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WO2023085175A1 - Film résistant à la chaleur - Google Patents

Film résistant à la chaleur Download PDF

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Publication number
WO2023085175A1
WO2023085175A1 PCT/JP2022/040883 JP2022040883W WO2023085175A1 WO 2023085175 A1 WO2023085175 A1 WO 2023085175A1 JP 2022040883 W JP2022040883 W JP 2022040883W WO 2023085175 A1 WO2023085175 A1 WO 2023085175A1
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WO
WIPO (PCT)
Prior art keywords
heat
resistant film
elongation
thermoplastic polyester
diol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/040883
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English (en)
Japanese (ja)
Inventor
幹也 林原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to KR1020247015276A priority Critical patent/KR20240089441A/ko
Priority to JP2023559583A priority patent/JPWO2023085175A1/ja
Priority to CN202280074592.4A priority patent/CN118215706A/zh
Publication of WO2023085175A1 publication Critical patent/WO2023085175A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention provides a heat-resistant film suitable for protecting the conductive and decorated surfaces of plastic products, glass products, ceramic products, etc., or when semiconductors are cut and separated to obtain chips. , a heat-resistant film suitable for fixing them, and a pressure-sensitive adhesive sheet using the same.
  • Plastic products, glass products, ceramic products, etc. have not only flat surfaces, but also curved surfaces, as well as uneven shapes.
  • a pressure-sensitive adhesive sheet obtained by laminating a pressure-sensitive adhesive on a film is required to have followability, it is required to have uniform followability in the plane.
  • a suitable rigidity is required in order to fix the wafer and substrate, and to prevent positional displacement and chip scattering during dicing with a blade. Extensibility is required for uniform expansion.
  • high performance such as TSV (Silicon Wafer Through Via) where multiple semiconductor chips are stacked, simplification of the process of directly applying sealing material by transfer molding, etc. Therefore, surface protective films and substrate films used for dicing pressure-sensitive adhesive sheets are required to have heat resistance.
  • the base material of the surface protective film or the adhesive sheet for dicing is, for example, a vinyl aromatic hydrocarbon or a resin composed of a hydrogenated conjugated diene hydrocarbon copolymer and a polypropylene resin.
  • Patent Document 1 A multilayer film characterized by laminating compositions has been disclosed.
  • Polyester resin has a high glass transition temperature and is a material with excellent heat resistance. Focusing on this, an amorphous polyester with a glass transition temperature of 0 to 50 ° C. is disclosed in order to obtain a certain expandability ( Patent document 2). Further, a method of laminating polyester resins having a glass transition temperature of ⁇ 100 to 0° C. and 0 to 100° C. has been disclosed (Patent Document 3).
  • thermoplastic polyester elastomer is composed of a hard segment composed of polyester units composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, and a soft segment composed of an aliphatic diol or an alicyclic diol.
  • block copolymers are known. These have higher heat resistance than polystyrene-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, and the like, and are used in various applications. However, since many block copolymers exhibit a yield point at an elongation of 10 to 30%, uniform elongation becomes difficult when this is exceeded. If measures such as increasing the ratio of soft segments are taken to deal with these problems, heat resistance will be lowered, making it difficult to achieve both heat resistance and expandability.
  • Patent Document 4 proposes a method for improving the extensibility.
  • JP 2009-094418 A Japanese Patent Application Laid-Open No. 2003-092273 JP 2017-034618 A Japanese Patent Application No. 2020-098640
  • Patent Document 1 has sufficient expandability (film elongation), but the heat treatment in the coating process of the adhesive layer, etc., which causes deflection depending on the weight of the wafer, and the high temperature treatment as described above. There is a problem that defects such as wrinkles and pressure marks are generated in the film, which is the base material, due to this.
  • Patent Documents 2 and 3 since the tension is not maintained even after being expanded, bending tends to occur, and when the glass transition temperature is exceeded, the elastic modulus tends to decrease.
  • the wafer basically includes a layer with a low melting point or softening point, there are problems such as defects such as wrinkles and pressure marks, and warping due to the weight of the wafer when subjected to high-temperature processing.
  • Patent Document 4 by the inventors of the present application also exhibits a sufficient effect, in recent years, there has been a demand for further improvement in extensibility.
  • the amount of the soft segment is 30% by mass or more in 100% by mass of the thermoplastic polyester elastomer
  • the thermoplastic polyester-based elastomer has a melting point of 150° C.
