WO2021246239A1 - 耐熱性フィルム - Google Patents
耐熱性フィルム Download PDFInfo
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- WO2021246239A1 WO2021246239A1 PCT/JP2021/019791 JP2021019791W WO2021246239A1 WO 2021246239 A1 WO2021246239 A1 WO 2021246239A1 JP 2021019791 W JP2021019791 W JP 2021019791W WO 2021246239 A1 WO2021246239 A1 WO 2021246239A1
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- polyester
- heat
- resistant film
- elongation
- hard segment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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]
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
- B32B2264/1021—Silica
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/20—Particles characterised by shape
- B32B2264/202—Solid spheres
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/30—Particles characterised by physical dimension
- B32B2264/303—Average diameter greater than 1µm
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- 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
- B32B2274/00—Thermoplastic elastomer material
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- 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
- C09J2469/00—Presence of polycarbonate
- C09J2469/006—Presence of polycarbonate in the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
Definitions
- the present invention protects the conductive and decorated surface states of plastic products, glass products, ceramic products, etc., or fixes them when cutting and separating semiconductors, etc. to obtain chips.
- the present invention relates to a heat resistant film suitable for the above.
- Plastic products, glass products, ceramic products, etc. have not only flat surfaces but also curved surfaces, and also have shapes such as irregularities, and films that protect these are required to be adaptable to various applications. For example, since a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive is laminated on a film is required to have followability, uniform in-plane followability is required.
- the semiconductor manufacturing process includes a dicing process that cuts wafers and substrates into chips, and an expanding process that widens the intervals between individual chips so that they can be easily picked up with a suction jig. It also goes through a pickup process for collecting chips.
- a dicing process that cuts wafers and substrates into chips
- an expanding process that widens the intervals between individual chips so that they can be easily picked up with a suction jig. It also goes through a pickup process for collecting chips.
- protective films, adhesive sheets, etc. that can reduce the load at that time in each process.
- the wafer and substrate are fixed, and appropriate rigidity is required to prevent misalignment and chip scattering due to dicing by blades, etc., and in the expanding process, the chip spacing can be expanded uniformly. Stretchability is required.
- high performance such as TSV (Through Silicon Via) in which multiple semiconductor chips are laminated, simplification of the process of directly applying the encapsulant in transfer molding, etc., processing to a high temperature of 150 ° C or higher for the wafer, etc. Therefore, the base material used for the surface protective film and the dicing tape is required to have heat resistance.
- the base material of the surface protective film or the pressure-sensitive adhesive sheet as a dicing tape is made of, for example, a vinyl aromatic hydrocarbon, a conjugated diene hydrocarbon copolymer hydrogenated additive, and a polypropylene-based resin.
- a multilayer film characterized by laminating a resin composition is disclosed.
- the base material has defects such as wrinkles and pressing marks due to the heat treatment in the coating process such as the adhesive layer, which causes bending due to the weight of the wafer, and the high temperature treatment as described above. There are problems such as (Patent Document 1).
- the polyester-based resin is a material having a high glass transition temperature and excellent heat resistance, and paying attention to this, an amorphous polyester having a glass transition temperature of 0 to 50 ° C. in order to obtain a certain expandability is disclosed. However, since the tension is not maintained even when expanded, bending or the like is likely to occur, and the elastic modulus decreases when the glass transition temperature is exceeded. Further, a method of laminating polyester resins having glass transition temperatures of ⁇ 100 to 0 ° C. and 0 to 100 ° C. is disclosed.
- Patent Documents 2 to 3 since it basically contains a layer having a low melting point or a softening point, there are problems such as defects such as wrinkles and pressing marks and bending due to the weight of the wafer when the treatment is performed at a high temperature.
- Polyester-based elastomers are block copolymers in which a hard segment composed of an aromatic dicarboxylic acid, an aliphatic diol or an alicyclic diol, and a soft segment mainly composed of an alicyclic diol are bonded.
- These have higher heat resistance than polystyrene-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, etc., and are being developed for various uses.
- many block copolymers develop a yield point at a low elongation of 10-25%, which makes uniform elongation difficult. If measures such as increasing the ratio of soft segments are taken to address these issues, the heat resistance will decrease, and both heat resistance and expandability will not be achieved.
