WO2008026751A1 - Composition pour films coulés et film formé à partir de cette composition - Google Patents

Composition pour films coulés et film formé à partir de cette composition Download PDF

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Publication number
WO2008026751A1
WO2008026751A1 PCT/JP2007/067093 JP2007067093W WO2008026751A1 WO 2008026751 A1 WO2008026751 A1 WO 2008026751A1 JP 2007067093 W JP2007067093 W JP 2007067093W WO 2008026751 A1 WO2008026751 A1 WO 2008026751A1
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Prior art keywords
film
cast
composition
mass
meth
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PCT/JP2007/067093
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English (en)
Japanese (ja)
Inventor
Toshiya Kobayashi
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Zeon Corporation
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Priority to JP2008532144A priority Critical patent/JPWO2008026751A1/ja
Publication of WO2008026751A1 publication Critical patent/WO2008026751A1/fr

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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a thread for a cast film and a film using the same, and more specifically, it is excellent in key marketability, printability, and shape followability, and in particular, has excellent resistance to I ⁇ .
  • Vehicles :: 3 ⁇ 4 Composition of cast molding film that gives a film made of non-vinyl chloride resin, which is affixed to the exterior of cars, containers, billboards, signs, traffic signs, etc.
  • the present invention relates to a film having a selfish property that is obtained by casting a product. Background sickle
  • Examples of the film replacing the vinyl chloride resin film include a polyolefin film, a polyurethane film, an attalinole resin resin, a polyester film, and a fluorine resin film.
  • a polyolefin film and the fluororesin film are inferior in printability, and the polyester film and the acrylic resin film have a problem that the three-dimensional shape of the vehicle body and the shape following the protrusions such as screws are lacking. Therefore, the polyurethane film has a problem of poor weather resistance.
  • the pot life of the raw material liquid during casting is high because of the high level of aminoplasts. Is short and storage stability is bad! Also, Due to the poor flexibility of the film, it is necessary to remove the polyurethane film. For polyurethane film alone, when it is applied to the vehicle body, etc., if the film surface is wiped and cleaned with a cloth impregnated with ij such as alcohol to remove dust and dirt on the film surface, There is a problem with the cat's U resistance.
  • This thread gives a film with favorable properties, such as mm, mark J ⁇ , excellent shape followability, good metamorphosis, etc. It was not possible.
  • Patent Document 2 Japanese Patent Laid-open No. 2 0 0 5-3 1 4 4 8 8 Disclosure of Invention
  • the present invention has a good pot life and can be swelled with good potency by the casting method, which is a production method suitable for a high-functional film, and has good printability and traceability.
  • the casting method which is a production method suitable for a high-functional film, and has good printability and traceability.
  • Threads for non-vinyl chloride resin film with excellent 1J property and film made by casting it shall be finished.
  • the present invention provides:
  • An allyl-uretan copolymer has a bulene group-containing urethane polymer and (meth) The cast film yarn U3 ⁇ 4 according to item (1), which is obtained by polymerizing an acrylic monomer with a mass ratio of 29:71 to 67:33.
  • the organotin compound is dibutyltin dilaurate, (6) for cast molded film, mechanical article,
  • the casting at 25 ° C has a viscosity of 80 0 to 10, 0 0 O mPa ⁇ s, and the cast molding according to item (1) to (16) Yarn for film SJ »
  • the yarn-discarded cast film of the present invention (hereinafter simply referred to as a yarn-disrupted product is S) is formed by polymerizing (A) a vinyl group-containing urethane polymer and a (meth) ataryl monomer. It contains a rouletane copolymer, (B) polyisocyanate compound and (C) an organic solvent.
  • the acrylB-urethane copolymer of the fulB (A) component is obtained by polymerizing a urethane polymer containing a bull group and a (meth) ataryl monomer.
  • Bure group-containing urethane polymers which are one component of the raw materials for anesthesia-acrylic urethane copolymers, are, for example, ubiquitous diisocyanate compounds, high-pure-weight polymers; one or more radicals and one or more radical polymerization products.
  • This vinyl group-containing urethane polymer has a radical canole polymerization ["Shinji 2 to 1 200 equivalents / ⁇ 0 OO kg force S preferred, 1 0 to 1 0 0 equivalent 4/1 0 0 0 0 kg It is more preferable S.
  • the content of the two compounds is too small, the copolymerization amount of the (meth) acrylic monomer is reduced, and the compatibility between the urethane polymer and the (meth) ataryl polymer is lowered, and cast molding is performed.