  • the heat-resistant film of the present invention is obtained through a heat treatment step at 110°C or higher, wherein the thermoplastic polyester-based elastomer has a melting point of 180°C or higher.
  • the hard segment of the thermoplastic polyester elastomer consists of polybutylene terephthalate units.
  • the main structural unit of the soft segment of the thermoplastic polyester elastomer is an aliphatic polycarbonate, and the elastomer has a melting point of 190°C or higher.
  • the heat-resistant film of the present invention is used as a protective film.
  • the heat-resistant film of the present invention provides a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive on at least one surface of the heat-resistant film described herein.
  • thermoplastic polyester-based elastomer of the present invention can be obtained as a heat-resistant film having heat resistance and high extensibility.
  • the heat-resistant film of the present invention includes the heat treatment according to the present invention, it is particularly suitable for use as a dicing tape for fixing semiconductors and the like when chips are obtained by cutting and separating them. It can be used for heat treatment in the coating process such as , and its excellent extensibility provides sufficient expandability, and the surface protects the surface condition of plastic products, glass products, ceramic products, etc. that have been subjected to electrical conductivity, decoration, etc. Applicable to protective films. Moreover, it becomes possible to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive.
  • the heat-resistant film of the present invention has the compounds and structures described below.
  • thermoplastic polyester-based elastomer used in the heat-resistant film of the present invention comprises a hard segment made of a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, A soft segment composed of an aliphatic diol, an alicyclic diol, or an aliphatic polycarbonate is bonded.
  • the heat-resistant film of the present invention contains the thermoplastic polyester elastomer.
  • aromatic dicarboxylic acids are widely used as the aromatic dicarboxylic acid that constitutes the polyester of the hard segment in the polyester-based elastomer.
  • the aromatic dicarboxylic acid includes terephthalic acid and naphthalenedicarboxylic acid, and terephthalic acid is desirable from the viewpoint of versatility.
  • these compounds can be included as main components of the aromatic dicarboxylic acid according to the present invention.
  • Other acid components include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid and 5-sodiumsulfoisophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride, succinic acid and glutaric acid. , adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and hydrogenated dimer acid.
  • the aliphatic dicarboxylic acid is used within a range that does not greatly lower the melting point of the resin, and the amount thereof is less than 30 mol %, preferably less than 20 mol % of the total acid component.
  • the aliphatic diol or alicyclic diol constituting the hard segment polyester is not particularly limited, but is preferably an alkylene glycol having 2 to 8 carbon atoms. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like, and 1,4-butanediol and 1 ,4-cyclohexanedimethanol is most preferred. Moreover, these compounds can be included as main components of the diols according to the present invention. Therefore, the polyester of the hard segment is preferably composed mainly of butylene terephthalate units or butylene naphthalate units, and more preferably composed of butylene terephthalate units from the viewpoint of physical properties, moldability and cost performance.
  • the aliphatic diol, alicyclic diol, or aliphatic polycarbonate that constitutes the soft segment in the thermoplastic polyester elastomer used in the heat-resistant film of the present invention is poly(ethylene oxide) glycol, poly(propylene oxide) glycol, Poly(alkylene oxides) such as poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of poly(propylene oxide) glycol, copolymers of ethylene oxide and tetrahydrofuran ) glycol and the like, and aliphatic diols having 5 to 12 carbon atoms are preferable from the viewpoint of heat resistance and extensibility.
  • Aliphatic polycarbonate diols are also preferred, and those having a low melting point (for example, 70° C. or lower) and a low glass transition temperature are preferred.
  • a low melting point for example, 70° C. or lower
  • a low glass transition temperature for example, 70° C. or lower
  • an aliphatic polycarbonate diol composed of 1,6-hexanediol has a low glass transition temperature of around ⁇ 60° C. and a melting point of around 50° C., so that it is suitable because it can obtain extensibility at room temperature.
  • an aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of, for example, 3-methyl-1,5-pentanediol with the above aliphatic polycarbonate diol has a glass transition point with respect to the original aliphatic polycarbonate diol.
  • an aliphatic polycarbonate diol composed of 1,9-nonanediol and 2-methyl-1,8-octanediol has a melting point of about 30°C and a glass transition temperature of about -70°C, which are sufficiently low. It corresponds to a good aliphatic polycarbonate diol.
  • These aliphatic polycarbonate diols may be those obtained by copolymerizing a small amount of other glycols, dicarboxylic acids, ester compounds, ether compounds, etc.
