TW200914272A - Method for producing acrylic resin film, and film laminate - Google Patents

Abstract

Disclosed is a process for producing an acrylic resin film, which can produce the film steadily without causing fracture or cracking in the film. Also disclosed is a film laminate for use in the process. The process for producing an acrylic resin film comprises the step of applying a protective film on an acrylic resin film comprising an acrylic resin having a glass transition temperature ranging from 110 to 200 DEG C inclusive, wherein the initial adhesion force in a surface of the protective film which contacts with the acrylic resin film is not less than 0.02 N/50 mm width to less than 0.15 N/50 mm width at 23 DEG C.

Description

[Technical Field] The present invention relates to a film laminate formed of an acrylic resin film and a protective film, and a method for producing an acrylic resin film using the laminate. [Prior Art] An acrylic resin typified by polydecyl acrylate (hereinafter referred to as "PMMA") is an optical isotropic material having excellent optical properties, high light transmittance, low complex refractive index, and low phase difference. Used in a variety of previous optical materials. In recent years, with the advancement of flat-panel displays, infrared sensors, optical waveguides, and the like, such as liquid crystal display devices, plasma displays, and organic EL display devices, demands for heat resistance of optical transparent polymer materials have increased. Even for acrylic resins, heat resistance is required to be high. A heat-resistant acrylic resin (hereinafter referred to as "heat-resistant acrylic resin") is known to contain a lactone ring obtained by a cyclization condensation reaction of a lactone with a polymer having a base group and an ester group in a molecular chain. Polymer (for example, refer to Patent Documents 1 to 4), a maleic imine copolymer obtained by copolymerizing maleic imine (for example, see Patent Document 5), and glutaric acid polymerization having a glutaric anhydride skeleton. (for example, refer to Patent Document 6). However, the film (acrylic acid-based resin film) containing the acrylic resin described in Patent Documents 1 to 6 lacks flexibility, and "the film is easily broken and cracked, and it is difficult to manufacture stably." [Patent Document 1] JP-A-2000-230016 (published on August 22, 2000) 5 200914272 [Patent Document 2] 曰本特开2〇〇1_151814号 (publication on June 5, 2) [Patent Document 3] Unexamined Japanese Patent Publication No. 2〇〇2_12〇326 (published on April 23, 2002) [Patent Document 4] JP-A-2002-254544 (September 11, 2002) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 09-324016 (published on Dec. 16, 1997) [Patent Document 6] JP-A-H06-283013 (published on October 19, 2006) DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing an acrylic resin film stably and capable of suppressing breakage and cracking, and a film laminate for use in the method. In order to solve the above-mentioned problems, the method for producing a propylene glycol-based resin film according to the present invention includes a step of attaching a protective film to an acrylic resin film containing an acrylic resin having a glass transition temperature of from UOt to 200 C. The method for producing an acrylic resin film is characterized in that the contact surface of the above-mentioned acrylic resin film and the acrylic resin film are adhered to the initial stage of the scratching, and the inner surface of the contact surface is in a range of more than the width and not widened. According to the above method, the step of attaching the protective film to the resin film can suppress the breakage and cracking of the propylene I (4). ^ The acrylic resin film is likely to be broken or cracked due to lack of flexibility (flexibility when it is bent to a part where the manufacturing apparatus is bent, or when it is wound in a tubular shape, etc.) By attaching the protective film, it is possible to suppress breakage and cracking of the acrylic resin film. Therefore, the acrylic resin film can be stably produced. Further, since the protective film has an initial adhesive force within the above range, The film is cracked when the protective film is peeled off. Therefore, according to the above method, the effect of "a stable production of an acrylic resin film having an excellent appearance" can be achieved. The method for producing an acrylic resin film according to the present invention is further included. The tension slope is set to a ratio in the range of 5% or more and 30% or less, and the tension is decreased as the diameter of the cylinder is increased, and the step of winding the acrylic resin film to which the protective film is attached into a tubular shape is preferred. According to the above method, since the film is wound into a cylindrical shape as the tension is decreased as the diameter of the cylinder is increased, the collapse of the obtained film roll can be suppressed. A film roll having a uniform shape is obtained. Therefore, according to the above method, a more effective effect such as "more efficient production and safe transportation" can be achieved. In the method for producing an acrylic resin film according to the present invention, the above acrylic resin The thickness of the film is preferably in the range of 50 μm or more and 600 μm or less. When the film roll is formed according to the above method, the collapse of the roll can be further suppressed. Therefore, a film roll having a more uniform shape can be produced. In the method for producing an acrylic resin film, the acrylic resin is preferably a polymer having a lactone ring structure. According to the above method, the polymer having a lactone ring structure has a high condensation reaction rate due to the ring 200914272. It is possible to prevent bubbles or silver streaks from being mixed into the molded article. Further, the polymer having a lactone ring structure has high heat resistance due to the lactone ring. Therefore, a film having an excellent appearance and excellent heat can be produced. According to the film laminate of the present invention, in order to solve the above problems, the protective film is attached to a glass transition temperature of 110 ° C or more and 20 〇 t: or less. A film laminate formed of an acrylic resin film of an acrylic resin, wherein the contact surface of the protective film with the acrylic resin film is in a crucible. The initial adhesion of the crucible is 〇. 2N/50 mm. More than the width and not within the range of i.i5N/5〇mm*. Further, the film-layered system according to the present invention is contained in the acrylic tree wax having a transition temperature of the slope wall of 110 ° C or more and 200 ° C or less.妇二=The membrane layer with a protective film attached to the lipid film is characterized in that the contact surface of the acrylic resin film is at 23 °C, and the adhesion force is 0.02. In the range of N/50 mm width or more and less than i.i5N/50 mm width, the protective film is attached to the inner resin film to suppress breakage and cracking of the acrylic resin film. In this case, it is possible to suppress breakage or cracking of the film due to tubular winding or handling. Further, the protective film described above has a set initial adhesive force 戋 adhesive force to suppress film cracking when the protective film is peeled off. According to the above configuration, it is possible to provide an olefinic resin film and provide stability and transportability. According to the film laminate of the present invention, the above-mentioned C The dilute acid, ^ M is preferably a polymer containing a lactone ring structure." 200914272 According to the above constitution, a polymer having a lactone ring structure can prevent bubbles or silver due to a high cyclization condensation reaction rate. A silver streak is mixed into the molded article. Further, a polymer having a lactone ring structure has high heat resistance due to a lactone ring. Therefore, a film excellent in appearance and heat resistance can be provided. [Embodiment] The present invention will be described in detail below, but the scope of the present invention is not limited thereto, and may be appropriately modified without departing from the scope of the present invention. In the present specification, "(mercapto)acrylic acid" means acrylic acid or methyl methacrylic acid, and "main component" means 50 mass% or more, and "ppm" means not limited by mass. The value obtained, for example, l〇, 〇〇〇ppm means 1% by mass. Further, "weight" is regarded as a synonym for "quality", and "% by weight" is regarded as a synonym for "% by mass", indicating that the range "A to B" means A or more and B or less. In the present specification, the "film" includes a film-like one and a sheet-like one. The film thickness of the acrylic resin film is not particularly limited, and is preferably in the range of 50 μm to 600 mm. In the present specification, "tension slope" means the rate of decrease in tension (rate of decrease) at the point of completion of winding at the initial tension. Among them, if the initial tension is within the range of more than 2N and less than 100N, any value is fine. The method for producing an acrylic resin film according to the present embodiment is a step of attaching a protective film to a propionic acid-based resin film containing an acrylic resin having a glass transition temperature of from ll ° C to 200 ° C. The method for producing a resin film of 200914272, wherein the initial adhesion of the contact surface of the protective film to the acrylic resin film at 23 ° C is more than N 2 N / 50 mm width and less than 0.15 N / 50 mm width. Within the scope. (I) Acrylic resin can form a glass material, generally in a low-temperature glass state and a high-temperature supercooled liquid state, the material is in an inherently narrow temperature region, at this time heat, expansion coefficient, conductivity, viscosity, etc. The temperature coefficient and other physical quantities change drastically. The glass transition temperature means the temperature region of this condition, which is the temperature at which the polymer molecules begin micro-Brownian motion. There are various methods for determining the glass transition