  • the stability of the spoiled film for film becomes poor and the overall size is poor, and if the content of ni ⁇ is too high, the ratio of precious bifunctional urethane polymer becomes high and contains vinyl group. It tends to be three-dimensional easily during the radial polymerization of urethane polymer and (meth) acrylonomer.
  • the weight average molecular weight is usually 10,000 to 20 ⁇ 3 ⁇ 4g.
  • * atoms and one or more radical polymerizations used in order to obtain a vinyl group-containing urethane polymer are the same as the hydroxyl group, mercapto.
  • Bull compounds having at least one group, imino group or amino group can be used.
  • 2-hydroxyethinoreatalylate, 2-hydroxypropyl acrylate, and 2-hydroxyethinoreacrylate are prolatatone adducts (for example, “FA-1, FA-2, FA-3 "etc.), glycerin mono (meth) acrylate, etc.
  • Active tens feK group-containing acrylic acid ester 2-hydrautic chinechinoremethacrylate 2-aminoethinoremethacrylate, trimethylo Mole valero, which is a power prolatatone adduct of norep oral bread monomethacrylate, 2-hydroxyethylenolemethacrylate (eg, Daisenolei Chemicals: ⁇ "Platasel FM-1, FM-2D", etc.) Rataton adduct, ethylene oxide adduct, propylene oxide adduct, etc.
  • 2-hydrautic chinechinoremethacrylate 2-aminoethinoremethacrylate
  • trimethylo Mole valero which is a power prolatatone adduct of norep oral bread monomethacrylate, 2-hydroxyethylenolemethacrylate (eg, Daisenolei Chemicals: ⁇ "Platasel FM-1, FM-2D", etc
  • Active I-fcK group-containing methacrylic acid ester Fatty female alcohols such as serine monoallyl ether, hydroxylated liquid polybutadiene (for example, those of Idemitsu Petrochemicals fc3 ⁇ 4); Fatty female amines such as allylamamine-aminated liquid polyptagene; Metataliloyloxychetyl isocyanate Radical polymerization I "monomers having a biounsaturated bond and a isocyanate group in the same molecule, adducts of glycerin or thioglycolone, arenoesters of mercaptocarboxylic acids such as thioglycolic acid, etc. can be used. In addition, these can be used as a mixture of 2 kg or more.
  • a compound having two or more active ten-feR elements and one or more radical polymerization H complexes in the same molecule. It can be introduced into the polyurethane chain as a polymer chain with a pendant shape as a Draft chain, and the defects inherent in Ureta Hf can be compensated with acrylic resin.
  • hexamethylene diisocyanate (HD I), lysine methyl ester diisocyanate, 2, 4, 4 —Trimethylhexamethylene disoocyanate, dimer acid diisocyanate and other fatty diisocyanates; isophorone disiocyanate (IPDI), 4,4'-methylenebis (dioxyhexylisocyanate) (H 1 2MD I) , ⁇ , ⁇ '-diisocyanate dimethyl cyclohexane hexane and other alicyclic diisocyanates;
  • HD I hexamethylene diisocyanate
  • IPDI isophorone disiocyanate
  • H 1 2MD I 4,4'-methylenebis (dioxyhexylisocyanate)
  • High molecular weight polymers used to obtain selfish Beer group-containing urethane polymers include polyester polyols, acryl polyols, polyether poly / polyether polyols, ester polyols, polycarbonate polyols, polyolefin polyols, You can use silicon poly ⁇ "NO! ⁇ ! /.
  • polyether 'ester polyol a polyester glycol obtained by ring-opening polymerization of cyclic etherol, a mixture of polyether dallicol and dicarponic acid, for example, poly (polytetramethylene ether) adipate, etc. are used. be able to.
  • Polycarbonate polyols include polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5,5) obtained by dealkalization or dealcoholization from low-preferred diol and alkylene carbonate or dialkyl strength carbonate. 1 pentylene) carbonate or the like can be used.
  • polyacrylic polymer examples include a copolymer of a (meth) atalinoleic acid ester such as methylmethacrylate apt / raretyrate and a 7-acid group-containing (meth) acrylate such as 2-hydroxyethyl methacrylate.
  • a copolymer of a (meth) atalinoleic acid ester such as methylmethacrylate apt / raretyrate and a 7-acid group-containing (meth) acrylate such as 2-hydroxyethyl methacrylate.