  • copolymer components include dimer diol, hydrogenated dimer diol, and Dicarboxylic acids such as glycols, dimer acids, and hydrogenated dimer acids, aliphatic, aromatic, or alicyclic dicarboxylic acids and glycol polyesters or oligoesters, ⁇ -caprolactone, etc.
  • Polyester, or oligoester, polytetramethylene glycol, polyalkylene glycol such as polyoxyethylene glycol, or oligoalkylene glycol, etc. can be used to the extent that the effect of the aliphatic polycarbonate segment is not substantially lost. can.
  • Copolymer components such as polyalkylene glycols such as polyethylene glycol and polyoxytetramethylene glycol, and polyesters such as polycap
  • thermoplastic polyester-based elastomer used for the heat-resistant film of the present invention
  • a hard segment made of a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, and an aliphatic diol or an aliphatic
  • the mass ratio of the soft segment (also referred to as the soft segment amount) composed of the group diol or aliphatic polycarbonate and optionally used copolymer component is 30 in 100% by mass of the thermoplastic polyester elastomer. % by mass or more. Under such conditions, good extensibility can be obtained, and heat resistance can be improved.
  • hard segment:soft segment 40:60 to 70:30.
  • the weight ratio of the hard segment contained in the thermoplastic polyester elastomer is greater than the weight ratio of the soft segment, and the weight ratio of the hard segment contained in the thermoplastic polyester elastomer is 45% or more. desirable from this point of view.
  • hard segment:soft segment 45:55 to 70:30, preferably 48:52 to 70:30.
  • hard segment:soft segment 51:49 to 70:30.
  • the melting point of the thermoplastic polyester elastomer is 150°C or higher, for example, 180°C or higher, and may be 190°C or higher. Also, the melting point is preferably 230° C. or less. When the elastomer exhibits such a melting point, the film strength, tensile elongation at break, and elastic modulus are good, and in addition, high heat resistance, extensibility, and coatability can be exhibited.
  • thermoplastic polyester-based elastomer used for the heat-resistant film of the present invention can be produced by a known method.
  • a lower alcohol diester of dicarboxylic acid, an excessive amount of low molecular weight glycol, and a soft segment component are transesterified in the presence of a catalyst, and the resulting reaction product is polycondensed. and a method of subjecting the soft segment component to an esterification reaction in the presence of a catalyst and polycondensing the resulting reaction product.
  • the hard segment and the soft segment in the thermoplastic polyester elastomer can be combined with a chain extender such as an isocyanate compound.
  • a blocked reaction product a product obtained by repeating a transesterification reaction and a depolymerization reaction for a certain period of time while melting various copolymerization components
  • thermoplastic polyester elastomer used for the heat-resistant film of the present invention has a low melting point, problems may arise in heat resistance, and if the melting point is high, the extensibility may decrease. Therefore, it is desirable that the hard segment consists of polybutylene terephthalate units, although it depends on the method of use. By having polybutylene terephthalate units, excellent heat resistance and extensibility can be provided in a well-balanced manner.
  • the reduced viscosity of the thermoplastic polyester-based elastomer used in the present invention is low, the tensile elongation at break will decrease. Therefore, the reduced viscosity is preferably 1.0 to 2.5 dl/g, more preferably 1.0 to 2.3 dl/g, although it largely depends on the composition of the hard segment and the soft segment and the mass ratio.
  • thermoplastic polyester-based elastomer used in the present invention includes known inorganic compound particles such as silica, talc, zeolite and aluminum borate, polymethyl methacrylate, melamine formalin resin, melamine urea resin, polyester resin, etc., as long as the purpose is not impaired. of organic compound particles can be added. Examples include hydrocarbons such as liquid paraffin, paraffin wax, and synthetic polyethylene wax, aliphatic/higher alcohols such as stearic acid and stearyl alcohol, and fatty acid amides such as stearic acid amide, oleic acid amide, and erucic acid amide.
  • hydrocarbons such as liquid paraffin, paraffin wax, and synthetic polyethylene wax
  • aliphatic/higher alcohols such as stearic acid and stearyl alcohol
  • fatty acid amides such as stearic acid amide, oleic acid amide, and erucic acid amide.
  • each organic slip agent should be 0.5 wt % or less, preferably 0.1 wt % or less.
  • the raw material to be applied to the thermoplastic polyester elastomer used in the present invention is not particularly limited, such as petroleum-derived or plant-derived, but it is preferably plant-derived from the environmental point of view.