- the present invention protects the conductive and decorated surface states of plastic products, glass products, ceramic products, etc., or cuts and separates wafers in the semiconductor manufacturing process.
- An object of the present invention is to provide a heat-resistant film suitable for fixing.
- a heat-resistant film made of a thermoplastic resin which is a polyester-based elastomer in which a hard segment and a soft segment are bonded.
- the hard segment has a polyester unit composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol.
- the soft segment is mainly composed of aliphatic polycarbonate and is composed of
- the weight ratio of the hard segment contained in the polyester elastomer exceeds 50%
- the film made of the thermoplastic resin has an elastic modulus of 30 to 500 MPa, a breaking elongation of 200 to 700%, and a ratio F50 / F25 of stress F50 at elongation 50% to stress F25 at elongation 25% of 1.05 or more.
- Heat resistant film [2] The heat-resistant film, wherein the hard segment of the polyester-based elastomer is composed of polybutylene terephthalate units, and the melting point of the polyester-based elastomer is 195 to 220 ° C.
- the heat-resistant film wherein the hard segment of the polyester-based elastomer is composed of polybutylene naphthalate units, and the melting point of the polyester-based elastomer is 210 to 240 ° C.
- the above-mentioned heat-resistant film used for protective film applications.
- An adhesive sheet having an adhesive on at least one surface of the heat-resistant film.
- the heat-resistant film of the present invention is formed from a specific polyester-based elastomer.
- the soft segment according to the present invention is included, a heat-resistant film having excellent heat resistance and high expandability can be obtained.
- the heat-resistant film of the present invention is mainly suitable for use as a dicing tape for fixing semiconductors and the like when cutting and separating them to obtain chips, and is also heat-treated in a coating process for an adhesive layer or the like. It is possible to apply it to a surface protection film that protects the surface condition of plastic products, glass products, ceramic products, etc. that has been subjected to conductivity, decoration, etc. .. Further, it becomes possible to provide an adhesive sheet having an adhesive.
- the heat-resistant film of the present invention has the compounds described below, the structure, and the like.
- the polyester-based elastomer used for the heat-resistant film of the present invention includes a hard segment made of polyester composed of an aromatic dicarboxylic acid, an aliphatic diol or an alicyclic diol, and a soft segment mainly made of an aliphatic polycarbonate. It is combined.
- the aromatic dicarboxylic acid constituting the hard segment polyester in the polyester-based elastomer an ordinary aromatic dicarboxylic acid is widely used.
- the aromatic dicarboxylic acid is preferably terephthalic acid or naphthalene dicarboxylic acid. Further, these compounds can be contained as the main component 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-sodium sulfoisophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrochloride phthalic acid, and succinic acid and glutaric acid.
- aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid and 5-sodium sulfoisophthalic acid
- alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrochloride phthalic acid
- succinic acid and glutaric acid succinic acid and glutaric acid.
- Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, hydrogenated dimer acid and other aliphatic dicarboxylic acids are added.
- the aliphatic dicarboxylic acid thereof is used within a range that does not significantly 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 polyester of the hard segment is not particularly limited, but is preferably alkylene glycols having 2 to 8 carbon atoms. Specific examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, etc., 1,4-butanediol, and 1 , 4-Cyclohexanedimethanol is most preferred.
- polyester of the hard segment a polyester mainly composed of a butylene terephthalate unit or a butylene naphthalate unit is preferable from the viewpoint of physical characteristics, moldability and cost performance.
- the aliphatic diol constituting the soft segment in the polyester-based elastomer used for the heat-resistant film of the present invention is preferably an aliphatic polycarbonate diol having a low melting point (for example, 70 ° C. or lower) and a low glass transition temperature.
- 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 is suitable because it has a low glass transition temperature of about -60 ° C and a melting point of about 50 ° C, so that extensibility at room temperature can be obtained.
- the aliphatic polycarbonate diol obtained by copolymerizing the above aliphatic polycarbonate diol with, for example, 3-methyl-1,5-pentanediol in an appropriate amount has a glass transition point with respect to the original aliphatic polycarbonate diol. Although slightly higher, the melting point is lowered or amorphous, which corresponds to a good aliphatic polycarbonate diol. Further, for example, the aliphatic polycarbonate diol composed of 1,9-nonane diol and 2-methyl-1,8-octane diol has a melting point of about 30 ° C. and a glass transition temperature of about ⁇ 70 ° C., which are sufficiently low.
