WO2019156383A1 - Film acrylique - Google Patents

Film acrylique Download PDF

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Publication number
WO2019156383A1
WO2019156383A1 PCT/KR2019/000690 KR2019000690W WO2019156383A1 WO 2019156383 A1 WO2019156383 A1 WO 2019156383A1 KR 2019000690 W KR2019000690 W KR 2019000690W WO 2019156383 A1 WO2019156383 A1 WO 2019156383A1
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WIPO (PCT)
Prior art keywords
formula
additive
film
acrylic
group
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PCT/KR2019/000690
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English (en)
Korean (ko)
Inventor
강경륜
강지혜
김경수
은종혁
Original Assignee
효성화학 주식회사
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Publication of WO2019156383A1 publication Critical patent/WO2019156383A1/fr

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Classifications

    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention relates to an acrylic film produced by controlling the amount of the residual solvent by adding a specific additive.
  • liquid crystal display devices for a car navigation system may have a very high temperature and humidity in a vehicle in which it is placed, and the required temperature and humidity conditions are severe when compared to a normal television or personal computer monitor.
  • a polarizing plate is used for a liquid crystal display device in order to enable the display, in the liquid crystal display device which requires such severe temperature and / or humidity conditions, it is calculated
  • the polarizing plate usually has a structure in which a transparent protective film is laminated on both surfaces or one side of a polarizing film made of a polyvinyl alcohol-based resin in which a dichroic dye is adsorbed and oriented. And conventionally, triacetyl cellulose (TAC) is widely used for this protective film, This protective film is adhere
  • TAC triacetyl cellulose
  • stacked has high water vapor transmission rate of triacetyl cellulose, when it uses for a long time in a high humidity heat environment, polarization performance may fall, or a protective film and a polarizing film may peel off. have.
  • Conventional acrylic protective film has been manufactured by the melt casting (Melt Casting) method, but has many advantages in terms of environment-friendly aspects such as thin film, mass production, resin recycling when manufacturing by the solvent casting (Solvent Casting) method.
  • the solvent casting method is to produce a film by extruding the main liquid prepared by dissolving an acrylic resin in a solvent with a T-Die and then drying the solvent on a belt. The above process is possible only if the strength is increased and sufficient slip property is required for film transfer. In addition, the added particles should not be dissolved or deformed in the solvent. In particular, it is important to control the amount of residual solvent since the amount of solvent remaining in the film acts as an important factor in terms of slip properties.
  • Korean Patent No. 1250057 discloses a self-adhesive polarizing plate in which light leakage of an image display device does not occur easily even when the use environment is changed.
  • the acrylic polymer constituting the pressure-sensitive adhesive layer has a predetermined amount of aromatic ring structure (meth)
  • the adhesive layer contains a transparent protective film when the acrylate monomer unit is contained and its content is determined according to the value of the photoelastic coefficient X of the transparent protective film, and the phase difference value of the transparent protective film changes due to environmental changes such as heating. It is proposed to adjust to generate a phase difference change of the opposite sign.
  • Korean Patent No. 1114354 discloses a protective film for an optical member having a pressure-sensitive adhesive layer containing a cured product of a photopolymerizable acrylic polymer, an antistatic agent and a polymerizing polymer composition, wherein a crosslinking reaction is carried out by radicals generated from an initiator by light irradiation.
  • An appropriate amount of an antistatic agent is further blended into the composition comprising a photopolymerizable acrylic polymer and a polymerization initiator into which a photoactive group that can be introduced is introduced at a predetermined ratio, thereby eliminating the aging step during curing, thereby simplifying the manufacturing process.
  • a protective film excellent in antistatic property at the time of peeling or use is disclosed.
  • Korean Patent Publication No. 2015-0061591 discloses a first layer (low moisture vapor barrier) formed by using a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond group, and a composition containing a urethane acrylate thereon.