  • the heat-resistant film of the present invention includes a hard segment made of a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, and an aliphatic diol or an aliphatic diol or an aliphatic polycarbonate
  • a thermoplastic polyester elastomer in which soft segments composed of are bonded is obtained by forming a film by melt extrusion or the like.
  • a sheet is extruded from a T-die through a single-screw or twin-screw extruder. At that time, it is also possible to obtain a heat-resistant film of different types and layers by using a feed block or a multi-manifold.
  • the extruded sheet material is cooled and solidified by pressing with an air knife, an air chamber, a hard rubber roll, a steel belt, a metal roll, etc. onto the surface of a metal roll in which cooling water and oil are circulating.
  • the sheet-like material can be sandwiched between steel belts on both sides and solidified by cooling.
  • the structure of the heat-resistant film is A: single layer, A/B, A/B/A, A/B/ Layer configurations such as C are possible.
  • another resin layer may be provided between the above layers so as not to cause problems such as delamination.
  • the coefficient of static friction on at least one surface is low, problems such as misalignment may occur during roll winding, and if the coefficient of static friction is high, wrinkles may remain. 0.10 or more is preferable, and 0.15 or more is more preferable.
  • the upper limit is preferably 0.9 or less, and more preferably 0.5 or less, especially when applied to a dicing tape used in the semiconductor manufacturing process, because uniform expandability may not be obtained in the expanding process.
  • the heat-resistant film of the present invention Depending on how the heat-resistant film of the present invention is used, if the overall thickness is small, the feeling of stiffness is small, and if it is large, there may be problems with handleability.
  • the total thickness is 60 ⁇ m. 80 ⁇ m or more is more preferable.
  • 180 micrometers or less are preferable from a viewpoint of a handleability.
  • the heat-resistant film of the present invention preferably has a pressure of 30 to 500 MPa, more preferably 30 to 100 MPa. Within such a range, it is possible to obtain good stretchability and to have an appropriate stiffness. Also, the tensile elongation at break is 200 to 700%, more preferably 350 to 700%. By having such characteristics, it is possible to suppress the occurrence of breakage due to defects that may occur in the cutting step.
  • the ratio F50/F25 of stress F50 at 50% elongation to stress F25 at 25% elongation is 1.10 or more, for example, 1.50 or less.
  • F50/F25 may be from 1.10 to 1.30.
  • abnormalities such as wrinkles and distortion are less likely to occur when stretched in one direction or in multiple directions.
  • the present invention since the present invention has specific hard segments and soft segments, wrinkles and distortion can be suppressed even when stretched in multiple directions.
  • the heat-resistant film of the present invention is subjected to heat treatment. If the heat treatment temperature is low, extensibility cannot be obtained, and it takes time.
  • the temperature is preferably 110° C. or higher, preferably 10° C. lower than the melting point.
  • the heat treatment time after the heat-resistant film reaches a predetermined heat treatment temperature depends on the thickness of the heat-resistant film and the heating method, but the heat treatment time is preferably 1 to 180 sec, and more preferably 2 to 180 sec. preferable.
  • the heat treatment method includes contact heating such as a heating roll, hot air, non-contact heating such as an IR heater, but is not particularly limited, and processes such as adhesive coating and printing. If the heat treatment temperature and heat treatment time are suitable, it is possible to utilize these in the drying step in , heat treatment for any layer laminated with the heat-resistant film, and the like.
  • the heat-resistant film is defined as a film obtained through a heat treatment process at 110°C or higher, as described above.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive is provided on at least one surface of the heat-resistant film according to the present invention.
  • adhesives that can be used in the adhesive sheet of the present invention include (meth)acrylic adhesives, silicone adhesives, urethane adhesives, olefin adhesives, and styrene adhesives. It can be selected according to the object of application, such as a surface protective film that protects the surface condition of plastic products, glass products, ceramic products, etc. that have been subjected to electrical conductivity and decoration.
  • (meth)acrylic pressure-sensitive adhesives are preferable for the dicing tape that fixes wafers and the like when cutting and separating them to obtain chips in the semiconductor process, etc., because the adhesive strength can be easily adjusted.
  • the thickness of the adhesive layer of the above-mentioned adhesive is not particularly limited, but when wafers are cut and separated to obtain chips in the semiconductor manufacturing process, dicing tapes for fixing them, plastic products, glass products, ceramics, etc.
  • the thickness is preferably 1 to 50 ⁇ m from the viewpoint of adhesive strength and uniformity of the thickness of the adhesive layer. More preferably, it is 3 to 30 ⁇ m.