temperature, however, it is defined in the present specification as the temperature obtained by the midpoint method in accordance with ASTM-D-3418 by a differential scanning calorimeter (DSC). According to the acrylic resin of the present embodiment, the glass transition temperature is in the range of 110 ° C to 200 ° C, and the acrylic resin is generally considered to be a heat-resistant acrylic resin. When the glass transition temperature is higher than 200 °C, the fluidity of the molten resin is deteriorated, and film formation tends to be difficult. The glass transition temperature is preferably in the range of 115 ° C or more and 180 ° C or less, and more preferably in the range of 120 ° C or more and 160 ° C or less. Further, the acrylic resin preferably has a viscosity at a resin temperature of 270 ° C at a shear rate of 100 (l/s) of 250 Pa·s or more and a range of 100 ° or less. Further, the shearing speed means a flow velocity change as the fluid flows along the wall surface as the position perpendicular to the wall surface is different. Shear speed 10 200914272 degrees, usually the maximum value of the wall surface, leaving the wall = person,) the shear catch, is the extruder =. Further, in the above-mentioned acrylic acid tree, it is preferable that the viscosity at the resin temperature of 25 于 is in the range of 2000 Pa.s or less in the case where the shearing degree is 22%. The method for measuring the above viscosity is not particularly limited, and the rheometer or the like can be measured. The viscosity and the sound described in the present specification are determined by the method described below. 41. The acrylic resin is not particularly limited as long as it is in the range of glass rotation ==, and an acrylic thermoplastic resin can be used. The ιτ formula (for the description of the acrylic acid tree pond) can be exemplified, for example, to have R2 I CH2 = C - CH ! COOR1

OH (1) (wherein R and R2 are each independently and represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue specifically represents a carbon I _ branched or cyclic alkyl group) knife A tree wax and an i derivative obtained by polymerizing a hydroxyl group-containing monomer, acrylic acid, methacrylic acid, and a monomer (composition) containing the biological component as a main component. ', j For a preferred specific example of the above (meth)acrylic acid derivative, it can be listed as 200914272 as methyl methacrylate, ethyl (meth) acrylate, (meth) acrylate:, __ N-butyl vinegar, (meth)acrylic acid =; ^ 2 acid is brewed, (meth)acrylic acid 2' chloroacetic acid, (meth)acrylic acid 2,3,4 5 6_5, "meth)acrylic acid 3 - by means of propyl vinegar, (meth)acrylic acid, & vinegar and (meth)acrylic acid 2,3,4,5-tetrahydroxypentene. =: Two can also be used. ^ 'α is preferably methyl (meth) acrylate. Ma Ershu: =: From the point of view, the main bone of the bismuth-polymer in the Ν-polymer such as the phenyl group substituted by the phenyl group and the methyl horse face imine 2 = ^ ^ ( It also refers to the structure, or the structure of the pentanediamine, and the tr structure and the glutaric acid scorpion: from the viewpoint of the difficulty of coloring (turning yellow), it does not contain nitrogen. Moreover, it is easy to make it Refractive index (疋 而 g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g In this way, when the main slung 5~6 (four) is the car's good ring, it can be the general formula (7): the inner vine ring is composed of 6 members.

'—-y 2 /1\ 12 200914272 (wherein R3, R4 and R5 are each independently, and represent a halogen atom or an organic residue having a carbon number of 1 to 20, and the organic residue specifically represents a carbon number of 1 to 20; The chain, the branched chain or the cyclic alkyl group, the organic residue may also contain an oxygen atom) or the structure shown in JP-A-2004-168882. Among them, when the polymer before the lactone ring structure is introduced into the synthetic main chain, the polymerization yield is high, and the lactone ring structure ratio is high in high polymerization yield - the viewpoint of the polymer and the methyl group From the viewpoint that the (mercapto) acrylate such as decyl acrylate is excellent in the polymerization property, the structure represented by the formula (2) is preferred. Further, the acrylic resin described above may be copolymerized with other monomer components copolymerizable, or may have a structural unit of another monomer component, insofar as the heat resistance is not impaired. Specific examples of the other monomer components which can be copolymerized include aromatic vinyl monomers such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile, and vinyl esters such as vinyl acetate. The weight average molecular weight of the acrylic resin is preferably in the range of 1,000 or more and 2,000,000 or less, more preferably 5,000 or more and 1,000,000 C. or less, more preferably 10,000 or more and 500,000 or less, and more preferably 50,000. It is particularly good in the range of 500,000 or less. The method for producing the above acrylic resin is not particularly limited, and a monomer composition containing a (fluorenyl) acrylate can be polymerized by a conventionally known method. The polymerization temperature and the polymerization time vary depending on the type of monomer (monomer composition) used, the ratio of use, and the like, but the polymerization temperature is in the range of 〇 ° C or more and 150 ° C or less, and the polymerization time is 0.5 hours or more and 20 hours. The range below is preferably in the range of from 80 ° C to 140 ° C, and the polymerization 13 200914272 is preferably in the range of from 1 hour to 10 hours. In the polymerization state using a solvent, the polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene, diphenylbenzene, and ethylbenzene, and ketone systems such as methyl ethyl ketone and decyl isobutyl ketone. The solvent, an ether solvent such as tetrahydrofuran, or the like may be used alone or in combination of two or more. When the following lactone ring-containing polymer is produced, if the boiling point of the solvent to be used is too high, since the polymer having the lactone ring finally obtained has a large amount of residual volatile matter, the boiling point is 50 ° C or more and 200 ° C or less. Those within the range are preferred. In the polymerization reaction, a polymerization initiator may be added as needed. The polymerization initiator is not particularly limited and may be, for example, cumene peroxide, diisopropylbenzene hydroperoxide, ditributyl peroxide, laurel SI-based peroxide, benzoquinone. Organic peroxides such as oxides, butyl peroxyacetate isopropyl ester, hexyl pentyl peroxy-2-ethyl hexanoate, 2,2,-arsenazo (isobutyronitrile), U An azo compound such as - azo (cyclohexylcarbonitrile) or 27-azo (2,4-dimethylvaleronitrile), which may be used alone or in combination of two or more. . The amount of the polymerization initiator to be used is not particularly limited as long as it is appropriately set depending on the combination of the monomers to be used, the reaction conditions, and the like. In the polymerization, it is preferred to control the gelation of the reaction liquid to control the concentration of the polymer formed in the polymerization reaction mixture to 50% by mass or less. Specifically, when the concentration of the polymer formed in the polymerization mixture exceeds 50% by mass, a polymerization solvent is appropriately added to the polymerization reaction mixture, and it is preferably controlled to 50% by mass or less. The concentration of the polymer formed in the polymerization mixture is preferably 45% by mass or less, and more preferably 40% by mass or less. Further, if the concentration of the polymer in the polymerization mixture is too low, 14 200914272, the productivity is lowered, so that the concentration of the polymer in the polymerization mixture is preferably 5% by mass or more, more preferably 20% by mass or more. The polymerization solvent is appropriately added to the polymerization reaction mixture, and is not particularly limited. The polymerization solvent may be continuously added, or the polymerization solvent may be added intermittently. By controlling the concentration of the polymer in the polymerization reaction mixture in this manner, the gelation of the reaction liquid can be more sufficiently suppressed, in particular, the ratio of the hydroxyl group and the ester group in the polymer chain is increased even if the content of the lactone ring is increased to increase the heat resistance. At time 5, gelation can also be sufficiently suppressed. The polymerization solvent to be added may be the same type of solvent as the solvent used in the initial stage of the polymerization reaction, or may be a different type of solvent, and is the same type of solvent as the solvent used in the initial stage of the polymerization reaction. good. Further, the polymerization solvent to be added may be one type of solvent or a mixture of two or more types. In the polymerization mixture obtained at the time of terminating the above polymerization reaction, a solvent is usually contained in addition to the obtained polymer. When the above polymer is formed into a polymer containing a lactone ring, the polymer can be taken out in a solid state without removing the solvent completely, and the lactone cyclization condensation step can be carried out in the state containing the solvent. Further, when necessary, it can be taken out in a solid state, and then an appropriate solvent is added to the lactone cyclization condensation step. The hue of the acrylic resin obtained by the polymerization reaction is not particularly critical, but it is preferable that the transparency and the yellowness are small, since the original characteristics of the acrylic resin are not impaired. When the acrylic resin is formed into a molded body having a thickness of, for example, 3 mm, the haze is preferably 3 or less, more preferably 2 or less, and 15 200914272 is preferably 1 or less. Further, the molded article has a YI (yellow index) of 10 or less, and preferably 5 or less. [Polyester-containing polymer] The acrylic resin is high in transparency, heat resistance, and optical properties, and can exhibit