  • the technique of obtaining the polarizing plate protective film which is excellent in interlayer adhesiveness and the nonuniformity tolerance by wind is proposed by using the specific amount of the fluoro aliphatic group containing copolymer which has a 2nd layer which becomes a 1st layer, and has a specific structure in a 1st layer.
  • Japanese Patent Application Laid-Open No. 2014-240905 discloses a protective film A having a film thickness and elastic modulus within a specific range and containing acrylic resin as a main component in order to manufacture a polarizing plate having excellent adhesion, rework, flatness and visibility with polarizers.
  • the retardation film B which has a polarizer, a cellulose derivative which has an ether bond and a substituent at least on a glucose frame
  • the present invention has been made in order to solve the above problems, the amount of residual solvent can be easily controlled by adding a compound having a specific structure to the acrylic resin when manufacturing the acrylic film by solvent casting, film forming process In the process of peeling in the middle to prevent the degradation caused by the amount of residual solvent to provide an acrylic film having excellent quality.
  • Acrylic film according to embodiments of the present invention the acrylic resin consisting of 70 to 96 parts by weight of methyl methacrylate (Methyl Methacrylate) units and 4 to 30 parts by weight of alkyl (meth) acrylate units excluding methyl methacrylate; And one type of additive selected from the group consisting of an aromatic ester-based additive, a phenol-based additive, and an acrylic-based additive, prepared through a solvent casting method, and The amount of the additive is 1 to 10% by weight based on 100% by weight of the main dope liquid containing the acrylic resin, the additive, and the solvent.
  • the aromatic ester additive may have a structure of Formula 1, Formula 2, Formula 3, or Formula 4.
  • X 1 , X 2 is a hydrocarbon group having 1 to 20 carbon atoms including an ester group, ether group, or carbonyl group, n is 1 or more, m, n, And l are each at least 1, m and n are each at least 1 in Formula 3, and m is at least 1 in Formula 4).
  • the phenolic additive may be one having a structure of Formula 5 below.
  • R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 12 carbon atoms, and X is 4 to 20 carbon atoms including an ester group, an ether group, or a carbonyl group). Is a hydrocarbon group, and n is 0 to 5.
  • the acrylic additive may have a structure of Formula 6 below.
  • R 1 , R 2 is a hydrogen atom or a hydrocarbon group of 1 or more carbon atoms
  • X is an ester group, an ether group, or a carbonyl group or a hydrocarbon group including the functional group
  • n is 1 or more.
  • the glass transition temperature (Tg) of the acrylic film is 94 °C or more, the residual solvent amount may be 150 to 2400ppm.
  • the acrylic film of the present invention is manufactured in a state in which the amount of the residual solvent is easily controlled, it is possible to prevent deterioration of the film quality that may occur due to excessively small or large amount of the residual solvent during peeling during the film forming process. It is possible to provide an acrylic film having.
  • Acrylic film according to embodiments of the present invention is an acrylic resin and an aromatic ester additive, phenol consisting of 70 to 96 parts by weight of methyl methacrylate units and 4 to 30 parts by weight of alkyl (meth) acrylate units excluding methyl methacrylate. It includes one type of additive selected from the group consisting of an additive and an acrylic additive, and is prepared through a solvent casting method, the amount of the additive when prepared by the method is the main containing the acrylic resin, the additive, and a solvent It is characterized in that 1 to 10% by weight based on 100% by weight of the dope liquid.
  • the acrylic resin of this invention is demonstrated.
  • the acrylic resin of the present invention is a copolymer resin including methyl methacrylate units and alkyl (meth) acrylate units except for methyl methacrylate, and each of the monomer units is included in a repeating unit form.
  • methyl methacrylate units and 4 to 30 alkyl (meth) acrylate units except methyl methacrylate based on 100 parts by weight of acrylic resin It is preferable to consist of a weight part.
  • the content of the alkyl (meth) acrylate unit except for the methyl methacrylate may be more preferably 5 to 20 parts by weight.
  • the content of the methyl methacrylate unit is in the above range, excellent retardation characteristics and optical characteristics can be obtained.