  • the film of the present invention can be used as a protective film.
  • the target film was attached to a frame with an inner diameter of 220 mm with double-sided tape and pressed with a rubber ring to fix it on the outer periphery of the stage below, and then four films were placed at the center point and 45 degrees apart from this.
  • the point of intersection of a straight line and a circle with a diameter of 100 mm is a score, and the stage (diameter 200 mm, rising speed 50 mm / min, holding 60 sec) is raised so that the set elongation obtained by the following formula on the stage is 20%.
  • the film was expanded, and the elongation between ratings was evaluated as follows.
  • Set elongation (%) (amount of stage elevation x 2) / stage diameter x 100 ⁇ : Elongation reaches (45)% or more of the set elongation in all directions, and the maximum difference is less than 2% ⁇ : Elongation reaches (45)% or more of the set elongation in all directions, but a maximum of 2 to 5 ⁇ : (30 to 45)% of the set elongation in some directions, with a maximum difference of 2 to 5% ⁇ : Less than (30)% of the set elongation in some directions, Or there is a maximum difference of 5% or more
  • Adhesive sheet does not curl ⁇ Adhesive sheet curls, but can be corrected by adjusting the tension of the sheet ⁇ Adhesive sheet curls It is difficult to adjust the tension of the material. ⁇ It is difficult to adjust the tension of the sheet material when laminating, and the adhesive thickness of the sheet material is uneven.
  • the resulting resin was passed through an extruder and extruded from a T-die, and pressed against an embossed metal cooling roll with a nip roll to obtain a film with a thickness of 100 ⁇ m.
  • heat treatment was performed for about 2 seconds by contact with an electric heating roll in the process. Examples and comparative examples are listed in Table 1.
  • Examples 4-6, Comparative Examples 4-7> Dimethyl terephthalate and 1,4-butanediol are charged together with a catalyst, and after transesterification by a conventional method, polytetramethylene glycol having a number average molecular weight of 1000 is added and polycondensed while increasing the temperature and reducing the pressure to obtain a predetermined soft segment mass ratio.
  • a resin having The resulting resin was passed through an extruder and extruded from a T-die, and pressed against an embossed metal cooling roll with a nip roll to obtain a film with a thickness of 100 ⁇ m.
  • heat treatment was performed for about 2 seconds by contact with an electric heating roll in the same process as in Examples 1 to 3. Examples and comparative examples are listed in Table 2.
  • Examples 7-9, Comparative Examples 8-10> Dimethyl nalephthalate and 1,4-butanediol are charged together with a catalyst, and after transesterification by a conventional method, polytetramethylene glycol having a number average molecular weight of 1000 is added and polycondensed while increasing the temperature and reducing the pressure to obtain a predetermined soft segment mass. A resin with a ratio was obtained. The resulting resin was passed through an extruder and extruded from a T-die, and pressed against an embossed metal cooling roll with a nip roll to obtain a film with a thickness of 100 ⁇ m. In this example, after cutting off the thick end portion of the obtained film, heat treatment was performed for about 2 seconds by contact with an electric heating roll in the same process as in Examples 1 to 3. Examples and comparative examples are listed in Table 3.
  • the polyester-based elastomer is composed of a hard segment made of a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, and an aliphatic diol or an alicyclic diol. It is a heat-resistant film using a resin composed of soft segments in which soft segments are bonded, and in the examples, it has a predetermined mass ratio of hard segments and soft segments. By applying it, high elongation and uniform elongation can be obtained, and in addition, high heat resistance, which is a characteristic of polyester elastomers, is maintained. In addition, it is easy to adjust the tension in the coating of the adhesive, so that unevenness in the thickness of the adhesive due to lamination of the release film and curling between sheets are reduced.
  • the heat-resistant film of the present invention uses a polyester-based elastomer and has high heat resistance, which is its characteristic.
  • high elongation and uniform elongation can be obtained in terms of expandability, and a stable pressure-sensitive adhesive sheet can be obtained even in processing steps such as coating. .
  • it is suitable as a surface protection film for protecting the surface state of conductive or decorated plastic products, ceramic products, etc.
