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WO2013038968A1 - Procédé de fabrication d'un film composite et film composite - Google Patents

Procédé de fabrication d'un film composite et film composite Download PDF

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Publication number
WO2013038968A1
WO2013038968A1 PCT/JP2012/072579 JP2012072579W WO2013038968A1 WO 2013038968 A1 WO2013038968 A1 WO 2013038968A1 JP 2012072579 W JP2012072579 W JP 2012072579W WO 2013038968 A1 WO2013038968 A1 WO 2013038968A1
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WIPO (PCT)
Prior art keywords
composite film
elongation
mixture
break
stretched
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PCT/JP2012/072579
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English (en)
Japanese (ja)
Inventor
栄一 井本
雄太 島▲崎▼
達也 北原
国夫 長崎
Original Assignee
日東電工株式会社
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Priority claimed from JP2011200799A external-priority patent/JP2013060546A/ja
Priority claimed from JP2011200802A external-priority patent/JP2013060547A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2013038968A1 publication Critical patent/WO2013038968A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a method for producing a composite film containing a urethane polymer and an acrylic polymer, and a composite film.
  • a composite film of an acrylic polymer and a urethane polymer is, for example, Japanese Patent Application Laid-Open No. 2003-96140, Japanese Patent Application Laid-Open No. 2003-171411, Japanese Patent Application Laid-Open No. 2004-10661, and Japanese Patent Application Laid-Open No. 2004-10661. It is disclosed in Japanese Patent Application Publication No. 2004-1062.
  • This composite film has tough physical properties such as high strength and high elongation as a film.
  • the mechanical properties of such a composite film can be controlled by adjusting the type and copolymer composition of the acrylic polymer, the composition of the urethane polymer, the ratio of the acrylic polymer to the urethane polymer, and the like.
  • measures such as using an acrylic polymer having a low glass transition temperature (Tg) or a high molecular weight urethane polymer can be employed.
  • the present invention has been made to solve the above-mentioned problems, and the present invention reduces the stress generated when the composite film is stretched by 20% without significantly changing the breaking strength when the composite film is stretched.
  • Another object of the present invention is to provide a method for producing a composite film capable of improving easily stretchability such as an increase in elongation when it is stretched and broken, and a composite film obtained by this production method.
  • the present invention is a method for producing a composite film containing a urethane polymer and an acrylic polymer, A reference mixture preparation step for preparing a reference mixture comprising the urethane polymer and at least one acrylic monomer; An additive mixture preparation step of adding 0.01 parts by weight or more and 5 parts by weight or less of a chain transfer agent to 100 parts by weight of the reference mixture; A composite film forming step of curing the additive mixture to form a composite film,
  • the elongation breaking strength S2 of the composite film P2 obtained by curing the additive mixture is a value of 85% to 115% of the elongation breaking strength S1 of the composite film P1 obtained by curing the reference mixture, and the composite film
  • the stress M2 when the P2 is stretched by 20% is 90% or less of the stress M1 when the composite film P1 is stretched by 20%, or when the composite film P2 is stretched and broken.
  • the elongation at break E2 is 120% or more of the elongation at break E1 when the composite film P1
  • the elongation rate of the composite film (ie, the elongation at break) E2 when the composite film is stretched and broken is added.
  • it is difficult to control both of them because of the positive correlation between the breaking strength at elongation and the stress at 20% elongation or the elongation at break, that is, when one is increased, the other is increased.
  • breaking strength at elongation when the stress at 20% elongation is lowered, the breaking strength at elongation is also lowered and the required breaking strength at elongation cannot be achieved, and conversely, when the elongation at break is increased, the breaking strength at elongation is also increased. It will become. It should be noted that the improvement in breaking strength at the time of expansion is not always required, and in some cases, excessive performance (so-called over spec) is obtained, or when easy breakability is required, it acts in the direction of inhibiting breakage. .
  • the urethane polymer preferably contains an acryloyl group-terminated urethane polymer.
  • the urethane polymer can be provided with copolymerizability with an acrylic monomer, the cohesive force of the whole polymer is improved, the elongation breaking strength is maintained, the stress at 20% elongation is reduced or the elongation at break is increased. It is possible to more easily achieve the increase.