  • the methyl methacrylate unit content is less than 70 parts by weight, the optical performance of the acrylic film may be deteriorated, and when it exceeds 96 parts by weight, the thickness uniformity of the acrylic film may be reduced.
  • the content of alkyl (meth) acrylate units other than methyl methacrylate can also obtain excellent retardation characteristics and optical properties in the above range. If the content of the alkyl (meth) acrylate units other than methyl methacrylate is less than 4 parts by weight, the optical performance of the protective film is deteriorated, and if it exceeds 30 parts by weight, the processability of the film may be deteriorated.
  • the alkyl (meth) acrylate is one or two selected from the group consisting of methyl acrylate, butyl acrylate, butyl methacrylate, and methacrylic acid. It may contain more than one copolymerization monomer.
  • the acrylic film of the present invention includes the acrylic resin and at least one additive selected from the group consisting of aromatic ester additives, phenolic additives and acrylic additives.
  • the quantity of a residual solvent can be easily controlled and the quality deterioration of the film by a residual solvent can be prevented.
  • the degradation of the film quality due to the residual solvent may occur when the main dope solution in which the acrylic resin is dissolved in the solvent is applied to the metal support in the solvent casting process to form a film in a semi-dry state and then peeled from the support. Due to this, after the manufacturing is completed, the physical properties as the optical and protective films are not sufficient. That is, the amount of residual solvent can have a significant impact on the quality of the acrylic film, so control thereof is essential.
  • the amount of the residual solvent when the amount of the residual solvent is too small, it is difficult to peel off the film from the support, which may cause damage to the film.
  • the amount of the residual solvent when the amount of the residual solvent is too large, the film is too soft and the self-supportability is insufficient, resulting in a peeling tension. This can cause problems with the film stretching.
  • the amount of the residual solvent in the stretching and / or drying step light tablet during the film forming process may cause excessive shrinkage in the film may adversely affect the physical properties of the film.
  • the amount of the organic solvent remaining in the film after manufacture may be a problem in terms of the hazard of the product.
  • the solvent mainly used in the solvent casting method is a highly volatile organic solvent, and it is not easy to control the amount of the residual solvent in the film.
  • the amount of the residual solvent can be easily controlled by adding the additive. have.
  • the content of the additive may be 1 to 10% by weight, preferably 3 to 10% by weight, more preferably 5 to 10% by weight.
  • the spacing between the molecular chains of the acrylic resin can be widened to promote diffusion of the residual solvent in the resin.
  • the solidification of the film is delayed as the solvent existing therein diffuses toward the surface of the film. Accordingly, the drying of the residual solvent can proceed more efficiently during the film forming process, thus making the amount of the residual solvent easier. Can be controlled.
  • the aromatic ester additive may have a structure of Formula 1, Formula 2, Formula 3, or Formula 4, but is not limited thereto.
  • X 1 , X 2 is a hydrocarbon group having 1 to 20 carbon atoms including an ester group, an ether group, or a carbonyl group
  • n is 1 or more
  • m, n, and l in Formula 2 are each 1 or more.
  • M and n are each at least 1, and m is at least 1 in Formula 4).
  • the phenolic additive may have a structure of Formula 5 below.
  • R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 12 carbon atoms, and X is 4 to 20 carbon atoms including an ester group, an ether group, or a carbonyl group). Is a hydrocarbon group, and n is 0 to 5.
  • phenolic additive may include, but are not limited to, those having the structures of Formulas 5-1 to 5-3.
  • R 1 is a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 12 carbon atoms
  • R 1 is a hydrogen atom, a halogen atom, a hydroxyl group, or 1 to 12 carbon atoms
  • Hydrocarbon group, iC 8 H 17 means isooctyl
  • the acrylic additive may have a structure of Formula 6 below.
  • R 1 , R 2 is a hydrogen atom or a hydrocarbon group of 1 or more carbon atoms
  • X is an ester group, an ether group, or a carbonyl group or a hydrocarbon group including the functional group
  • n is 1 or more.