various properties suitable for various optical applications. In the copolymer, a lactone ring structure is introduced by an intramolecular cyclization reaction, and it is preferably a polymer containing a lactone ring, and the lactone ring-containing polymer is mainly composed of a lactone ring structure. Very good. Further, 'the main component' means that it is contained in an amount of 50% by mass or more based on the total mass of the bismuth acrylate resin. The polymer containing a lactone ring is not particularly limited. However, it is preferred to have a ring structure represented by the formula (2). In the polymer structure containing a lactone ring, the content of the lactone ring structure represented by the formula (2) is preferably in the range of 5 mass% or more and 90 mass% or less, and preferably 10 mass% or more and 70 mass% or less. The range is preferably in the range of 10% by mass or more and 60% by mass or less, and particularly preferably in the range of 10% by mass or more and 50% by mass or less. When the content is less than 5% by mass, the heat resistance, solvent resistance, and surface hardness are insufficient. In addition, when the content ratio is more than 90% by mass, the formability is insufficient, which is not preferable. The polymer containing a lactone ring may have a structure other than the structure of the lactone ring represented by the formula (2). The structure other than the lactone ring structure represented by the formula (2) is not particularly limited, but is, for example, (fluorenyl) decyl acrylate, a monomer having a hydroxyl group, an unsaturated carboxylic acid, and the following formula (3) : 16 200914272

~2 C

C

6 R

X \—/ 3 /, (wherein R6 represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an -OAc group, a -CN group, a -CO-R7 group, Or a C-0-R8 group, the Ac group represents an ethyl group, and R7 and R8 represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue specifically means a linear chain having a carbon number of 1 to 20, It is preferred to select at least one polymer structural unit (repeated structural unit) to be polymerized in the monomer represented by the branched chain or cyclic alkyl group. In the polymer containing a lactone ring, when the polymer structural unit (repeated structural unit) is formed by polymerizing a (mercapto) acrylate, the content thereof is in the range of 10% by mass or more and 95% by mass or less. Preferably, it is preferably in the range of 10% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. Very good. In the case of a polymer structural unit (repeated structural unit) which is formed by polymerizing a hydroxyl group-containing monomer, the content thereof is preferably in the range of 〇% by mass or more and 30% by mass or less, and more preferably 0% by mass or more. It is more preferably in the range of 20% by mass or less, more preferably in the range of 0% by mass or more and 15% by mass or less, and particularly preferably in the range of 〇% by mass or more and 10% by mass or less. Further, in the case of a polymer structural unit (repeated structural unit) which is obtained by polymerizing an unsaturated carboxylic acid, the content thereof is preferably in the range of 0% by mass to 30% by mass, and preferably 〇 by mass. The above-mentioned range of 20% by mass or less is preferable, and it is preferably in the range of 〇% by mass or more and 15% by mass or less, and particularly preferably in the range of 0% by mass or more and 10% by mass or less. Further, in the case of polymerizing a polymer structural unit (repeated structural unit) formed by polymerizing a monomer represented by the general formula (3), the content thereof is preferably in the range of 〇% by mass or more and 30% by mass or less. It is preferably in the range of 0% by mass or more and 20% by mass or less, more preferably in the range of 0% by mass or more and 15% by mass or less, and particularly preferably in the range of 0% by mass or more and 10% by mass or less. The method for producing the polymer containing a lactone ring is not particularly limited. Preferably, the polymer having a hydroxyl group and an ester group in the molecular chain can be obtained by a polymerization step, and then the inner vinegar ring is heated by the polymer. The structure is obtained by introducing an vinegar ring condensation reaction into the polymer. By forming a lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), the polymer can be imparted with high heat resistance. When the reaction rate of the cyclization condensation reaction in which the lactone ring structure is introduced is insufficient, the heat resistance cannot be sufficiently improved, and on the other hand, the condensation reaction may be caused during the molding by heat treatment at the time of molding, and the alcohol may be bubbled. Or silver streak is present in the molded article, which is not preferable. In order to carry out the lactone ring condensation reaction, the method of heat-treating the above polymer is not particularly limited, and a known method can be used. For example, the polymerization reaction mixture containing the solvent obtained by the polymerization step can be subjected to heat treatment as it is. Further, it is also possible to carry out heat treatment using a closed-loop catalyst in the presence of a solvent, if necessary. Further, a heating furnace or a reaction apparatus including a vacuum apparatus or a devolatilization apparatus for removing volatile components may be used, and heat treatment may be carried out by using a φ 麟 Lin of 18 200914272 or a U devolatilization apparatus. In the case of the deuteration condensation reaction, in addition to the above polymer, it is also possible to coexist with the olefinic acid tree wax. Further, when carrying out the cyclization condensation reaction, an esterification catalyst such as p-toluenesulfonic acid or a transesterification catalyst cyclization condensation reaction catalyst, or acetic acid, propionic acid, benzoic acid, or propyl group may be used as needed.夂曱基丙(四) and other organic (four) divisions for Gu. As shown in Japanese Patent Laid-Open No. 1 254608 #u and Japanese Unexamined-Japanese-Patent No. 61-261303, it is also used to detect compounds, organic oxalates, carbonates, etc. By using an organic phosphorus compound as a catalyst: by using an organic filler compound as a catalyst, the condensation condensation can be increased, and the obtained polymer containing the lactone ring can be used. Further, by using an organic filler compound as a catalyst, the use of the following devolatilization step can suppress the possibility of a decrease in molecular weight and impart excellent mechanical strength. For the organophosphorus compound which can be used as a catalyst, = such as methyl phosphinic acid 'ethyl phosphinic acid, phenyl cresyl acid, etc., ^ 或 袖 or sleeve, dimethyl Glycosylphosphonic acid, diethyl secondary: the base: human, phenylmethylphosphinic acid, phenylethyl cyanoic acid and = (square) phosphinic acid and these esters; Phosphonic acid, ethyl methyl lysine, phenyl phenyl (aryl) phosphonic acid and these second-instar or monoterpene, methyl sub-riding Ethyl phosphinic acid, ester, sulphuric acid benzene S, phosphite dimethyl g, sulphuric acid, sulphuric acid (aryl) cylinic acid and vinegar; 19 200914272 Diphenyl ester, tridecyl phosphite, triethyl phosphite phosphite diester or monoester or triester; methyl hexyl phosphate such as methyl phosphate, hydrazine, triphenyl phosphate, isodecyl phosphate, Lauryl phosphate, 驮 ethyl ester, phosphoric acid 2-isostearyl vinegar, acetoic acid benzene vinegar, diterpene phosphate bismuth oleate, stearic acid-2-ethylhexanoacetic acid, diisomeric vinegar phosphate, Dish B, Phosphoric acid S, bismuth diacetate, diphenyl vinegar, bismuth diacetate, distearyl citrate, triisodecyl phosphate, trilauryl phosphate, Tri-acid triisostearyl vinegar, triphenyl phenolic acid, etc., such as diterpene bismuth ^=distearyl vinegar, wall-based phosphine, ethyl phosphine, phenylphosphine, dimethyl phenyl, diterpenoid, early or three Vinegar; methyltrimethylphosphine, triethylphosphine, triphenylphosphine, etc. single: phosphine: diphenylphosphine, phosphine; methyldichlorophosphine., ethyldichlorophosphine, phenyl digas;: or three Acyl (aryl) chlorophosphine, diphenyl chlorophosphine, etc. )_,;=, emulsified ethyl phosphine, oxidized phenyl m 1 decylphosphine, M ju - ^ ^ ^ butyl, emulsified diethyl phosphine, deuterated monophosphine, trimethyl phosphine oxide, Oxygen dimethyl phosphine and other oxygen, -ethyl phosphine, oxidized triphenyl sulphide sputum, early di- or tri-alkyl (aryl-free tetraethyl sulphate, gasified four jasmine accounted for #虱化tetramethyl Scales, chlorinated bases, tetraalkyl (aryl) scales, etc.. Due to high catalytic activity and low coloration, thiol (aryl) sub, =, phosphite diester or Monoester, phosphodiester or monoester, alkyl (aryl) = oxime is preferred, alkyl (aryl) phosphinic acid, phosphite diester or monoester, phosphorus or monoester is preferred, The alkyl (arylene) phosphinic acid, the phosphoric acid diester, or the monoterpene is particularly preferred. These organic phosphorus compounds may be used alone or in combination of two or more. - There is no particular limitation on the amount of the catalyst used in the cyclization condensation reaction, but it is preferably in the range of 0.001 to 5% by mass in the range of 0.001 to 5% by mass in the range of 0.001 to 5% by mass in the range of 0.01 to 2.5. The range of % is preferably in the range of 0.01 to 1% by mass, more preferably in the range of 0.05 to 0.5% by mass. If the amount of the catalyst used is less than 0.001% by mass, the reaction rate of the cyclization condensation reaction may not be sufficiently increased. On the other hand, if it exceeds 5% by mass, it is caused by coloration and is melted by crosslinking of the polymer. The shape becomes difficult and therefore not good. The period of addition of the catalyst is not particularly limited, and may be added at the beginning of the reaction, may be added during the reaction, or may be added during both periods. Among them, a cyclization condensation reaction is carried out in the presence of a solvent, and a devolatilization step is preferably employed in the