  • the urethane polymer is preferably formed by a reaction between a polyol and an isocyanate in the presence of at least one acrylic monomer.
  • the range of types of monomers used as a raw material can be widened, and the additive mixture can be easily formed into a film.
  • the radiation-curable additive mixture is applied onto a substrate to form a coating film, and the coating film is irradiated with radiation to be cured to form a composite film. preferable.
  • the present invention includes a composite film obtained by the method for producing the composite film.
  • the elongation break strength of the composite film is maintained without changing the composition of each of the urethane polymer and the acrylic polymer, the composition ratio of the both, and the like, and the decrease in stress at 20% elongation and the elongation at break It is possible to easily produce a composite film having improved easy stretchability, such as an increase in.
  • the present invention relates to a method for producing a composite film containing a urethane polymer and an acrylic polymer, a reference mixture preparation step for preparing a reference mixture containing the urethane polymer and at least one acrylic monomer, and 100 wt% of the reference mixture.
  • the elongation breaking strength S2 of the composite film P2 obtained by curing the additive mixture is a value of 85% to 115% of the elongation breaking strength S1 of the composite film P1 obtained by curing the reference mixture, and the above
  • the stress M2 when the composite film P2 is stretched by 20% is that the composite film P1 is stretched by 20%.
  • Is a value of 90% or less of the stress M1 at the time of breaking, or the elongation at break E2 when the composite film P2 is stretched and broken is the breakage when the composite film P1 is stretched and broken It is a value of 120% or more of the time expansion rate E1.
  • an acrylic monomer alone or in a mixture of two or more, a polyol and a diisocyanate are reacted to form a urethane polymer, and a mixture containing the urethane polymer and the acrylic monomer is subjected to, for example, a peeling treatment. It is applied onto a polyethylene terephthalate film and cured by irradiation with radiation to produce a composite film.
  • a polyethylene terephthalate film subjected to the release treatment an appropriate base material can be used, or an adhesive layer is provided on the release substrate such as the polyethylene terephthalate film subjected to the release treatment.
  • a composite film may be formed thereon.
  • the adhesive layer produced separately may be laminated
  • Reference mixture preparation process In the reference mixture preparation step, a reference mixture including a urethane polymer and at least one acrylic monomer is prepared.
  • the urethane polymer is obtained by reacting a polyol and diisocyanate.
  • a catalyst may be used for the reaction between the hydroxyl group of the polyol and the isocyanate.
  • a catalyst generally used in urethane reaction such as dibutyltin dilaurate, tin octoate, 1,4-diazabicyclo (2,2,2) octane can be used.
  • Polyols are polyether polyols obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc., or dihydric alcohols (for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, etc.) and adipic acid.
  • polyester polyols composed of a polycondensation product with a divalent basic acid such as azelaic acid and cepatic acid, acrylic polyols, carbonate polyols, epoxy polyols and caprolactone polyols.
  • polyether polyols such as polyoxytetramethylene glycol (PTMG) and polyoxypropylene glycol (PPG), non-crystalline polyester polyols, non-crystalline polycarbonate polyols and the like are preferably used. These polyols can be used alone or in combination.
  • the number average molecular weight of the polyol component is not particularly limited, and may be set in consideration of the characteristics of the intended composite film. Among these, from the viewpoint of stably preparing the reference mixture, for example, 400 to 2000 is preferable, and 600 to 1000 is more preferable.
  • the measuring method of a number average molecular weight can be measured with the following method. A sample is dissolved in THF at 0.1 wt%, and the number average molecular weight is measured by polystyrene conversion using GPC (gel permeation chromatography). Detailed measurement conditions are as follows.
  • GPC device Tosoh HLC-8120GPC Column: manufactured by Tosoh Corporation, (GMHHR-H) + (GMHHR-H) + (G2000HHR) Flow rate: 0.8ml / min Concentration: 0.1 wt% Injection volume: 100 ⁇ l Column temperature: 40 ° C Eluent: THF
  • diisocyanate examples include aromatic, aliphatic, and alicyclic diisocyanates.
  • Aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate.
  • diisocyanates can be used alone or in combination. From the viewpoint of urethane reactivity, compatibility with acrylic, and the like, the type and combination of polyisocyanates can be appropriately selected.