  • acrylic additive may have a structure of Chemical Formula 6-1, but are not limited thereto, and other acrylic compounds may also be used.
  • the acrylic resin used in the present invention preferably has a molecular weight of 300,000 to 2,500,000 g / mol. In this case, when the molecular weight is less than 300,000g / mol, the production efficiency of the film is lowered, and when it exceeds 2,500,000g / mol, the molding may not be easy.
  • Glass transition temperature (Tg) of the acrylic film according to embodiments of the present invention is preferably 94 °C or more. If the glass transition temperature is less than 94 ° C., sagging occurs in the heated film during the film forming process, and thus the handleability of the film is deteriorated, which is not preferable.
  • the residual solvent amount of the acrylic film of the present invention may be 150 to 2400ppm, preferably 150 to 850ppm, more preferably 150 to 600ppm.
  • the residual solvent amount means the residual solvent amount of the film finally produced. Since the acrylic film of the present invention is peeled in the most suitable range for peeling in order to transfer the film in a semi-dry state from the support during the film forming process, it is possible to prevent the deterioration of the film quality which may occur due to the excessively small or large amount of residual solvent. . In addition, since the acrylic film finally produced is peeled off in a state containing a residual solvent amount of 150 to 2400 ppm, the amount of residual solvent may be excessively small or large, thereby preventing the deterioration of the film. In addition, the acrylic film of the present invention includes a low residual solvent amount as described above may not cause harmful problems when using the film.
  • the acrylic film of this invention is 10-60 micrometers in film thickness. If the thickness of the protective film is less than 10 ⁇ m does not express sufficient retardation characteristics as an optical film, when the thickness of the protective film exceeds 60 ⁇ m is not suitable for use in a thin polarizing plate.
  • the copolymer resin (acrylic resin) solution of the alkyl (meth) acrylate monomer except the methyl methacrylate monomer and methyl methacrylate is manufactured first.
  • the alkyl (meth) acrylate is one or two selected from the group consisting of methyl acrylate, butyl acrylate, butyl methacrylate, and methacrylic acid. It may contain more than one copolymerization monomer.
  • copolymer production method of these monomers there is no particular limitation on the copolymer production method of these monomers, and it can be prepared according to a copolymer resin production method well known in the art such as suspension polymerization, emulsion polymerization, bulk polymerization or solution polymerization.
  • a film is manufactured by the solvent casting method (solution film formation method).
  • the solvent casting method is a method of casting a main dope liquid obtained by dissolving an acrylic resin in a solvent (casting solvent) on a support, and evaporating the solvent to form a film.
  • the main dope liquid is prepared by mixing the acrylic resin and the additive prepared above in a solvent.
  • the solvent for producing the main dope liquid is preferably an organic solvent.
  • organic solvent halogenated hydrocarbons are preferably used, and halogenated hydrocarbons include chlorinated hydrocarbons, methylene chloride and chloroform, and methylene chloride is most preferably used.
  • Organic solvents other than halogenated hydrocarbons include esters, ketones, ethers, alcohols and hydrocarbons.
  • ester methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acylate, ethyl acylate, pentyl acylate, etc.
  • ketone acetone, methyl ethyl ketone, diethyl ketone, di Isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.
  • ether is diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4- dioxane, 1, 3- dioxane Solan, tetrahydrofuran, anisole, phentol, etc.
  • alcohol methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2 -Pentanol, 2-methyl-2-butanol, cyclohexanol, 2-fluoroethanol, 2,2,2, -trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol
  • alcohol methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2 -Pentanol, 2-methyl-2-butanol, cyclohexanol, 2-fluor
  • methylene chloride may be used as the main solvent and alcohol may be used as the subsolvent.
  • the mixed solvent of methylene chloride and alcohol is preferably mixed in a weight ratio within the range of 80:20 to 95: 5.
  • one type of additive selected from the group consisting of an aromatic ester additive, a phenol additive and an acrylic additive is used as an additive, and the content of the additive is 1 to 10% by weight.