cyclization condensation reaction. In this case, a state in which the entire cyclization condensation reaction is carried out, a step of using a devolatilization component, and a step of using a devolatilization component in addition to the entire cyclization condensation reaction, but only in a part of the process is used. . Further, by the method of the devolatilization step, since the by-produced alcohol is forcibly volatilized and removed during the cyclization condensation reaction, it is advantageous for the equilibrium side of the reaction equilibrium. The devolatilization step means a step of removing the volatile component such as a solvent or a residual monomer and the alcohol produced by the cyclization condensation reaction introduced into the lactone ring structure, and if necessary, under reduced pressure heating. If the removal treatment is insufficient, the amount of residual volatiles in the resulting resin increases, which causes coloring due to deterioration during molding, or problems such as poor formation due to foaming or silver streak. In the aspect of the cyclization condensation reaction step and the devolatilization step, the apparatus to be used is not particularly limited, but in order to carry out the present invention more efficiently, the devolatilization using a heat exchanger and a devolatilization tank is used. 21 200914272 A component device, or an extruder with a vent hole, or a device in which the devolatilization device and the above-described extruder are arranged in series, wherein a devolatilization device including a heat exchanger and a devolatilization tank is used, or An extruder with a vent hole is preferred. The reaction treatment temperature in the case of using the above-mentioned devolatilization device containing a heat exchanger and a devolatilization tank is preferably in the range of 150 to 350 T: and preferably in the range of 200 to 300 °C. If the reaction temperature is lower than 15 〇〇 c, the cyclization condensation reaction will become insufficient, and the residual volatile component will increase, and if it is higher than 350 ° C, coloring and decomposition may occur. When the above-mentioned devolatilization device including a heat exchanger and a devolatilization tank is used, the pressure at the time of the reaction treatment is preferably in the range of 931 to 1.33 hPa (700 to 1 mmHg), and is preferably 798 to 66.5 hPa (600~). A range of 50 mmHg) is more preferable. When the pressure is higher than 931 hPa, there is a problem that "the volatile components of the alcohol are easily retained", and if it is less than 1.33 hPa, there is a problem that "industrial implementation becomes difficult". When the above-described extruder with a vent hole is used, the vent hole may be one or plural, but it is preferable to have a plurality of vent holes. The reaction treatment temperature at the time of using the above-mentioned extruder with a vent hole is preferably in the range of 150 to 350 ° C, and preferably in the range of 200 to 300 ° C. If the above temperature is lower than 15 〇 ° C, the cyclization condensation reaction may become insufficient, and the residual volatile component may increase, and if it is higher than 35 〇〇 c, coloring and decomposition may occur. When the above-mentioned extruder with a vent hole is used, the pressure during the reaction treatment is preferably in the range of 931 to 1.33 hPa (700 to 1 mmHg), and in the range of 22 200914272 798 to 13.3 hPa (600 to 10 mmHg). Preferably. When the pressure is higher than 93 lhPa, there is a problem that "the volatile matter of the alcohol is liable to remain", and if it is less than 1.33 hPa, there is a problem that "industrial implementation becomes difficult". Further, in the case where the entire cyclization condensation reaction process is carried out in the same manner as in the devolatilization step, it is preferable to use the properties of the lactone ring-containing polymer obtained under severe heat treatment conditions as described below. The above-mentioned catalyst for the dealcoholization reaction is preferably carried out by using an extruder having a vent hole as much as possible under mild conditions. Further, in the case of the entire cyclization condensation reaction step and the devolatilization step, it is preferred that the polymer obtained by the polymerization step is introduced into the cyclization condensation reaction device together with the solvent, but at this time, it may be passed again as needed. The above reaction apparatus such as an extruder having a vent hole. It is also possible to use a devolatilization step which is not used in the entire cyclization condensation reaction, but only in a part of the process. For example, the apparatus for producing a polymer is further heated, and a part of the devolatilization step is used as needed, and the cyclization condensation reaction is carried out to some extent in advance, and then the cyclization condensation reaction of the devolatilization step is simultaneously carried out to complete the reaction. The way. In the above-mentioned entire cyclization condensation reaction process and the devolatilization step, for example, when the polymer is heat-treated by a biaxial extruder at a high temperature of around 250 ° C or higher, the ring is caused by the heating history. A part of decomposition or the like occurs before the condensation reaction, and the physical properties of the polymer containing the lactone ring may be deteriorated. Then, before the cyclization condensation reaction in which the devolatilization step is used in combination, the cyclization condensation reaction is carried out in advance to 23 200914272 to some extent, the reaction conditions in the latter half can be alleviated, and the obtained polymer containing the internal vinegar ring can be suppressed. Physical properties are deteriorated, so it is preferred. A particularly preferred aspect is a step of performing a devolatilization step after a cyclization condensation reaction starts, that is, pre-cyclizing a hydroxyl group and an ester group present in a molecular chain of the polymer obtained by the polymerization step. The condensation reaction, and when the cyclization condensation reaction rate reaches a certain level, the cyclization condensation reaction step of the devolatilization step is continued. Specifically, it is preferable to use a reactor in a tank type in advance, to carry out a cyclization condensation reaction to a certain degree of reaction rate in the presence of a solvent, and then to use a reactor equipped with a devolatilization device. For example, a devolatilization component device composed of a heat exchanger and a devolatilization tank, an extruder with a vent hole, and the like complete the cyclization condensation reaction. In particular, in such a case, it is more preferable to use a catalyst for the cyclization condensation reaction. As described above, the hydroxyl group and the ester group present in the molecular chain of the polymer obtained in the polymerization step are subjected to a cyclization condensation reaction in advance, and when the cyclization condensation reaction rate reaches a certain level, the ring of the devolatilization step is continuously used. The method of the condensation reaction is to obtain a preferred aspect of the polymer containing a lactone ring. By such an aspect, the cyclization condensation reaction rate can be further increased, and a polymer containing a lactone ring having a higher glass transition temperature and excellent heat resistance can be obtained. In this case, the degree of the cyclization condensation reaction rate is preferably 2% or less at 150 to 300 ° C in the dynamic TG (Dynamic TG) measurement shown in the examples, and preferably 1.5% or less. It is better to be 1% or less. Before carrying out the cyclization condensation reaction in which the devolatilization step is used in combination, the reactor used in the prior cyclization condensation reaction is not limited to a specific one, and is preferably a hot-pressed reactor. Further, a devolatilization unit comprising a heat exchanger and a devolatilization tank, or a venting extruder suitable for the cyclization condensation reaction in which the devolatilization step is used in combination may be used. The autoclave and the kettle type reactor were f. J bauxite. However, even when a venting extruder or the like is used as the reactor, the temperature or the barreling condition is adjusted by adjusting the exhausting condition to a gentle state or without using the exhaust gas: a screw shape, a screw operating condition, and the like. Can react with autoclave and kettle type π

The cyclization condensation reaction is carried out in the same state as the reaction state. When the cyclization condensation reaction is carried out in advance on the same day and the cyclization condensation step of the devolatilization step is carried out, the following formula is preferably used. The polymer obtained by the I combination step is preferably used. a mixture of a solvent, a method of heating a reaction with a small amount of a knife (1) by adding a catalyst, (ii) a method of introducing a catalyst without adding a catalyst, and a method of heating the reaction, and (i) or (ii) performing under pressure The method. Further, "the mixture containing a polymer and a solvent" introduced in the cyclization condensation reaction in the vinegar cyclization condensation step means that the polymerization mixture obtained in the polymerization step can be used as it is - or after the solvent is removed once A solvent suitable for the cyclization condensation reaction is further added. The solvent which can be further added in the case where the cyclization condensation reaction is carried out before the cyclization condensation reaction in the devolatilization step is not particularly limited, and may be, for example, an aromatic hydrocarbon such as toluene, xylene or ethylbenzene; A ketone such as a benzyl group or a methyl isobutyl ketone; chloroform, DMSO or tetrahydrofuran, wherein the same kind of solvent as the solvent which can be used in the polymerization step is preferred. The catalyst to be added to the above method (1) may, for example, be an esterification catalyst such