力を測定した。 (4) Normal peel strength of release agent layer Acrylic adhesive tape No. 25 mm wide 31B (manufactured by Nitto Denko Corporation) was bonded to the surface of the release agent layer using a hand roller and stored at 23 ° C. for 24 hours, and then the mold release material was 3.0 m / min in the 180 ° direction with a tensile tester. The normal peel strength was measured in an atmosphere at 23 ° C.
表3および4に示すように、非有機錫化合物であるカルボン酸金属塩を使用する実施例1~6では、ウレタン化触媒として有機錫化合物を用いる比較例5と同様に、優れた特性の剥離剤層が得られた。これに対して、カルボン酸金属塩を使用するが、炭化水素系溶媒(トルエン、キシレンまたはノルマルヘキサン)のみを使用する比較例1~4では、外観が悪い剥離剤層しか形成されなかった。さらに、ノルマルヘキサンのみを使用する比較例4の剥離剤では、イソシアネートが析出した。
As shown in Tables 3 and 4, in Examples 1 to 6 using a carboxylic acid metal salt which is a non-organotin compound, as in Comparative Example 5 using an organotin compound as a urethanization catalyst, excellent peeling properties were obtained. An agent layer was obtained. In contrast, in Comparative Examples 1 to 4 using a carboxylic acid metal salt but using only a hydrocarbon solvent (toluene, xylene or normal hexane), only a release agent layer having a poor appearance was formed. Furthermore, in the release agent of Comparative Example 4 using only normal hexane, isocyanate precipitated.
本発明の剥離剤は、環境に問題のある有機錫化合物を使用せずに、優れた特性の剥離剤層を形成することができる。この剥離剤層を有する離型材および粘着テープは、電子部品関連等の様々な用途に好適に使用することができる。
The release agent of the present invention can form a release agent layer having excellent characteristics without using an organic tin compound having a problem with the environment. The release material and the adhesive tape having the release agent layer can be suitably used for various applications such as those related to electronic components.
Claims (15)
- ポリオレフィン、イソシアネート、ポリオレフィンポリオール、カルボン酸金属塩および有機溶媒を含有する剥離剤であり、
カルボン酸金属塩が、非有機錫化合物であり、
有機溶媒が、炭化水素系溶媒および非プロトン性極性溶媒の混合溶媒である剥離剤。 A release agent containing polyolefin, isocyanate, polyolefin polyol, carboxylic acid metal salt and organic solvent,
The carboxylic acid metal salt is a non-organotin compound,
A release agent in which the organic solvent is a mixed solvent of a hydrocarbon solvent and an aprotic polar solvent. - 炭化水素系溶媒が、芳香族炭化水素系溶媒である請求項1に記載の剥離剤。 The release agent according to claim 1, wherein the hydrocarbon solvent is an aromatic hydrocarbon solvent.
- 芳香族炭化水素系溶媒が、トルエンおよびキシレンからなる群から選ばれる少なくとも一つである請求項2に記載の剥離剤。 The release agent according to claim 2, wherein the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene and xylene.
- 非プロトン性極性溶媒が、ケトン系溶媒である請求項1~3のいずれか一項に記載の剥離剤。 The release agent according to any one of claims 1 to 3, wherein the aprotic polar solvent is a ketone solvent.
- ケトン系溶媒が、メチルエチルケトン、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つである請求項4に記載の剥離剤。 The release agent according to claim 4, wherein the ketone solvent is at least one selected from the group consisting of methyl ethyl ketone, acetylacetone, and cyclohexanone.
- 炭化水素系溶媒が、キシレン、またはトルエンおよびキシレンであり、非プロトン性極性溶媒が、アセチルアセトンおよびシクロヘキサノンからなる群から選ばれる少なくとも一つであるである請求項1に記載の剥離剤。 The stripping agent according to claim 1, wherein the hydrocarbon solvent is xylene, or toluene and xylene, and the aprotic polar solvent is at least one selected from the group consisting of acetylacetone and cyclohexanone.
- 炭化水素系溶媒と非プロトン性極性溶媒との重量比が、99:1~90:10である請求項1~6のいずれか一項に記載の剥離剤。 The release agent according to any one of claims 1 to 6, wherein the weight ratio of the hydrocarbon solvent to the aprotic polar solvent is 99: 1 to 90:10.
- カルボン酸金属塩が、カルボン酸ビスマスである請求項1~7のいずれか一項に記載の剥離剤。 The stripping agent according to any one of claims 1 to 7, wherein the metal carboxylate is bismuth carboxylate.
- イソシアネートが、1分子中にイソシアネート基を3個以上有するポリイソシアネートである請求項1~8のいずれか一項に記載の剥離剤。 The release agent according to any one of claims 1 to 8, wherein the isocyanate is a polyisocyanate having 3 or more isocyanate groups in one molecule.
- ポリイソシアネートが、芳香族ポリイソシアネートおよび脂環式ポリイソシアネートからなる群から選ばれる少なくとも一つである請求項9に記載の剥離剤。 The release agent according to claim 9, wherein the polyisocyanate is at least one selected from the group consisting of an aromatic polyisocyanate and an alicyclic polyisocyanate.
- ポリイソシアネートが、芳香族ジイソシアネートの多価アルコール付加体および脂環式ジイソシアネートの多価アルコール付加体からなる群から選ばれる少なくとも一つである請求項10に記載の剥離剤。 The release agent according to claim 10, wherein the polyisocyanate is at least one selected from the group consisting of a polyhydric alcohol adduct of an aromatic diisocyanate and a polyhydric alcohol adduct of an alicyclic diisocyanate.
- ポリオレフィンポリオールの数平均分子量が、1500~50000である請求項1~11のいずれか一項に記載の剥離剤。 The release agent according to any one of claims 1 to 11, wherein the number average molecular weight of the polyolefin polyol is 1500 to 50000.
- 基材および剥離剤層を有する離型材であり、
請求項1~12のいずれか一項に記載の剥離剤から形成された剥離剤層を、基材の少なくとも片面に有する離型材。 A release material having a base material and a release agent layer,
A release material having a release agent layer formed from the release agent according to any one of claims 1 to 12 on at least one surface of a substrate. - 粘着剤層および請求項13に記載の離型材を有する粘着テープであり、
粘着剤層と離型材の剥離剤層とが接触している粘着テープ。 It is an adhesive tape having an adhesive layer and a release material according to claim 13,
An adhesive tape in which the adhesive layer and the release agent layer of the release material are in contact. - 基材、粘着剤層および剥離剤層を有する粘着テープであり、
請求項1~12のいずれか一項に記載の剥離剤から形成された剥離剤層を、基材の片面に有し、
剥離剤層が形成されていない基材の他方の面に、粘着剤層を有する粘着テープ。 A pressure-sensitive adhesive tape having a base material, a pressure-sensitive adhesive layer and a release agent layer;
Having a release agent layer formed from the release agent according to any one of claims 1 to 12 on one side of a substrate;
A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.
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JP6141701B2 (en) * | 2013-06-28 | 2017-06-07 | ライオン株式会社 | Stripping treatment agent and method for producing the same |
JP6287285B2 (en) * | 2014-02-05 | 2018-03-07 | 東洋インキScホールディングス株式会社 | Adhesive and adhesive sheet |
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