  • Hitachi: “Hitaroid 300 1”, Dai Nippon Ink “Lastrazole A-8 0 1”, etc. can be used.
  • these high molecular weight polymers can also be used as a mixture of two or more of the above.
  • the weight average molecular weight of the high molecular weight poly (vinyl) is usually from 200 to 10,000, preferably from 500 to 600. If the molecular weight is too small, the number of soft cars tends to be poor, and if it is too large, the leaky bow girl tends to decrease.
  • the ⁇ Stb ⁇ amount of ⁇ socyanate and high molecular weight polyol is usually 0.8 to 103 ⁇ 4 !, preferably 0.9 to 3 in terms of NCO / OH equivalent ratio. If this ratio is too small, the amount of hard segments tends to be small, and the target arch power S tends to be low. On the other hand, when it is too large, there is a tendency that the melting angle needle is poor and the viscosity is high.
  • the boat S3 ⁇ 4J is typically used with low molecular weight diol or low diamine content.
  • Monoamines include methylamine, ethylamine, pu, tyramine, dibutylamine and the like.
  • monoalcohol examples include methanol, ethanol, propanol, ptanol, and hexanol.
  • a depolymerizing agent can be used to prevent radical polymerization.
  • deuterium inhibitors include methylhydroquinone, tert-butylcateconole, chloranino! ⁇ Phenolic compounds; dipheninoreviclinolehydrazine, diphenylamine, and other amines; ferric chloride, cupric chloride, etc. ⁇ JS salt;
  • the production of the bur group-containing urethane polymer can be carried out by a one-shot method or prepolymerization in accordance with a known method.
  • Depleted state, non-vacuum state, or, as required, inert inertness commonly used in the industry for polyurethanes for example, toluene, key Carbon dioxide such as silene, hexane, etc.
  • Glycol ether esters such as ethylene glycol alcohol ether etherate, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate IJ
  • Ether cats such as tetrahydrofuran, dioxane IJ Dimethylformamide; dimethylacetamide; N-methylpyrrolidone; polar conversion U of furfura A; one or two or more _h), preferably at 100 ° C. or less, each in the above compounding condition range
  • the components can be mixed uniformly.
  • Examples of the (meth) acrylic monomer that is the other component of the acrylic mono-urethane copolymer (A) component include, for example, methyl acrylate, ethyl acrylate, n mono or isobutyl acrylate.
  • Atalenolic acid ester such as rate, hexyl acrylate, succinoxy hexyl acrylate, laurinole acrylate, stearinole acrylate; attalinoleic acid; methyl methacrylate, ethynole methacrylate, n- or isobutyl methacrylate, hexinomethacrylate
  • Methacrylic acid esters such as hexyl methacrylate, lauryl methacrylate and stearyl methacrylate; methacrylic acid; and the like can be used.
  • This (meth) acrylic monomer can also be used as a mixture of two or more.
  • bur group-containing compounds can be used in combination with the (meth) acryloyl t-nomer.
  • examples of other bur group-containing compounds include styrene, methyl styrene, butyl acetate, acrylonitrile, maleic acid, and the like.
  • the acrylouletane copolymer of component (A) is provided with an active IfeK base group that can be a isocyanate group such as a water imino group, an amino group, or a force carboxy group. Then, the weather resistance can be further improved.
  • 2-hydroxyethenoreacrylate, 2-hydroxyethinolemethacrylate, aminoethinoremethacrylate, 2-hydroxyethenoreacrylate force prolataton adduct,
  • 2-hydroxymethacrylate power prolactone adducts together with the above (meth) acrylic monomers 2-hydroxymethacrylate power prolactone adducts together with the above (meth) acrylic monomers.
  • the polymerization of the bur group-containing urethane polymer and the (meth) ataryl monomer is carried out by the usual midnight polymerization method, in an inert gas stream such as nitrogen, in the organic solvent IJ, and then heated by heating.
  • Tanaban 1J can use the same inert material used as necessary in the production of the aforementioned bier group-containing urethane polymer.
  • organic solvents can be re-introduced, and can be the same cat IJ as the inactive individual U that is used as needed, or a different translation IJ.
  • As the different organic amount IJ there can be used carbon dioxide such as benzene, toluene, xylene, hexane, etc., and these can be used as a mixture of two or more kinds.
  • an azo compound such as azobisisobutyronitrile; an oxide such as benzoyl peroxide, tert-butyl peroxide or cumene hydroperoxide; and the like can be used.