as p-toluenesulfonic acid or a transesterification catalyst or an intrinsic compound, 25 200914272 organic carboxylate or carbonate. In the present embodiment, it is preferred to use the above-mentioned organic compound. The period of addition of the catalyst is not particularly limited, and may be added at the beginning of the reaction, or added during the reaction, or may be added during both periods. The amount of the catalyst to be added is not particularly limited, but is preferably in the range of 0.001 to 5% by mass based on the mass of the polymer, and preferably 0.01 to 2.5% by mass in the range of 0.01 to 2.5% by mass. It is more preferably in the range of 0.1% by mass, and particularly preferably in the range of 0.05 to 0.5% by mass. The heat temperature and heating time of the method (i) are not particularly limited, but the heating temperature is preferably room temperature or higher, preferably 50 ° C or higher; and the heating time is preferably in the range of 1 to 20 hours. It is preferably in the range of 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, "there is a case where the resin is colored and decomposed", which is not preferable. In the above method (ii), a method in which the polymerization reaction mixture obtained in the polymerization step is heated as it is, for example, using a pressure-resistant kettle can be mentioned. The heating temperature is preferably 100 ° C or more, more preferably 150 ° C or more, and the heating time is preferably in the range of 1 to 20 hours, more preferably in the range of 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored and decomposed, which is not preferable. The above methods (i) and (ii) have no problem depending on conditions even under pressure. Further, when the cyclization condensation reaction is carried out in advance before the cyclization condensation reaction of the devolatilization step, a part of the solvent is naturally volatilized in the reaction, and there is no problem. 26 200914272 At the same time as the cyclization condensation reaction before the cyclization condensation reaction of the devolatilization step is completed, that is, the mass reduction rate at 150 to 300 ° C in the dynamic TG measurement immediately before the start of the devolatilization step It is preferably 2% or less, more preferably 1.5% or less, and still more preferably 1% or less. If the mass reduction rate is higher than 2%, even if the cyclization condensation reaction of the devolatilization step is continued, the cyclization condensation reaction cannot be raised to a sufficiently high level, and the physical properties of the polymer containing the internal vinegar ring may be obtained. Will decrease. Further, when the above cyclization condensation reaction is carried out, other thermoplastic resins may be coexisted in addition to the polymer. Other thermoplastic resins are preferably thermoplastic resins which are thermodynamically compatible with the polymer containing the lactone ring. For example, a copolymer containing a vinyl cyanide monomer unit and an aromatic vinyl monomer unit, specifically, an acrylonitrile-styrene copolymer, a polyvinyl chloride resin, or a mercapto-acrylic acid-containing vinegar 5 may be mentioned. 0% by mass or more of the polymer. Among them, the acrylonitrile-styrene copolymer has the best compatibility, and a transparent molded body can be obtained without impairing heat resistance. Further, the polymer containing a lactone ring is thermodynamically compatible with other thermoplastic resins, and can be confirmed by measuring the glass transition point of the thermoplastic resin composition obtained by mixing them. Specifically, when the glass transition point is measured by a differential scanning calorimeter, only one point is observed for the mixture of the polymer containing the lactone ring and the other thermoplastic resin, which is called thermodynamic compatibility. In the case where an acrylonitrile-styrene copolymer is used as the other thermoplastic resin, an emulsion polymerization method or suspension polymerization can be used for the method of polymerizing the lactone ring-containing polymer and the acrylonitrile-styrene copolymer. Method, 27 200914272 Solution polymerization method, bulk polymerization method, etc. However, from the viewpoint of transparency and optical performance of the obtained acrylic resin film, it is preferred to obtain it by a solution polymerization method or a bulk polymerization method. The cyclization condensation reaction of the hydroxyl group and the ester group in the molecular chain of the polymer obtained in the polymerization step is carried out in advance to increase the cyclization condensation reaction rate to a certain extent, followed by cyclization condensation using the devolatilization step simultaneously In the case of the reaction, the polymer obtained by performing the cyclization condensation reaction in advance (the polymer having a cyclization condensation reaction of at least a part of the hydroxyl group present in the molecular chain with the ester group) may be separated from the solvent. Next, a cyclization condensation reaction in which a devolatilization step is used in combination is carried out. Further, if necessary, the polymer (the polymer in which the hydroxyl group present in the molecular chain and at least a part of the ester group are subjected to a cyclization condensation reaction) may be separated, and after further treatment such as adding a solvent, simultaneous devolatilization may be carried out. The cyclization condensation reaction of the component steps. The devolatilization step is not limited to completion at the same time as the cyclization condensation reaction, and may be carried out after some time has elapsed after the completion of the cyclization condensation reaction. The polymer containing a ring of the inner s. As described above, it is preferred to use a catalyst for the cyclization condensation reaction. However, if the catalyst remains in the resin, the unreacted ring-forming unit is heated when the resin is heated (also That is, the radical of the unit which has not formed a ring, or the active hydrogen such as water which is present in a small amount in the system, is produced by vinegar exchange with the burnt ester group to cause alcohol, thereby causing foaming. In order to prevent this foaming phenomenon, it is preferred to add a deactivating agent. In general, when the catalyst used in the cyclization condensation reaction is an acidic substance, in order to deactivate the catalyst remaining after the reaction, it is only necessary to neutralize with a basic substance. Therefore, when the catalyst used in the cyclization condensation reaction is an acidic substance 28 200914272, it is preferred to use an inert substance as a deactivating agent. The test substance is not particularly limited as long as it does not cause physical properties which hinder the physical properties of the resin composition during hot working. For example, it may be a metal carboxylate, a metal complex, a metal oxide or the like. For example, when a polymer containing a lactone ring is used as the acrylic resin, as described above, in the inner vinegar cyclization condensation step, the hydroxyl group present in the polymer molecular chain is cyclized and condensed with the ester group to cause transesterification. In the dealcoholization reaction, a lactone ring structure is formed in the molecular chain of the polymer (in the main skeleton of the polymer). In general, when the catalyst used for the transesterification is an acidic substance, in order to deactivate the catalyst remaining after the reaction, it is only necessary to neutralize with a basic substance. Therefore, the test substance to be used as the deactivating agent at this time is not particularly limited as long as it does not cause a substance composition that hinders the resin composition during hot working, and may be, for example, a metal salt or a wholly-form complex. And metal compounds such as metal oxides. In addition, the metal constituting the metal compound is not particularly limited as long as it does not impair the physical properties of the resin composition and the like, and does not cause environmental pollution at the time of disposal, and may be, for example, a metal such as a chain, a sodium or a potassium; And earthworms such as earthworms; dimorphic substances such as resignation, Ming, tin, and wrong, and errors. Among these metals, from the viewpoint of less coloring of the resin, a typical metal element is preferred, and an alkaline earth metal or an amphoteric metal is particularly preferred, and fishing, magnesium, and rheology are preferred. The metal salt is preferably a metal salt of an organic acid, and a metal salt of an organic carboxylic acid, an organic phosphoric acid compound or an acidic organic sulfur compound, from the dispersibility to the resin and the solubility in a solvent. The organic carboxylic acid constituting the organic 29 200914272 carboxylic acid metal salt is not particularly limited, and may, for example, be citric acid, acetic acid, propionic acid, butyric acid, shikimic acid, caproic acid, heptanoic acid, caprylic acid, citric acid, citric acid, Lauric acid, meat stem citrate, palmitic acid, stearic acid, camellic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, Fumaric acid, maleic acid, adipic acid, and the like. The organophosphorus compound constituting the organic metal phosphate may be an alkyl (aryl) phosphinic acid such as decylphosphinic acid, ethylphosphinic acid or phenylphosphinic acid (however, these may also be formed as mutual Alkyl (aryl) phosphinic acid of the isomer and such monoester or diester; dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethyl a dialkyl(aryl)phosphinic acid such as phosphonic acid or phenylethylphosphinic acid and the like; an alkane such as decylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid or phenylphosphonic acid Alkyl (aryl) phosphonic acid and such monoester or diester; alkyl (aryl) phosphinic acid such as methyl phosphinic acid, ethyl phosphinic acid, phenyl phosphinic acid and the like Ester; decyl phosphite, ethyl phosphite, phenyl phosphite, dinonyl phosphite, diethyl phosphite, diphenyl phosphite, tridecyl