  • the usage amount of the polyol component and the diisocyanate component for forming the urethane polymer is not particularly limited.
  • the usage amount of the polyol component is NCO / OH (equivalent ratio) with respect to the diisocyanate component. ) Is preferably 1.0 or more, and more preferably 2.0 or less.
  • NCO / OH is less than 1.0, the terminal functional group of the urethane molecular chain becomes a hydroxyl group, and the strength of the film tends to decrease.
  • NCO / OH is 2.0 or less, elongation and flexibility can be ensured.
  • a hydroxyl group-containing acrylic monomer may be added to the urethane polymer.
  • an acryloyl group can be introduced into the molecule (particularly the terminal) of the urethane polymer, and copolymerization with an acrylic monomer can be imparted.
  • the cohesive force of the whole polymer can be improved, and both the maintenance of the elongation break strength and the reduction of the stress at 20% elongation or the increase of the elongation at break can be more easily achieved.
  • hydroxyl group-containing acrylic monomer hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, or the like is used.
  • the amount of the hydroxyl group-containing acrylic monomer used is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the urethane polymer.
  • acrylic monomers contained in the reference mixture include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t -Butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, acrylic Carboxyl group-containing monomers such as acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and crotonic acid; (meth)
  • amide monomers such as N-substituted (meth) acrylamide such as (meth) acrylamide and N-methylolacrylamide, N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, Succinimide monomers such as N- (meth) acryloyl-8-oxyoctamethylenesuccinimide, vinyl monomers such as vinyl acetate, N-vinylpyrrolidone, N-vinylcarboxylic acid amides, N-vinylcaprolactam; acrylonitrile, methacrylonitrile Cyanoacrylate monomers such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate Acrylic ester monomers such as fluorine, (meth)
  • acrylic monomers are appropriately determined in terms of type, combination, amount of use and the like in consideration of compatibility with urethane, polymerizability upon photocuring such as radiation, and characteristics of the high molecular weight obtained.
  • the acrylic monomer includes not only a monomer having a structure derived from acrylic acid but also a monomer having a structure derived from methacrylic acid.
  • Polyfunctional monomers can be added within a range that does not impair the characteristics.
  • Polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, and polyester acrylate.
  • the content of the polyfunctional monomer is preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the acrylic monomer. If the content of the polyfunctional monomer is 1 part by weight or more, sufficient cohesive force can be obtained in the resulting composite film, and the tensile strength at break can be secured. If the content is 5 parts by weight or less, the elastic modulus is high. Without being too much, the stress at 20% elongation can be reduced or the elongation at break can be increased.
  • the reference mixture may be prepared by reacting a polyol and diisocyanate to separately form a urethane polymer, and mixing the urethane polymer and an acrylic monomer at a predetermined ratio. At least one acrylic monomer may be mixed.
  • the urethane polymer may be formed by a reaction between a polyol and an isocyanate. Since the range of types of monomers used as a raw material can be widened and the additive mixture can be easily formed into a film, the urethane polymer can be reacted with a polyol and an isocyanate in the presence of at least one acrylic monomer. Is preferably formed.
  • the diisocyanate and the like are added and reacted with the polyol to adjust the viscosity.
  • the acrylic monomer may be added all at once during the synthesis of the urethane polymer, or may be added in several divided portions.
  • the polyol may be reacted after the diisocyanate is dissolved in the acrylic monomer.
  • the molecular weight is not limited and a high molecular weight polyurethane can be produced, so that the molecular weight of the finally obtained urethane can be designed to an arbitrary size.
  • the urethane polymer can be formed by mixing the polyol and the diisocyanate and, if necessary, a catalyst and reacting at 60 to 90 ° C. for 2 to 24 hours. Furthermore, a predetermined amount of a hydroxyl group-containing acrylic monomer may be added and reacted at 60 to 90 ° C. for 1 to 12 hours in order to impart copolymerizability with an acrylic polymer. Thereby, a reference mixture can be prepared.