  • the amount of the polymerization initiator used here is a force that is selected so that the weight average molecular weight of the acryl-urethane copolymer is 20,000 to 50 y, preferably 30,000 to 200,000. It is 0.;! To 5 mass parts with respect to (meth) acrinomer (100 mass parts).
  • the polymerization temperature is usually about 10 to about 140 ° C, preferably about 30 to L20 ° C.
  • Examples of the embarrassing IJ include polyisocyanate compounds, amino resins, epoxy compounds, silanized ⁇ ), chelate compounds, etc.
  • polyisocyanate is used from the viewpoint of increasing the pot life of the liquid. ⁇ ! It is essential to use [component (B)].
  • this polysocyanate compound for example, P 1 phenylene disocyanate, naphthalene di socyanate, tolylene di socyanate, diphenyl methane disocyanate, hexamethylene disocyanate (HD I), Trimethylhexamethylene diisocyanate, isophorone disocyanate (IPDI), xylylene disocyanate, tetramethino lexylylene disocyanate, lysine disocyanate, etc., and their trimers, water adducts, or These low-molecular-weight polyadducts and the like can be used. Among them, isocyanate average raids of 2.5 to 4.0 are preferred.
  • the powerful polyisocyanate compound is an ethanolic compound that suppresses the isocyanate ®S properties at room temperature! It can also be used as a so-called block-type isocyanate that is pre-arranged with isocyanate such as isopropyl alcohol, acetylacetone, methyl acetyl ketyl, acetyl acetoacetate, epsilon prolactam.
  • This polyisocyanate can be used as a mixture of two or more.
  • the blending amount of the polyisocyanate compound of the component ( ⁇ ) is 8 to 15 parts by mass with respect to 100 parts by mass of the acryl-urethane copolymer of the component ( ⁇ ). It is specified by the range. If the blending amount of this ( ⁇ ) component is less than 8 parts by mass, the resulting film will have insufficient solvent resistance, while if it exceeds 15 parts by mass, other products such as the elongation at break of the resulting film will be reduced. (Ii) Component preference LV, distribution * is 9 to 12 parts by mass.
  • the normally used mouth square butterfly B may be excited in the yarn JJ ⁇ 3 ⁇ 4I for cast silk film of the present invention.
  • triethylenediamine, Min Trietinoleamine, Bis (2-dimethylamino) E) tertiary amines such as ethers; organic key compounds such as dibutino dilaurate; bases such as acetic acid ryumoctinoleic acid rium; Can be used for horns.
  • polyisocyanate ⁇ it is also possible to use a combination other than polyisocyanate ⁇ .
  • bisphenol A type epoxy epoxy compounds such as fat; silane compounds such as acetoxy silane, alkoxy silane, ketoxime silane, amino silane, and amino silane; fine compounds such as titanium (T i), zirconium (Z r), and aluminum (A 1) ⁇
  • Metal chelate compounds such as S-anoloxide, acetyl cetate, acylate, etc. can be used in combination.
  • the spun product for cast-molded film of the present invention can be blended with other resins as necessary to obtain a swollen film.
  • the other resin used has compatibility with the tHfB acryl-urethane copolymer, it can be a resin at the mouth.
  • other shelves that can be used include Atalinole Shelf, Polyesterol, Polyurethane, Polyetherol, Polyamide, Polycarbonate, Phenolic Resin, Alkyd Resin, and the like.
  • the blend ratio of these resins and acrylic monourethane copolymer is preferably in the range of 50Z50 to 0Z100 depending on the quality of other resin / acrylic urethane copolymer. If the ratio of the other resin is too large, the effect of the acrylic mono-urethane copolymer is lost.
  • the yarn for cast-molded film according to the present efforts may be blended with a supplementary reinforcing agent such as a loading reinforcing agent, sensitive U, a glaze agent, or a lift-off agent as necessary.
  • a supplementary reinforcing agent such as a loading reinforcing agent, sensitive U, a glaze agent, or a lift-off agent as necessary.
  • the filler and reinforcing agent include carbon black, aluminum hydroxide, calcium carbonate, titanium oxide, silica, glass, wood powder, wood flakes, and the like.
  • Examples of possible U include dibutyl phthalate and dioctyl phthalate.
  • agents include chloroanoloxy / rephosphate, dimethinorephosphonate, Ammopolyphosphate, elementalized ⁇ ! Etc.
  • Examples of sequestering agents are wax, sarcophagus, and silicon oizo! You can mention ⁇ .