  • auxiliary additives may be further used in addition to the additive.
  • the main dope liquid may contain various auxiliary additives depending on the use in each manufacturing process, for example, ultraviolet rays inhibitors, core shell rubber (CSR) particles or fine particles such as silica particles, infrared absorbers, release agents, and the like. Co-additives may be added.
  • CSR particles are made of one or two or more selected from the group consisting of styrene butadiene rubber, polybutadiene (PBD), and acrylic esters, and methyl methacryl (MMA).
  • Styrene Styrene
  • acrylic esters Acrylic Ester
  • Styrene Styrene
  • acrylic Ester is selected from the group consisting of one or two or more graft copolymers having a core-shell structure, but is not limited thereto.
  • specific kind of these additives may be used without limitation as long as it is conventionally used in the art, the content is preferably used in a range that does not lower the physical properties of the film.
  • the timing of adding the additive and the auxiliary additive is determined according to the type of each additive.
  • the process of adding an additive at the end of main dope liquid preparation can also be performed.
  • the main dope liquid obtained as mentioned above can be manufactured by normal temperature, high temperature, or low temperature dissolution method.
  • the main dope is cast on the metal support from the nozzle of the pressurized die for a predetermined time to form a film in a semi-dry state. Thereafter, the semi-dried film is peeled off from the metal support, transferred to a drying system, and dried to remove the solvent. And a uniaxial stretching process or a biaxial stretching process is performed with respect to the dry film. By carrying out this extending process, it is possible to improve the film uniformity and retardation value of a protective film.
  • the main dope liquid obtained as described above is cast on the support through a casting die to form an acrylic sheet.
  • the support serves to evaporate the solvent present in the main dope liquid while transferring the main dope liquid extruded from the die to form a film into an acrylic film.
  • the support or the surface thereof is made of a metal, and the surface is mirror-finished, and a metal belt such as a stainless steel belt is preferably used as the support.
  • the surface temperature of the metal support is advantageous because the higher the temperature, the faster the evaporation of the solvent present in the main dope liquid.
  • the surface temperature of the metal support is too high, the main dope liquid may foam or the planarity may deteriorate. Therefore, the surface temperature of the metal support may vary depending on the solvent used, preferably 0 to 75 ° C, more preferably 5 to 45 ° C.
  • the support may be a metal support in the form of a planar conveyor belt.
  • the acrylic sheet thus formed is transferred to the tender and subjected to the stretching step in the tender.
  • the film may be completed through the drying step in the dryer after removing the left and right ends of the film damaged by the clip or pin of the tender.
  • the apparatus which can control the grip length of a film from left to right by the right and left holding means of a tender.
  • the stretching operation may be performed by dividing into multiple stages, and it is also preferable to perform biaxial stretching in the casting direction and the width direction.
  • simultaneous biaxial stretching may be performed and you may carry out in steps. In this case, with stage, it is also possible to perform extending
  • simultaneous biaxial stretching also includes the case where the stretching is performed in one direction and the other is relaxed by shrinking the tension.
  • the preferable draw ratio of simultaneous biaxial stretching can be taken in the range of 1.01 time-2.0 time in both the width direction and the longitudinal direction.
  • the drying means generally blows hot air on both sides of the web, but there is also a means of heating the micro web instead of the wind. Too rapid drying tends to impair the planarity of the finished film.
  • the acrylic film of the present invention prepared according to the above method is manufactured by controlling the amount of residual solvent, it is excellent in slip properties during the film forming process, and appearance stains do not occur after production, and thus excellent quality can be exhibited.
  • the main dope liquid was prepared by fully mixing the wt% with an in-line mixer.
  • the main dope liquid was uniformly cast on a stainless band support having a width of 2000 mm using a belt casting apparatus.
  • the solvent was evaporated off the stainless band support and peeled off from the stainless band support.