  • the acrylic monomer As a compounding ratio of the urethane polymer and the acrylic monomer, the acrylic monomer with respect to a total of 100 parts by weight of the components constituting the urethane polymer (polyol, diisocyanate, and other optional components (such as a hydroxyl group-containing acrylic monomer)). Is preferably added in an amount of 70 to 130 parts by weight, more preferably 80 to 120 parts by weight.
  • the standard mixture contains, as necessary, commonly used additives such as ultraviolet absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents and the like that do not impair the effects of the present invention. Can be added within. These additives are used in normal amounts depending on the type. These additives may be added in advance before the polymerization reaction between the polyol and the diisocyanate, or may be added after the formation of the urethane polymer and before the polymerization of the acrylic monomer.
  • additives such as ultraviolet absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents and the like that do not impair the effects of the present invention. Can be added within. These additives are used in normal amounts depending on the type. These additives may be added in advance before the polymerization reaction between the polyol and the diisocyanate, or may be added after the formation of the urethane polymer and before the polymerization of the acrylic monomer.
  • a small amount of solvent may be added to the reference mixture in order to adjust the viscosity when the additive mixture described below is applied.
  • the solvent can be appropriately selected from commonly used solvents, and examples thereof include ethyl acetate, toluene, chloroform, dimethylformamide and the like.
  • a solvent may be added at a reference
  • additive mixture preparation process In the additive mixture preparation step, 0.01 to 5 parts by weight of the chain transfer agent is added to 100 parts by weight of the reference mixture to prepare an additive mixture.
  • Chain transfer agent examples include linear or branched alkyl mercaptans such as n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan or t-dodecyl mercaptan, mercaptoacetic acid (thioglycolic acid), tri Sulfur compounds containing mercapto groups such as methylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate), halogenated hydrocarbons such as carbon tetrabromide, ethanol, isopropanol, ethyl acetate And the like. These chain transfer agents can be used alone or in combination.
  • the amount of the chain transfer agent used is 0.01 parts by weight or more and 5 parts by weight or less, and 0.01 parts by weight or more and 1 part by weight with respect to 100 parts by weight of a urethane polymer and an acrylic monomer alone or a mixture of two or more. Part or less. If the amount of chain transfer agent used is less than 0.01 parts by weight, the stress generated when the composite film is stretched by 20% is less likely to decrease, or the elongation when the composite film is stretched and broken is difficult to increase. Or On the other hand, when the amount of chain transfer agent used is 5 parts by weight or more, there is a problem that the gel fraction of the composite film is excessively lowered and the solvent resistance and the like are lowered as a film.
  • Photopolymerization initiator When imparting radiation curability to the additive mixture, a photopolymerization initiator may be added. When a photopolymerization initiator is added to impart radiation curability to the additive mixture, a composite film can be formed only by undergoing radiation curing of the coating film of the additive mixture, and productivity can be improved.
  • photopolymerization initiator examples include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one; substituted benzoin ethers such as anisole methyl ether; Substituted acetophenones such as diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenyl ketone; substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone; 2-naphthalenesulfonyl chloride, etc.
  • benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one
  • substituted benzoin ethers such as anisole methyl ether
  • Substituted acetophenones such as diethoxyacetophenone,
  • Aromatic sulfonyl chlorides such as 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime; 2,4,6-trimethylbenzoyl-diphenyl-thiol Scan fins oxide, bis (2,4,6-trimethylbenzoyl) - such as acylphosphine oxide, such as triphenylphosphine oxide.
  • the photopolymerization initiator is added in the additive mixture preparation step, but the photopolymerization initiator is not limited to this and may be added in the reference mixture preparation step.
  • the addition amount of the photopolymerization initiator is not particularly limited, but is selected from the range of 0.01 to 3 parts by weight (preferably 0.1 to 1 part by weight) with respect to 100 parts by weight of the reference mixture (excluding the solvent). can do.
  • An addition mixture can be prepared by adding a chain transfer agent and, if necessary, a photopolymerization initiator to the above reference mixture, and mixing at room temperature (about 25 ° C.) or under heating (eg, 40 to 70 ° C.). it can.
  • the additive mixture is cured to form a composite film.
  • the process of forming the composite film is not particularly limited, in the present embodiment, the additive mixture that has been made radiation curable is applied onto the substrate to form a coating film, and the coating film is irradiated with radiation to be cured. It is preferable to form a film.
  • polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyethylene (PE), and polypropylene (PP).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • Polyolefin resin such as high density polyethylene, biaxially oriented polypropylene, polyimide (PI), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polyvinylidene chloride resin, polyamide resin, polyurethane resin, polystyrene Thermosetting resins and the like are used in addition to thermoplastic resins such as resin, acrylic resin, fluorine resin, cellulose resin, and polycarbonate resin.
  • PET is preferably used because it has an appropriate hardness when used for processing precision parts, and is advantageous in terms of variety and cost.
  • the material of the film is preferably determined as appropriate depending on the application and the type of pressure-sensitive adhesive layer provided as necessary. For example, when a UV-curable pressure-sensitive adhesive is provided, a substrate having a high UV transmittance is used. preferable.
  • Formation of the coating film of the additive mixture can be performed by a conventionally known method, and examples thereof include roll coating, screen coating, and gravure coating. What is necessary is just to determine the thickness of a coating film in consideration of the thickness of the target composite film.
  • the additive mixture is applied onto a release-treated substrate to form a coating film, and ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron rays, electron beams, etc., depending on the type of photopolymerization initiator.
  • ionizing radiation radiation such as ultraviolet rays, visible light or the like
  • the coating film can be cured to form a composite film.
  • the release-treated sheet may be placed on the coating film formed on the substrate to block oxygen, or filled with an inert gas.
  • a release liner may be placed in the container to reduce the oxygen concentration.
  • the type of radiation and the like and the type of lamp used for irradiation can be selected as appropriate, such as low-pressure lamps such as fluorescent chemical lamps, black lights, and sterilization lamps, metal halide lamps, high-pressure mercury lamps, and the like.
  • low-pressure lamps such as fluorescent chemical lamps, black lights, and sterilization lamps
  • metal halide lamps such as metal halide lamps, high-pressure mercury lamps, and the like.
  • a high pressure lamp or the like can be used.
  • Irradiation amounts such as ultraviolet rays can be arbitrarily set according to required film characteristics.
  • the dose of ultraviolet rays 50 ⁇ 5000mJ / cm 2, preferably 100 ⁇ 4000mJ / cm 2, more preferably 100 ⁇ 3000mJ / cm 2.
  • the dose of ultraviolet ray is less than 50 mJ / cm 2, may not sufficient polymerization rate can be obtained, when it is more than 5000 mJ / cm 2, which may cause deterioration.
  • the temperature at the time of ultraviolet irradiation is not particularly limited and can be arbitrarily set. However, if the temperature is too high, a termination reaction due to the heat of polymerization is likely to occur, which tends to cause deterioration of characteristics. Is 70 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower.
  • the acrylic monomer is polymerized to become an acrylic polymer, and a composite film cured as a whole can be obtained.
  • a drying step may be provided after radiation curing.
  • the drying temperature may be set according to the type of solvent, and is, for example, about 80 to 160 ° C.
  • the urethane polymer has an acryloyl group at the terminal, crosslinking between the urethane polymer and the acrylic polymer occurs, and this can be used to control the mechanical properties or chemical properties of the composite film.
  • a photopolymerization initiator is added to the reference mixture without adding a chain transfer agent, and this mixture is irradiated with radiation in the same procedure as described above to cause a curing reaction. Just do it.
  • the elongation breaking strength S2 of the composite film P2 obtained by curing the additive mixture is a value of 85% to 115% of the elongation breaking strength S1 of the composite film P1 obtained by curing the reference mixture, preferably The value is 90% or more and 110% or less.
  • the stress M2 when the composite film P2 is stretched by 20% is 90% or less, preferably 80% or less of the stress M1 when the composite film P1 is stretched by 20%. .
  • the lower limit of the 20% elongation stress M2 is preferably as low as possible. However, if it is too low, the elongation breaking strength S2 may be less than 85% of the elongation breaking strength S1, and therefore it is preferably 10% or more. Alternatively, the elongation at break E2 when the composite film P2 is stretched and broken at the same time as satisfying the stretch breaking strength is equal to the elongation at break E1 when the composite film P1 is stretched and broken.