phosphite, triethyl phosphite, etc. Phosphate monoester, dimonoester or triester; decyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate Benzene phosphate , Didecyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisononyl phosphate, dilauryl phosphate, distearyl phosphate, diisostearyl phosphate, diphenyl phosphate, phosphoric acid Phosphate monoester, diester or triester such as tridecyl ester, triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; a mono-, di- or trialkyl group such as phosphine, ethylphosphine, phenylphosphine, dimercaptophosphine, diethylphosphine, diphenylphosphine, tridecylphosphine, triethylphosphine, 30 200914272 triphenylphosphine ( Alkyl phosphine, decyl dichlorophosphine, ethyl dichlorophosphine, phenyl dichlorophosphine, dinonyl chlorophosphine, diethyl chlorophosphine, diphenyl chlorophosphine, etc. alkyl (aryl phosphine; oxidized Oxidation of phosphine, oxyethylphosphine, phenylphosphine oxide, dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide, etc. Mono-, di- or trialkyl (aryl) phosphine; tetramethyl sulfonium chloride, tetraethyl chlorinated tetrachloride, tetraphenylphosphonium chloride or the like tetraalkyl (aryl) scales, etc. The acidic organic sulfur compound of the metal salt of the organic sulfur compound may be p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, etc. There is no special organic component in the metal complex. In addition, when the catalyst used for transesterification is an test substance, an acid substance such as an organic acid-inducing compound can be used to deactivate the catalyst remaining after the reaction. The inactivating agent may be used singly or in combination of two or more. Further, the deactivating agent may be added in any form such as a solid, a powder, a granule, a dispersion, a suspension, an aqueous solution or the like without any limitation. The amount of the agent to be added is appropriately adjusted depending on the amount of the catalyst used for the cyclization and condensation reaction, and is not particularly limited. For example, based on the mass of the polymer containing the internal vinegar ring, it is 10 ppm or more and 10,000 ppm or less. The range is preferably in the range of 50 ppm or more and 5,000 ppm or less, more preferably in the range of 100 ppm or more and 3,000 ppm or less. If the above-mentioned addition amount is less than 10 ppm, the effect of the deactivator becomes insufficient, and bubbles are generated during heating, which is not preferable. When the above-mentioned addition amount exceeds 10,000 ppm, since the action of the deactivating agent is saturated, it is not preferable because the above-mentioned deactivating agent is required to use the above-mentioned depleted agent. The above deactivating agent may be added as long as the lactone ring structure is formed. For example, in the production of a lactone-containing cyclic polymer, it may be added at a set stage to obtain a polymer containing a lactone ring, and then the polymer containing a lactone ring, an inactivating agent, other components, and the like may be simultaneously heated and melted. And a method of kneading; after the lactone ring-containing polymer is produced, a deactivating agent is added, and a lactone ring-containing polymer, an inactivating agent, other components, and the like are simultaneously heated and melted and kneaded; and the lactone-containing ring is polymerized. A method in which a substance, other components, and the like are heated and melted, and a deactivator, other components, and the like are added thereto and kneaded. The lactone ring-containing polymer preferably has a weight average molecular weight of 1 or more and 2,000,000 or less, preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less. It is particularly good in the range of 50,000 or more and 500,000 or less. The lactone ring-containing polymer has a mass reduction ratio of 150 ° C or more and 300 ° C or less in the dynamic TG measurement, preferably 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less. Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage of "incorporating bubbles or silver streak into the molded article after forming." Further, the lactone ring structure can be sufficiently introduced into the polymer by a high cyclization condensation reaction rate, and the obtained lactone-containing ring polymer has very high heat resistance. The lactone ring-containing polymer has a 5% mass reduction temperature in thermogravimetric analysis (TG) of preferably 280 ° C or more, more preferably 290 ° C or more, and still more preferably 300 ° C or more. The 5% mass reduction temperature in thermogravimetric analysis (TG) is an indicator of thermal stability. If it does not reach 280 °C, it may not be able to exert sufficient thermal stability. 32 200914272 The inner vinegar ring polymer contains a total amount of residual volatile matter of 5,000 ppm or less, preferably 2,000 ppm or less. When the total amount of the remaining volatile matter is more than 5,000 ppm, it is colored or foamed due to deterioration during molding, and causes a molding failure such as a silver streak. The molded article obtained by injection molding from the vinegar-containing bad polymer method has a total light transmittance of 85% or more, preferably 88% or more, more preferably 90% or more, according to the method of ASTM-D-1003. For better. The total light transmittance is a degree of transparency, and if it is less than 85%, the transparency is lowered, and it may not be used for the purpose of the original purpose. (Π) Protective film The protective film according to this embodiment is a film having an initial adhesive force at 23 ° C which is a surface of a width of 0.02 N / 50 mm or more and a range of not more than 0.15 N / 50 mm. In the present specification, the initial adhesive force means a value measured by a 180° peel test in accordance with JIS Z-0237. Specifically, PMMA (poly(meth) methacrylate) was placed on a stainless steel plate, and a test piece (protective film) was attached to the PMMA, and the test piece was peeled off at a speed of 300 mm/min in a 180° direction. The load at four places was measured at intervals of 20 mm, and the average value was used as the initial adhesion. The protective film may be a film obtained by coating or co-pressing an adhesive layer on a substrate. The substrate may be a polyhydrocarbon resin such as polyethylene or the like. The adhesive layer is not particularly limited as long as it can impart the initial adhesion, and EVA (ethylene-vinyl acetate copolymer), metallocene 33 200914272 (metallocene) L-LDPE (polymerization using metallocene catalyst) The linear chain of polyethylene is preferred. The film thickness of the above-mentioned protective film is preferably in the range of 1 〇 to 1 μm, and preferably in the range of 20 to 90 μm. The adhesive layer of the protective film of the earth may be provided by the above-mentioned acrylic resin, and may be provided on the surface of the contact with the acrylic tree, or may be provided only on the portion. . /3, (ΪΠ) Method for Producing Acrylic Resin Film <Film Forming Step> The acrylic resin film according to the present embodiment can be obtained from the acrylic resin according to the above-described abhorm.膜膜, 曰Η山 丹耆 The film is continuously formed in the above acrylic resin molding method. Method ^%t (four) compared to the object, the liquid is compiled into the sputum melting method, the factory squeezing method (caI (four) and the factory squeezing liquid film forming method. In these film forming methods, the solution 4 solution The law) and the melt extrusion method are particularly good. The solvent of the clear casting method (solution casting method) and the fat of the moon; the ethyl acetate 1 butyl, the hand-based bismuth, the acetophenone, acetone, decyl isobutanol, two = Equivalent class; methanol, ethanol, isopropanol, butanol, sub-T base> gluten, B, 交, 丨 tetrahydrofuran, - earth / Μ, butyl cellosolve and other alcohols; Deficit hospitals _ class; - Chatian b, - 虱 貌, 仿, tetrachloride 竣 34 200914272 and other halogenated H - methyl amide amine; dimethyl hydrazine and so on. These solvents may be used singly or in combination of two or more. The apparatus used for the 饤 ♦ liquid washing tungsten method (solution casting method) may, for example, be a roller type casting, a belt scale machine, a _coating machine, or the like. For example, a die method, a blown film method (in addition, η), etc., such that the τ is appropriately adjusted according to the glass transition temperature of the film material, is not particularly limited, but for example, i5Q The range of ~3 is better for the second and the range for the 200~ bay is better. When the T-head method is used to form the film, a τ die can be attached to the front end portion of a known uniaxial extruder or a biaxial extruder, and the film extruded in a film form can be taken up to obtain a roll-shaped film. . At this time, the temperature of the reel can be appropriately adjusted and extended in the extruding direction to perform "uniaxial stretching". Alternatively, the resin film may be an unstretched film by extending the film in the extrusion direction and the vertical direction or the "secondary biaxial extension" direction. When extending into a biaxially stretched film, the film can be stretched. Any kind. When the film is biaxially stretched: :=: or the sequential biaxially stretched film. Even if the film is stretched, the phase can be suppressed and the film properties can be improved. An isotropic membrane. If it is large, it is possible to obtain optical retention. Further, the acrylic resin is preferably in a range of 600 μm or less. The pancreas; a film of 50 μm or more or more may contain the above-mentioned acrylic resin or a component other than the enamel resin by the above-mentioned acryl. The components other than the acrylic resin may be included in the above-mentioned 35 200914272, and may be a polymer (other polymer) other than the acrylic resin, or other additives. The other polymer may be a hydrocarbon-based polymer such as polyethylene, polypropylene, ethylene-propylene copolymer, poly(4-mercapto-1-pentene), or a dentate-based polymer such as vinyl chloride or vinyl chloride resin; Acrylic polymer such as