- aliphatic polycarbonate diols may be obtained by copolymerizing a small amount of other glycols, dicarboxylic acids, ester compounds, ether compounds, etc., and examples of the copolymerization components include dimer diols, hydrogenated dimer diols, and modifications thereof.
- Glycol such as body, dicarboxylic acid such as dimer acid and hydrogenated dimer acid, polyester composed of aliphatic, aromatic or alicyclic dicarboxylic acid and glycol, or polyester composed of oligoester, ⁇ -caprolactone and the like.
- polyalkylene glycols such as oligoesters, polytetramethylene glycols and polyoxyethylene glycols, or oligoalkylene glycols can be mentioned, and can be used to the extent that the effect of the aliphatic polycarbonate segment is not substantially lost.
- ethylene glycol 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2-dimethyl-1,3- Mainly 2 carbon atoms such as propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc.
- aliphatic diol residues is composed of ⁇ 12 aliphatic diol residues, and in particular, an aliphatic diol having 5 to 12 carbon atoms is preferable from the viewpoint of heat resistance and extensibility, and these components may be used alone or as needed. You may use two or more kinds together. Further, even if a copolymerization component such as polyalkylene glycol such as polyethylene glycol or polyoxytetramethylene glycol or polyester such as polycaprolactone or polybutylene adipate is introduced as a soft segment to the extent that the effect of the invention is not lost. good.
- a copolymerization component such as polyalkylene glycol such as polyethylene glycol or polyoxytetramethylene glycol or polyester such as polycaprolactone or polybutylene adipate is introduced as a soft segment to the extent that the effect of the invention is not lost. good.
- a hard segment made of a polyester composed of an aromatic dicarboxylic acid, an aliphatic diol, or an alicyclic diol, an aliphatic polycarbonate, and, if necessary, an aliphatic polycarbonate.
- the mass ratio of the soft segment composed of the copolymerized component used in the above the extensibility may decrease when the mass ratio of the hard segment increases, and the heat resistance may decrease when the mass ratio of the soft segment increases.
- Hard segment: Soft segment 40:60 to 80:20.
- the weight ratio of the hard segment contained in the polyester-based elastomer is larger than the weight ratio of the soft segment, and the weight ratio of the hard segment contained in the polyester-based elastomer exceeds 50%.
- the polyester-based elastomer used in the heat-resistant film of the present invention includes a hard segment made of polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol, and a soft segment mainly made of an aliphatic polycarbonate. It is preferable that the units constituting the hard segment and / or the soft segment are directly bonded by an ester bond or a carbonate bond.
- the hard segment and the soft segment in the polyester-based elastomer are bonded with a chain extender such as an isocyanate compound.
- a chain extender such as an isocyanate compound.
- the polyester constituting the hard segment, the polycarbonate constituting the soft segment, and the necessary If there is, the polycarbodiimide compound 0 is obtained by repeating the transesterification reaction and the depolymerization reaction for a certain period of time under melting of various copolymerization components (hereinafter, also referred to as a blocking reaction product) with respect to 100 parts by mass. It is desirable to contain 5 to 10 parts by mass, for example, 0.5 to 6 parts by mass of the polycarbodiimide compound, and more preferably 1.0 to 3.0 parts by mass.
- the above polycarbodiimide compound can be obtained, for example, by a decarbonation reaction of a diisocyanate compound, and applicable diisocyanates include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and 1,3.
- the terminal isocyanate can be used as it is, but the degree of polymerization can be controlled by reacting the terminal isocyanate, and a part of the terminal isocyanate can be blocked.
- polycarbodiimide compounds alicyclic polycarbodiimides containing dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate and the like as main raw materials are preferable. Further, those having an isocyanate group at the terminal and having an isocyanate group content of about 0.5 to 4% by mass are preferable in terms of stability and handleability, and the isocyanate group content is about 1 to 3% by mass. Is more preferable.
- polycarbodiimides derived from dicyclohexylmethane diisocyanate or isophorone diisocyanate preferably having an isocyanate group content of 0.5 to 4% by mass, and more preferably having an isocyanate group content of 1 to 3% by mass.
- the isocyanate group content can be measured by a conventional method (a method of dissolving with amine and performing back titration with hydrochloric acid).