  • the value is 120% or more, preferably 140% or more.
  • the upper limit of the elongation at break E2 is preferably as high as possible, but is preferably 1000% or less from the balance between required characteristics and productivity.
  • the thickness of the composite film of the present embodiment can be appropriately selected according to the purpose and the like, but is generally about 5 to 500 ⁇ m, preferably about 50 to 200 ⁇ m.
  • the composite film of this embodiment can be used as it is, but it can also be used as an adhesive sheet by forming an adhesive layer on one or both sides. It does not specifically limit as an adhesive composition, A general thing, such as an acryl type and a rubber type, can be used.
  • the method of forming the pressure-sensitive adhesive is not particularly limited, and a method of directly applying a solvent-based or emulsion-based pressure-sensitive adhesive to a composite film and drying it, applying these pressure-sensitive adhesives to a release paper, and pre-adhesive layer And a method of sticking the pressure-sensitive adhesive layer to the composite film can be applied.
  • a method can also be applied in which a radiation curable pressure-sensitive adhesive is applied to a composite film, and both the pressure-sensitive adhesive layer and the film are irradiated with radiation to simultaneously cure and form the composite film and the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer and the composite film layer can be applied so as to have a multilayer structure.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be arbitrarily set. Usually, it is preferably 3 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, particularly about 10 to 30 ⁇ m. It is preferable that
  • the composite film in the present embodiment can be laminated with another film on one side or both sides.
  • materials for forming other films include polyester resins such as polyethylene terephthalate (PET), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), and polyetheretherketone (PEEK).
  • PET polyethylene terephthalate
  • PP polypropylene
  • PI polyimide
  • PEEK polyetheretherketone
  • thermoplastic resins such as polyvinyl chloride (PVC), polyvinylidene chloride resins, polyamide resins, polyurethane resins, polystyrene resins, acrylic resins, fluorine resins, cellulose resins, polycarbonate resins, etc., thermosetting Resin etc. are mentioned.
  • the other film may have a single layer structure, but may be a film having a multilayer structure composed of a plurality of layers made of the same or different materials.
  • the use of the composite film of the present embodiment is not particularly limited, and can be used as a film substrate or a protective film that can be applied to various uses such as home use, medical use, agricultural use, and industrial use.
  • the reference mixture A ′ was applied onto a 38 ⁇ m-thick polyethylene terephthalate (PET) subjected to a release treatment so that the thickness after curing was 100 ⁇ m to form a coating film.
  • the coated PET film was overlaid on the coating film, and then the coated PET film surface was irradiated with ultraviolet rays (illuminance 9 mW / cm 2 , light amount 1200 mJ / cm 2 ) using a black light and a metal halide lamp. And cured to form a urethane-acrylic composite film on the PET film.
  • Example 1 To 100 parts by weight of the reference mixture A, as a photopolymerization initiator, Irg. Addition mixture A was obtained by adding 0.15 part of 651 and 0.1 part of thioglycolic acid (hereinafter abbreviated as “TGA”) as a chain transfer agent. In the same manner as in the Reference Example, a coating film was formed with the additive mixture A and radiation curing was performed to form a urethane-acrylic composite film.
  • TGA thioglycolic acid
  • Example 2 To 100 parts by weight of the reference mixture A, as a photopolymerization initiator, Irg. Addition mixture B was obtained by adding 0.15 part of 651 and 0.5 part of TGA as a chain transfer agent. In the same manner as in the Reference Example, a coating film was formed with the additive mixture B and radiation curing was performed to form a urethane-acrylic composite film.
  • Example 3 To 100 parts by weight of the reference mixture A, as a photopolymerization initiator, Irg. Addition mixture C was obtained by adding 0.15 part of 651 as a chain transfer agent and 1.0 part of TGA. In the same manner as in the Reference Example, a coating film was formed with the additive mixture C and radiation curing was performed to form a urethane-acrylic composite film.
  • TMPTA trimethylolpropane triacrylate
  • the acryloyl group-terminated urethane polymer-acrylic system was the same as in the reference example.
  • a reference mixture ⁇ which is a monomer mixture, was obtained.
  • the reference mixture ⁇ Into 100 parts by weight of the reference mixture ⁇ , as a photopolymerization initiator, Irg.