  • both ends of the web were gripped with a tender and stretched so that the stretching ratio in the TD direction was 1.5 times in a 130 ° C temperature environment.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 27 wt% of the acrylic resin and 3 wt% of the aromatic ester additive having the structure represented by Formula 2 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 25 wt% of the acrylic resin and 5 wt% of the aromatic ester additive having the structure represented by Formula 2 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 20 wt% of the acrylic resin and 10 wt% of the aromatic ester additive having the structure represented by Formula 2 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 27 wt% of the acrylic resin and 3 wt% of the phenolic additive having the structure represented by Chemical Formula 5-1 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 25 wt% of the acrylic resin and 5 wt% of the phenolic additive having the structure represented by Formula 5-1 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 20 wt% of the acrylic resin and 10 wt% of the phenolic additive having the structure represented by Formula 5-1 were added.
  • the acrylic resin had a structure represented by 29 wt% and the following Chemical Formula 6-1, and the weight average molecular weight was 1000 g / mol, except that 1 wt% of an acrylic additive was added in the same manner as in Example 1. Was carried out.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 27 wt% of the acrylic resin and 3 wt% of the acrylic additive having the structure represented by Chemical Formula 6-1 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 25 wt% of the acrylic resin and 5 wt% of the acrylic additive having the structure represented by Chemical Formula 6-1 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1, except that 20 wt% of the acrylic resin and 10 wt% of the acrylic additive having the structure represented by Chemical Formula 6-1 were added.
  • the preparation of the main dope liquid was carried out in the same manner as in Example 1, except that 30 wt% of the prepared acrylic resin was added without adding the additive.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1 except that 15 wt% of the acrylic resin and 15 wt% of the aromatic ester additive having the structure represented by Formula 2 were added.
  • the preparation of the main dope solution was carried out in the same manner as in Example 1 except that 15 wt% of the acrylic resin and 15 wt% of the phenolic additive having the structure represented by Chemical Formula 5-1 were added.
  • the amount of solvent component released while each acrylic film sample was slowly heated was measured by Gas Chromatography.
  • DSC Differential scanning calorimeter
  • Example 1 Aromatic esters One 2400 109 Example 2 3 800 106 Example 3 5 600 102 Example 4 10 200 94 Example 5 Phenolic One 2100 112 Example 6 3 700 110 Example 7 5 400 105 Example 8 10 150 100 Example 9 Acrylic system One 2300 110 Example 10 3 850 108 Example 11 5 600 103 Example 12 10 200 97 Comparative Example 1 - - 4000 114 Comparative Example 2 Aromatic esters 15 150 85 Comparative Example 3 Phenolic 15 100 90 Comparative Example 4 Acrylic system 15 100 87
  • the film prepared without the additive of Comparative Example 1 is too much residual solvent, when the additive content of Comparative Examples 2 to 4 is more than 10% by weight, the amount of residual solvent is not high, but the glass Low transition temperatures make them unsuitable for making films.
  • the acrylic film of Examples 1 to 12 since the acrylic film of Examples 1 to 12 has a low residual solvent amount and has a glass transition temperature suitable for producing into a film, the acrylic film according to the embodiments of the present invention may exhibit excellent quality.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne un film acrylique préparé en régulant la quantité d'un solvant résiduel en ajoutant d'un additif spécifique, et fournit un film acrylique qui comprend une résine acrylique comprenant 70 à 96 parts en masse d'un motif méthacrylate de méthyle, et 4 à 30 parts en masse d'un motif (méth)acrylate d'alkyle à l'exclusion du méthacrylate de méthyle, et un type d'additif choisi dans le groupe constitué par un additif à base d'ester aromatique, un additif phénolique et un additif acrylique, et est préparé par un procédé de coulage avec solvant, la quantité d'injection de l'additif étant de 1 à 10 % en masse par rapport à 100 % en masse d'une solution dopée principale comprenant la résine acrylique, l'additif et un solvant lorsque la préparation est réalisée par le procédé.
PCT/KR2019/000690 2018-02-06 2019-01-17 Film acrylique WO2019156383A1 (fr)

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