  • the antifungal agent include pentachlorophenol, pentachlorophenol, bis (tree ⁇ -butino! ⁇ ) Oxide, and the like.
  • component (C) In the spoiled material for cast expansion film of the present invention, shelving IJ is blended as component (C), As this organic ij, it is possible to dissolve or disperse (A) component, ( ⁇ ) component and various kinds of exciter components used as necessary, and to impart good cast strength to the destruction. Anything can be used, and there are no particular restrictions. Examples of such organic cats ij include toluene, xylene, hexane and other charcoal cats iJ; g ether, buteno acetate wisteria u, methyl ether ketone, hexanone, etc.
  • Keto ⁇ agent diacetone alcohol, isopropanol, sec-butanol, tert-butanol ⁇ 3 ⁇ 4 alcohol; ethylene glycol ether ethyl acetate, propylene glycol methyl alcohol ether acetate, ethyl / ethyl 3-ethyloxy propionate, etc.
  • Glycol ether ester solvents Tetrahydrofuran, dioxane and other ether solvents; Dimethylformamide, Dimethinoreacetamide, N-methylpyrrolidone, Furfurano polar cat lj;
  • This organic translation IJ can be used in a mixture of two or more.
  • solid content preferably 5-8 0 weight 0 do more preferably 1 0-6 0% by weight, preferably in more 2 0 ⁇ 5 0 mass 0/0, viscosity, 2 5 ° preferably 8 0 0-1 0 at C, 0 0 OMP a ⁇ s, more preferably 1, 0 0 0 to 5, 0 0 0 mP a ⁇ s.
  • the composition for cast transfer film of the present invention is formed into a film by a casting method.
  • the liquid cast yarn film of the present invention containing the polyisocyanate compound, which is the above-mentioned crosslinking agent is used as a support that is made of polyester and has a detachability. After coating, it is usually formed into a film by heating the mixture at a temperature of 50 to 200 ° C. @S.
  • the application is not particularly limited.
  • a gravure coater a comma coater, a reno-coa coater, a knife coater, a sprayer.
  • a device such as a gun Apply to the paper.
  • the structure of the film of the present invention can be used by laminating with other films such as an acrylic resin film and a polyurethane film, which can be produced by a single layer made of only the spoiled material of the present invention.
  • the removal can be performed in the same manner as the above application.
  • the thickness of the film of the present invention (the total thickness for a laminated film) is not particularly limited, but it is 20 0 to 2500 ⁇ m. Thickness force S When the age is too small, the stiffness (hardness) strength S of the sheet decreases and the personality decreases, and the thickness is too large. 3 ⁇ 4 ⁇ tends to deteriorate the followability to the three-dimensional surface.
  • the cast molded film composition of the present invention has the following effects.
  • the film made up of this discerning object has excellent features of both the metamorphic properties of atalyl polymer and the flexibility of urethane polymer. Excellent printability and agitation.
  • the film formed by swelling the spoiled material by a casting method has a cross-insoluble cross-linking structure and has excellent ⁇ IJ resistance. Excellent durability.
  • the vinyl group-containing urethane polymer obtained in tfjfB (l) was used in 200. 5 parts by mass, 110 parts by mass of methinore methacrylate, 20 parts by mass of petitenoacrylate, and 2-hydroxide. After adding 2 parts by mass of shetyl methacrylate and 140 parts by mass of methyl ethyl ketone, and adding 1 part by mass of nitrile azobisisobuti, followed by 3 hours at 80 ° C, further adding azobisisobutyronitrile. 0.3 parts by mass was added, and KJ was performed at 80 ° C. for 2 hours to obtain acryl-uretan copolymerization night.
  • the copolymerization ⁇ parent night solid Yuritsu is 49 mass 0/0, the viscosity was 700 OmP a ⁇ s / 25 ° C.
  • the mass ratio of the bullet group-containing urethane polymer to the (meth) acrylic monomer was 100: 131. The results are shown in Table 1.
  • Measurement was performed at 25 ° C using a B-type wheel occupancy meter mi.
  • the ftjf film was measured for 100% modulus, fracture daughter, elongation at break, Ikki IJ property, and rivet shape tracking. These results are shown in Table 2.
  • Example 2 In the same manner as in Example 1 except that the amount of the polyisocyanate compound was changed as shown in Table 2 in the same manner as in Example 1, to prepare a yarn for cast wisteria film, In addition, he played Huinolem. The results are shown in Table 2.