polymethyl methacrylate; styrene such as polystyrene, styrene-mercapto methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Ethylene polymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.; nylon 6, nylon 66, nylon 610 and other polyamines; Polycarbonate; polyphenylene sulfide; polyetheretherketone; polyetheretherketone; polyfluorene; polyether oxime; polyoxybenzylene; polylinamide A polybutadiene rubber, an ABS resin to which an acrylic rubber is added, or a rubber polymer such as an ASA resin. The content of the other polymer in the acrylic resin film is preferably in the range of 〇% by mass or more and 50% by mass or less, and more preferably 0% by mass or more and 40% by mass or less, and 0% by mass or less. The range of 30% by mass or less is more preferably in the range of 0% by mass or more and 20% by mass or less. The other additives mentioned above may be, for example, an oxidation inhibitor such as a blocking lanthanide, a filling system, or a sulfur system, a stabilizer for a light stabilizer, a weathering stabilizer, a heat stabilizer, a reinforcing material such as glass fiber or carbon fiber, or a benzene salicylate. Ultraviolet absorbers such as esters, (2,2'-hydroxy-5-nonylphenyl)benzotriazole, 2-hydroxydiphenyl ketone; near-infrared absorbing agent, bis(dibromopropyl acrylate), phosphoric acid Allyl ester, 36 200914272 == Agent: anionic, cationic, non-separating interface agent, · organic fine, dye and other coloring machine filler; plasticizer, slip agent, anti-static agent, flame retardant == grease The content of the above-mentioned other additives in the film is preferably in the range of 5% by mass or less, and more preferably 〇 mass% or more. 2::=r is preferable, and enamel-mass core is smelted in =:=additive' to the film. Before the formation, the protective film attaching step is applied to the protective film, and the protective film is attached to the acrylic resin film obtained by the film forming step. The above-mentioned side of the protective film is not particularly limited, and for example, a drive having a motor such as a spinning machine (or a winding machine) is provided on the lower side or the upper side of the film traveling path of the film forming apparatus. The film is manufactured by attaching a protective film to a protective film by two rubber wheels. Further, the protective film may be bonded only to one side of the acrylic resin film or may be bonded to both sides. <Winding step> The winding step is obtained by winding the acrylic resin film (film layered body) to which the protective film is attached, into a cylindrical shape. More specifically, a winding core is attached to the winding machine, and the film laminated body is wound around the winding core so that the winding speed is adjusted so as to be about the same as the linear velocity of the film laminated body. Among them, it is preferable to adjust the tension gradient to a ratio of 5% or more and 30% or less in the range of 5% or more and 30% or less, and to reduce the tension as the diameter increases, and it is preferable to wind the film laminate into a cylindrical shape. Further, the initial tension at the time of winding up can be appropriately set depending on the film thickness of the film to be wound, etc., and can be set, for example, in a range of more than 2N and less than 100N. Further, the above winding speed can be set within a range of, for example, 1 to 1 〇〇m/min. Further, it is known that knurling to a certain thickness is applied to the film to prevent wrinkles or loosening of the wrap (for example, refer to Japanese Laid-Open Patent Publication No. 2-2-2mf). However, according to the method of the present embodiment, it is also possible to suppress the collapse of the film cylinder and to produce a film roll having a uniform shape. The film laminated body of the film is affixed to the film, and is transported by the acrylic system.制 丙烯酸 特 ( 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四After f-breaking and peeling, it can be used as the acrylic tree contact surface at the beginning of 2 3 _ f ^ with the above acrylic resin film: 〇.〇 〇 1 纩: 围 = system 纟〇. Above and above, the resin film is broken or the turtle is plowed. It is possible to suppress the propylene i from peeling off the protective film. The peeling protective film is not particularly limited as long as it is provided in the film laminate traveling direction/method, and includes orbital horses and other directions (for example, a film laminated film, The protective film is peeled off from the coil of the crucible resin in a coiler of a drive shaft such as a sizzling machine. 200914272 In addition, in the above description, the case of winding the film laminate into a cylindrical shape is used. In addition, it is not limited thereto, and the film laminate may not be wound into a cylindrical shape, for example, cut at a predetermined length, as long as the contact surface with the acrylic resin film is adhered at an initial temperature of 23 ° C. The force is applied to the acrylic resin in a range of 0.02 N/50 mm width or more and less than 15 N/5 〇 mm width, and the same effect as the present embodiment can be obtained. According to the aspect of the present embodiment, the film laminate can be wound into a cylindrical shape, and the film can be produced more efficiently. (IV) The film laminate is according to the film laminate of the present embodiment. Containing glass transition temperature 110° C. or more and 200. (: An agglomerate layer in which a protective film is adhered to an acrylic resin film of an acrylic resin in the following garden. In summary, the film laminate according to the embodiment is according to the embodiment. The film laminated body obtained by attaching the above-mentioned protective film to the above-mentioned acrylic resin film according to the present embodiment. In the film laminated body according to the embodiment, the protective film is in contact with the acrylic resin film. The initial adhesion or adhesion at 23 ° C is in the range of 0.02 N / 50 mm or more and less than 0.15 N / 50 mm. The above "adhesion" can be measured by the same method as the initial adhesion described above. Specifically, PMMA (polymethyl methacrylate) was placed on a stainless steel plate and a protective film peeled off from the film laminate as a test film was attached to the PMMA, and the test piece was placed in the 180° direction. The film was peeled at a speed of 300 mm/min, and the load at four places was measured at intervals of 20 mm, and the average value of 200914272 was used as the turtle. As described above, the method for producing the acrylic resin film of the present invention includes attaching the protective film to Containing glass transfer The method for producing an acrylic-based t-fat medium having a step of using an acrylic resin film of an acrylic resin in a range of 200 ° C or less, wherein the contact surface of the protective film with the acrylic film is The initial adhesive force of 23 C is in the range of 〇.〇2N/50mm width and less than 〇.l5N/50mm width. Therefore, it achieves the effect of “stablely producing an acrylic resin film with excellent appearance. Very according to this (4) The film laminate body is contained in a film-containing layer having a glass transition temperature of 11 υ C or more and 200 ° C or less, and a protective film is attached to the enamel layer 0 _ crypto-acrylic acid film and the above-mentioned acrylic resin. The contact surface of the film is the same as the adhesive force of the above protective period of 0.02 N / 50 mm width and 23 C or the initial circumference. Therefore, the invention is not limited to the above-mentioned invention. The present invention is not limited to the above embodiments, and the present invention is not limited thereto. Further, the present invention will be described below, and the following is a convenient , "Quality and genre, and various configurations within the scope of the patent range, and the technical means disclosed in the application can be combined as appropriate to implement the technology of the present invention in different embodiments". For "parts", "liters" is abbreviated as "L". <Dynamic TG> Once the compound (or the compound salt or the colloidal particles) is dissolved or diluted with tetrahydrocyanate, an excess of hexane or methanol is added for reprecipitation, and the precipitate is taken out by vacuum. Drying (ImmHg (l.33hPa), 80〇C, 3 hours or more), removing volatile components, and obtaining the white solid resin according to the following method (dynamic TG method); measuring device: Thermo Plus2 TG-8120 Dynamic TG (manufactured by Physicochemical Co., Ltd.) Measurement conditions: sample amount 5 to 10 mg Heating rate: 10 ° C / min Meng gas: nitrogen flow 200 ml / min Method: Stage isothermal control method (controlled at 60 ° C ~ 500 ° C The mass reduction rate value is 0.005%/sec or less. <Weight average molecular weight> The weight average molecular weight of the polymer is obtained by conversion of polystyrene to GPC (GPC system manufactured by Tosoh Corporation). The liquid system used was chloroform. <Thermal analysis of resin> The thermal analysis of the acrylic resin was carried out under the conditions of a sample of about 10 mg, a temperature increase rate of 10 ° C/min, and a nitrogen gas flow of 50 cc / min, using DSC (physical and chemical company, device name: DSC-8230). Further, the glass transition temperature (Tg) was determined by the midpoint method in accordance with ASTM-D-3418. <Fused Viscosity> The melt viscosity of the sufficiently dried acrylic resin micelles is used 41 200914272