  • the reference mixture ⁇ ' was obtained by adding 0.15 part of 651.
  • a coating film was formed with the reference mixture ⁇ 'and radiation curing was performed to form a urethane-acrylic composite film.
  • rate of change (each measured value of Examples and Comparative Examples / each measured value of Reference Example) ⁇ 100 (%)
  • the stress when the composite film breaks is obtained to obtain the elongation break strength, and the elongation rate when it is subsequently broken (the chuck at break relative to the initial distance between chucks) The ratio of the distance between them was defined as the elongation at break.
  • PTMG poly (oxytetramethylene) glycol having a number average molecular weight of 650
  • PPG720 poly (oxypropylene) glycol having a number average molecular weight of 700
  • HXDI hydrogenated xylylene diisocyanate
  • HEA hydroxyethyl acrylate
  • IBXA isobornyl acrylate
  • BA n-butyl Acrylate
  • AA Acrylic acid
  • TMPTA Trimethylolpropane triacrylate
  • Irg. 650 2,2-dimethoxy-1,2-diphenylethane-1-one
  • TGA thioglycolic acid
  • the tensile strength at break of the urethane-acrylic composite film to which the chain transfer agent TGA was added was 89.8 to 105.0% of the tensile strength at break of the reference example. It was almost the same value.
  • the stress at 20% elongation was 87.2 to 31.2% of the stress at 20% elongation of the reference example, which was lower than that of the reference example.
  • Comparative Example 1 in which the acrylic composition was changed the tensile strength at break showed the same value as 105.5% of the reference example, but the stress at 20% elongation was 142.0% higher than that of the reference example. showed that.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention a pour but de proposer un procédé de fabrication d'un film composite ayant une facilité d'étirage améliorée et ayant une petite quantité de changement dans la résistance à la rupture une fois étiré. Ce procédé de fabrication d'un film composite consiste en : une étape de préparation d'un mélange standard contenant le polymère d'uréthane et un ou plusieurs types de monomères acryliques ; une étape de préparation d'un mélange contenant un additif par addition d'un agent de transfert de chaîne dans la quantité de 0,01-5 partie en poids, bornes comprises, à 100 parties en poids du mélange standard ; et une étape de formation du film composite par durcissement de ce mélange contenant un additif. Ici, la résistance à la traction à la rupture (S2) d'un film composite (P2) obtenu par durcissement du mélange contenant un additif est de 85-115 %, bornes comprises, de la résistance à la traction à la rupture (S1) d'un film composite (P1) obtenu par durcissement du mélange standard, et la contrainte (M2) lorsque le film composite (P2) est étiré de 20 % est de 90 % ou moins de la contrainte (M1) lorsque le film composite (P1) est étiré de 20 %, ou le pourcentage d'étirage à la rupture (E2) lorsque le film composite (P2) est étiré et rompu est de 120 % ou plus du pourcentage d'étirage à la rupture (E1) lorsque le film composite (P1) est étiré et rompu.
PCT/JP2012/072579 2011-09-14 2012-09-05 Procédé de fabrication d'un film composite et film composite WO2013038968A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-200799 2011-09-14
JP2011200799A JP2013060546A (ja) 2011-09-14 2011-09-14 複合フィルムの製造方法及び複合フィルム
JP2011-200802 2011-09-14
JP2011200802A JP2013060547A (ja) 2011-09-14 2011-09-14 複合フィルムの製造方法及び複合フィルム

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010083137A (ja) * 2008-09-02 2010-04-15 Nitto Denko Corp 複合フィルム
JP2010254853A (ja) * 2009-04-27 2010-11-11 Bridgestone Corp エネルギー線硬化型エラストマー組成物
JP2011068727A (ja) * 2009-09-24 2011-04-07 Lintec Corp シートおよび粘着シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010083137A (ja) * 2008-09-02 2010-04-15 Nitto Denko Corp 複合フィルム
JP2010254853A (ja) * 2009-04-27 2010-11-11 Bridgestone Corp エネルギー線硬化型エラストマー組成物
JP2011068727A (ja) * 2009-09-24 2011-04-07 Lintec Corp シートおよび粘着シート

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