  • it can be used as a surface protection film in the semiconductor manufacturing process or as a dicing tape. , is preferred.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un film résistant à la chaleur approprié pour protéger l'état d'une surface de, par exemple, un produit en plastique, un produit en verre ou un produit en céramique, la surface ayant une conductivité électrique, une décoration, etc., étant conférée à celle-ci. La solution selon l'invention porte sur un film résistant à la chaleur qui comprend un élastomère à base de polyester thermoplastique comprenant un segment dur ayant une unité polyester formée à partir d'un acide dicarboxylique aromatique et d'un diol aliphatique ou alicyclique et un segment souple lié au segment dur et comprenant un diol aliphatique, un diol alicyclique ou un polycarbonate aliphatique, la quantité du segment souple étant égale ou supérieure à 30 % en masse par rapport à 100 % en masse de l'élastomère à base de polyester thermoplastique et l'élastomère à base de polyester thermoplastique ayant un point de fusion de 150 °C ou plus. Le film résistant à la chaleur a un module d'élasticité en traction de 30 à 500 MPa, un allongement à la rupture par traction de 200 à 700 % et un rapport de la contrainte F50 à 50 % d'allongement à la contrainte F25 à 25 % d'allongement, F50/F25, de 1,10 ou plus.
PCT/JP2022/040883 2021-11-10 2022-11-01 Film résistant à la chaleur Ceased WO2023085175A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2025115683A1 (fr) * 2023-11-28 2025-06-05 東洋紡株式会社 Film adhésif résistant à la chaleur

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JP2000094579A (ja) * 1998-09-22 2000-04-04 Toyobo Co Ltd 熱可塑性ポリエステルエラストマー積層体
WO2007072748A1 (fr) * 2005-12-19 2007-06-28 Toyo Boseki Kabushiki Kaisha Elastomere de polyester thermoplastique, composition d'elastomere de polyester thermoplastique, et procede pour la production d'elastomere de polyester thermoplastique
WO2008093574A1 (fr) * 2007-01-29 2008-08-07 Toyo Boseki Kabushiki Kaisha Procédé de fabrication d'un élastomère de polyester thermoplastique de type polyester-polycarbonate et élastomère de polyester thermoplastique de type polyester-polycarbonate
JP2008291238A (ja) * 2007-04-24 2008-12-04 Toyobo Co Ltd ポリエステルエラストマー組成物及びその用途、並びにポリエステルエラストマー組成物の製造方法
JP2014047222A (ja) * 2012-08-29 2014-03-17 Toyobo Co Ltd 熱可塑性ポリエステルエラストマー、およびそれからなる成形体
WO2021246239A1 (fr) * 2020-06-05 2021-12-09 東洋紡株式会社 Film résistant à la chaleur

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JP2003092273A (ja) 2001-09-19 2003-03-28 Mitsubishi Plastics Ind Ltd 半導体ウエハ用ダイシングフィルム
JP5053026B2 (ja) 2007-10-12 2012-10-17 グンゼ株式会社 多層ダイシング用基体フィルム及びダイシングフィルム
JP2017034618A (ja) 2015-08-06 2017-02-09 日立マクセル株式会社 放送受信装置及び出力映像情報生成方法
WO2019115812A1 (fr) 2017-12-14 2019-06-20 Universite De Strasbourg Peptides pour le traitement et la prévention d'une stéatose hépatique non alcoolique et d'une fibrose

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JP2000094579A (ja) * 1998-09-22 2000-04-04 Toyobo Co Ltd 熱可塑性ポリエステルエラストマー積層体
WO2007072748A1 (fr) * 2005-12-19 2007-06-28 Toyo Boseki Kabushiki Kaisha Elastomere de polyester thermoplastique, composition d'elastomere de polyester thermoplastique, et procede pour la production d'elastomere de polyester thermoplastique
WO2008093574A1 (fr) * 2007-01-29 2008-08-07 Toyo Boseki Kabushiki Kaisha Procédé de fabrication d'un élastomère de polyester thermoplastique de type polyester-polycarbonate et élastomère de polyester thermoplastique de type polyester-polycarbonate
JP2008291238A (ja) * 2007-04-24 2008-12-04 Toyobo Co Ltd ポリエステルエラストマー組成物及びその用途、並びにポリエステルエラストマー組成物の製造方法
JP2014047222A (ja) * 2012-08-29 2014-03-17 Toyobo Co Ltd 熱可塑性ポリエステルエラストマー、およびそれからなる成形体
WO2021246239A1 (fr) * 2020-06-05 2021-12-09 東洋紡株式会社 Film résistant à la chaleur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025115683A1 (fr) * 2023-11-28 2025-06-05 東洋紡株式会社 Film adhésif résistant à la chaleur

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