The Capillary Rheometer RH10 manufactured by Bohlin Instruments was used for the measurement. <The ratio of the dealcoholization reaction rate and the ratio of the lactone ring structure> First, the "mass reduction amount due to the dehydration of the polymer composition obtained by polymerization from the polymerization of all hydroxyl groups in the form of decyl alcohol" is used as a reference. In the TG measurement, the mass loss caused by the dealcoholization reaction from 15 CTC before the start of the mass reduction to 300 ° C before the start of the decomposition of the polymer was determined, and the dealcoholization reaction rate was determined. That is, in the dynamic TG measurement of the polymer having a lactone ring structure, the mass reduction rate from 15 (TC to 30 〇t: is measured, and the obtained mass reduction rate is regarded as (X). On the other hand, From the composition of the polymer, all the hydroxyl groups contained in the polymer composition are regarded as alcohols involved in the formation of the lactone ring, assuming a theoretical mass reduction rate at the time of dealcoholation (that is, assuming 100/〇 of the composition The mass reduction rate calculated by the alcohol reaction is taken as (Y). Further, the theoretical mass reduction rate (Y), specifically, the molar amount of the raw material monomer having the structure (hydroxyl group) participating in the dealcoholization reaction in the polymer The ratio, that is, the content of the raw material monomer in the polymer composition can be calculated. Substituting the value (χ, γ) into the dealcoholation formula: 1 - (the actual mass reduction rate (X) / theory Mass reduction rate (γ)) 'The value is obtained and expressed in %, and the dealcoholization reaction rate is obtained. For example, the ratio of the lactone ring structure is calculated for the colloidal particles obtained in the following Production Example 1. The theoretical mass reduction rate of the substance (Υ), the molecular molecule 1 of methanol is 32,2-(hydroxy fluorenyl) The molecular weight of methyl acrylate is 116, and the content (mass ratio) of methyl 2-(hydroxymethyl) acrylate in the polymer is 42.14272, which is 30.0% by mass, and becomes (32/116) χ 30· 0 and 8.28%. On the other hand, the measured mass reduction rate (X) by dynamic TG measurement is 0.25 mass%. If this value is substituted into the above-described dealcoholization formula, it becomes 1-(0.25/8.28) and 0.97. The dealcoholization reaction rate is 97.0%. Thus, only the dealcoholization reaction rate portion is regarded as a lactone cyclization which can be set, and a raw material monomer having a structure (hydroxyl group) participating in the lactone cyclization is subjected to the copolymerization. The content ratio (mass ratio) in the composition is multiplied by the dealcoholization reaction rate to calculate the content ratio of the lactone ring unit structure. In the case of Production Example 1, the copolymerization of 2-(hydroxymethyl) acrylate is carried out. The content of the product was 30.0% by mass, the calculated dealcoholization reaction rate was 97.0% by mass, and the lactone cyclization structure formed when methyl 2-(hydroxymethyl)acrylate having a molecular weight of 116 was condensed with methyl methacrylate The formula of the unit is 170, and the content of the lactone ring in the copolymer is determined. The rate was 42.6 (30.0 乂 0.97 >< 170/116)% by mass. [Production Example 1] In a volume lm3 reaction dad with a stirring device, a temperature sensor, a cooling condenser, and a nitrogen introduction tube, 150 kg was added. Ethyl methacrylate (MMA), 75 kg of 2-(hydroxydecyl)acrylic acid vinegar (MHMA), 25 kg of n-butyl decyl acrylate (BMA), 250 kg of terpene benzene, and nitrogen gas was introduced therein while raising temperature to 105 ° C. After the start of reflux, 15 g of perylene isononanoate (made by Atofina Co., Ltd., trade name: Lupazole 570) was added as a polymerization initiator, and 300 g of polymerization was contained. A solution of the starting agent and 3.5 kg of toluene was added dropwise over 6 hours, and solution polymerization was carried out under reflux (about 150 ° C to 11 ° C), followed by aging for 2 hours. 43 200914272 Into the obtained polymer solution, 50 〇g of octyl phosphate / dioctyl phosphate mixture (manufactured by Sigma Chemical Co., Ltd., trade name: Phoslex A-8) was added under reflux (about 85 to 105). The hydrazine is subjected to a cyclization condensation reaction for 2 hours. Then, the polymer solution obtained by the above cyclization condensation reaction is heated to 220 ° C by a heat exchanger, and is introduced into a barrel at a processing rate of 15 kg / hr in terms of a resin amount. Temperature 25〇t:, the number of revolutions is 17〇 rpm, the degree of pressure is 13.3~400hPa (10~300mmHg), the number of exhaust vents is one, and the number of exhaust vents is 4, the exhaust type screw double-axis extruder (ψ =42ιηηι, L/D=42) 'The cyclization condensation reaction and the devolatilization component were carried out in the extruder, and the transparent rubber particles (1A) were obtained by extrusion. The glass transition temperature of the obtained rubber particles (1A) was 132. At a shear rate of 100 (l/s), the viscosity at a resin temperature of 270 ° C is 670 Pa·s, the weight average molecular weight is 128,000, and the lactone ring content in the copolymer is 42.6 mass%. The rubber pellet (1A) is added to \|/65mm, L/D=32, with a barrier flight type screw A venting uniaxial extruder is attached. The temperature of the rubber pellet (ia) is adjusted to (9) by dehumidifying air heated in the feed hopper, and a nitrogen introduction tube is placed in the lower portion of the feed hopper to introduce the nitrogen gas. The stack is evacuated from the exhaust port at 40 Torr, and melt-kneaded by blocking the threaded screw. After melt-kneading, a gear pump (gear) is used to pass the rubber pellet (1A) through the T die on the 9CTC cooling roller. An acrylic resin film having a thickness of 35 μm was formed. [Example 1] A film of a film thickness of 3 μm μm 44 200914272 was attached to the acrylic resin film obtained in Production Example 1 (trade name: Toratec 7332, East) Latex Film Processing Co., Ltd., initial adhesion at 23 ° C: 〇〇 7N / 5 〇 mm width). Moreover, using the winding clothes (maximum winding width: ψ 6 〇〇 ππη), in the beginning The tension is 5〇N, the tension slope is 15%, and the film (film laminate) to which the protective film is attached is wound into a cylindrical shape. In the winding of the film laminate, the acrylic resin film can be broken for more than 100 hours. The shape of the broken layer is obtained, and the tubular film layer body is obtained. The winding is performed by repeating the operation of "using a core having an inner diameter of 76 mm, winding up to a diameter of 6 mm, and then changing the reel, and then starting to take up." The body was not wound up and collapsed, and no crack occurred at the edge portion of the reel. x When the protective film was peeled off, the acrylic resin film was not damaged. [Comparative Example 1] - A protective film having a film thickness of 6 μm is used (trade name: T〇ratec 7M1, manufactured by Dongf Film Processing Co., Ltd., and the initial adhesion at 23 :: G5 (m/5 〇 mm width) is used as a retention material. A tubular film laminate was produced in the same manner as in Example 。. The shape of the (6) domain body was not taken up, and no crack occurred at the edge portion of the roll. However, when it was protected (4), scratches were caused on the film of the bismuth acrylate resin film. [Comparative Example 2] Except that the operation of Example (5) was carried out, the four cracks and the broken shaft were generated before the film was wounded by the working machine, and the operation could not be continued. X, the roll of the machine has not been wound up and collapsed. However, due to the cracks on both sides of the roll, a lot of fine film fragments are attached, but only 45 200914272 has a poor appearance. [Comparative Example 3] Except for the fixed tension (50 N) of the rod amine + # ττ μ. The winding of the enamel film, the same operation as in Comparative Example 2, except for the product reel "Β, Α命~, 丨 _ In addition to the cracks on both sides, the reeling of the reel is also caused. [Industrial Applicability] As described above, it can be stably manufactured by using the method for producing an acrylic resin film of the present invention. The present invention is applicable to various acrylic resins such as a thin plate, an antireflection film, a retardation film, and a polarizing film which are used in a flat display device such as liquid crystal display cracking. Manufacture of film. [Simple description of the diagram] 益〇ν >*\ [Description of main component symbols] None. 46

Claims (1)

200914272 X. Patent Application Range: 1. A method for preparing an acrylic resin film comprising attaching a protective film to a glass containing transfer temperature of 110. The method for producing an acrylic resin film in the step of the acrylic resin film of the acrylic resin in the range below the above-mentioned range is the same as the initial adhesion of the contact surface of the health and the propylene (four) film to the 23 C. 〇〇 2N/5 〇 wide and above 〇.15N/5〇mm wide. ^The method for preparing the acrylic erbium film according to the scope of the patent application, the progress of which includes the case where the tension slope is set to be in the range of 5% or more and 3% or less, and the tension is decreased as the diameter of the cylinder is increased, and Attached to the above-mentioned steps of the above-mentioned acrylics. The method for producing a propylene-based resin film according to the first or second aspect of the patent, wherein the thickness of the acrylic resin ruthenium is within a range of 50 μm or less. A method for producing an acrylic resin film according to Item 1 or 2, wherein the 5 ^ (tetra) resin comprises a polymer having an inner ring structure. .2—The type of compound is 0.02N/5~~ (4) in addition to the acrylic resin film containing the acrylic resin in the flat above the iurc, and the initial adhesion is in the 6.-species Membrane:::==/5. Within the range of brewing width. The following: L transfer temperature is above the Cong. Attach: Z-acrylic resin on the acrylic resin film. Further, the film laminate of the film is characterized in that the adhesion between the protective film A and the contact surface of the C 47200914272 olefinic resin film at 23 ° C is 0.02 N / 50 mm or more and less than 0.15 N / 50 mm width. Within the scope. 7. The film laminate according to claim 5, wherein the acrylic resin comprises a polymer having a lactone ring structure. 48 200914272 VII. Designation of representative representatives: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: Benefit. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: i