  • the cast film composition of the present invention is excellent in m, printability, and shape tracking, and in particular excellent in sickle I, and is suitable for vehicles, motorcycles, containers, billboards, signs, traffic signs, etc.
  • a film made of non-vinyl chloride resin that is affixed to the outer surface can be cast.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition pour films coulés, ladite composition comprenant 100 parties par masse de (A) un copolymère acrylique/uréthane obtenu en polymérisant un polymère d'uréthane vinylé avec un monomère (méth)acrylique, 8 à 15 parties en masse de (B) un composé de polyisocyanate et (C) un solvant organique ; ainsi qu'un film obtenu en moulant la composition pour films coulés par coulage. La composition présente une vie en pot modérée et peut être moulée avec une maniabilité satisfaisante par coulage, qui constitue un procédé de fabrication approprié pour les films hautement fonctionnels. À partir de cette composition, il est possible d'obtenir un film de chlorure de vinyle sans résine, présentant d'excellentes propriétés d'apparence, notamment une excellente capacité d'impression et une excellente adaptabilité de forme, ainsi qu'une excellente résistance aux intempéries et une excellente résistance aux solvants.
PCT/JP2007/067093 2006-08-28 2007-08-27 Composition pour films coulés et film formé à partir de cette composition WO2008026751A1 (fr)

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JP2008532144A JPWO2008026751A1 (ja) 2006-08-28 2007-08-27 キャスト成形フィルム用組成物及びそれを用いてなるフィルム

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JP2006-230929 2006-08-28
JP2006230929 2006-08-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011062187A1 (fr) * 2009-11-18 2011-05-26 日東電工株式会社 Film stratifié
JP2015000945A (ja) * 2013-06-15 2015-01-05 日東電工株式会社 粘着剤組成物、粘着剤層および粘着シート
US11180682B2 (en) 2018-10-05 2021-11-23 Voxel Evolution, Llc Method and system to provide a repositionable translucent cast vinyl film with an air-egress adhesive layer
JP7419968B2 (ja) 2020-05-26 2024-01-23 東ソー株式会社 ウレタンプレポリマー組成物溶液

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04100831A (ja) * 1990-08-21 1992-04-02 Japan Atom Energy Res Inst 形状記憶膜の製造方法
JPH09239753A (ja) * 1996-03-08 1997-09-16 Sekisui Chem Co Ltd 光学用透明フィルムの製造方法
JP2004203933A (ja) * 2002-12-24 2004-07-22 Seikoh Chem Co Ltd キャスティング皮膜
JP2004323707A (ja) * 2003-04-25 2004-11-18 Toyo Ink Mfg Co Ltd 成型加工用シート、成型加工用粘着シート、およびそれらを用いて製造される着色成型体
JP2005314488A (ja) * 2004-04-27 2005-11-10 Zeon Kasei Co Ltd キャスト成形フィルム用組成物およびこれを成形してなるフィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04100831A (ja) * 1990-08-21 1992-04-02 Japan Atom Energy Res Inst 形状記憶膜の製造方法
JPH09239753A (ja) * 1996-03-08 1997-09-16 Sekisui Chem Co Ltd 光学用透明フィルムの製造方法
JP2004203933A (ja) * 2002-12-24 2004-07-22 Seikoh Chem Co Ltd キャスティング皮膜
JP2004323707A (ja) * 2003-04-25 2004-11-18 Toyo Ink Mfg Co Ltd 成型加工用シート、成型加工用粘着シート、およびそれらを用いて製造される着色成型体
JP2005314488A (ja) * 2004-04-27 2005-11-10 Zeon Kasei Co Ltd キャスト成形フィルム用組成物およびこれを成形してなるフィルム

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011062187A1 (fr) * 2009-11-18 2011-05-26 日東電工株式会社 Film stratifié
JP2011127103A (ja) * 2009-11-18 2011-06-30 Nitto Denko Corp 複合フィルム
CN102666679A (zh) * 2009-11-18 2012-09-12 日东电工株式会社 复合薄膜
JP2015000945A (ja) * 2013-06-15 2015-01-05 日東電工株式会社 粘着剤組成物、粘着剤層および粘着シート
US11180682B2 (en) 2018-10-05 2021-11-23 Voxel Evolution, Llc Method and system to provide a repositionable translucent cast vinyl film with an air-egress adhesive layer
JP7419968B2 (ja) 2020-05-26 2024-01-23 東ソー株式会社 ウレタンプレポリマー組成物溶液

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