- the number of carbodiimide groups in the carbodiimide compound is preferably 2 to 50, more preferably 5 to 30, in terms of thermal stability and the like. Further, in the case of such a degree of polymerization, since it is solid at around room temperature, it is excellent in workability and compatibility when mixed with a polyester-based elastomer by being powdered, so that a uniform reaction and bleed-out resistance can be expected. preferable.
- the number of carbodiimide groups is the number of carbodiimides in the polycarbodiimide compound, and if it is a polycarbodiimide obtained from a diisocyanate compound, it corresponds to the degree of polymerization.
- polycarbodiimide is a mixture of molecules of various lengths, the number of carbodiimide groups is represented by an average value, and the number of carbodiimide groups is also the same as described above by the conventional method (dissolved in amine and back titrated with hydrochloric acid). Method) can be used for measurement.
- JIS K 7210 "Plastic − Thermoplastic Melt Mass Flow Rate”
- MFR melt volume flow rate
- a glycidyl group containing 2 or more per molecule is 4,000 to 25,000 weight average molecular weight, and, applying a reactive compound epoxy value of from 400 to 780 eq / 10 6 g
- the reactive compound preferably contains 0.1 to 30 parts by mass, more preferably 0.5 to 5 parts by mass.
- the ratio F50 / F25 of the stress F50 at the elongation of 50% to the stress F25 at the elongation of 25% becomes large, and uniform extensibility can be obtained.
- the ratio F50 / F25 of the stress F50 at an elongation of 50% to the stress F25 at an elongation of 25% is 1.05 or more, for example, 2.0 or less.
- F50 / F25 may be 1.05 or more and 1.6 or less. When F50 / F25 is within such a range, abnormalities such as wrinkles and distortion are less likely to occur when the F50 / F25 is stretched in one direction or in multiple directions.
- a hard segment made of a polyester composed of an aromatic dicarboxylic acid, an aliphatic diol or an alicyclic diol, and a soft segment mainly made of an aliphatic polycarbonate, which are contained in the heat-resistant film of the present invention, are bonded to each other.
- the polyester-based elastomer may have a problem in heat resistance when the melting point is low, and when the melting point is high, the extensibility may be lowered.
- the polyester-based elastomer has a melting point of 195 ° C. or higher, and when the hard segment is composed of polybutylene terephthalate units, the melting point is preferably 195 to 220 ° C.
- the melting point is preferably 210 to 240 ° C.
- the polyester-based elastomer includes known inorganic compound particles such as silica, talc, zeolite and aluminum borate, and organic compounds such as polymethyl methacrylate, melamine formalin resin, melamine urea resin and polyester resin, as long as the purpose is not impaired. It is possible to add particles and the like. However, it is exemplified by 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, and fatty acid amides such as stearic acid amide, oleic acid amide and erucic acid amide.
- the extraction amount by soxley extraction with chloroform in accordance with JIS K 6229 "Rubber − Solvent Extract Determination (Quantitative)" is 1 wt% or less. It is important that it is not substantially contained, and when it is added, the amount of each organic slip agent is preferably 0.5 wt% or less, more preferably 0.1 wt% or less.
- the raw material applied to the polyester-based elastomer is not particularly limited, such as petroleum-derived or plant-derived, but plant-derived is preferable from the viewpoint of the environment.
- the heat-resistant film of the present invention is a polyester-based film in which a hard segment made of a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol or an alicyclic diol is bonded to a soft segment mainly made of an aliphatic polycarbonate. It can be obtained by forming an elastomer into a sheet by melt extrusion or the like.
- melt extrusion As melt extrusion, it is extruded as a sheet from the T die through a single-screw or twin-screw extruder.
- the extruded sheet-like material is cooled and solidified by pressing it against the surface of a metal roll in which cooling water and oil circulate with an air knife, an air chamber, a hard rubber roll, a steel belt, a metal roll, or the like. Further, both sides of the sheet-like material can be sandwiched between steel belts to be cooled and solidified. Further, the above-mentioned sheet-like material can also be obtained as a heterogeneous multi-layer sheet-like material by using a feed block or a multi-manifold.
- the above-mentioned sheet-like material can be stretched uniaxially or biaxially as needed, and if the total draw ratio is high, the extensibility may be impaired, and if it is low, the thickness may be impaired. Since the fluctuation may be large, 3 to 12 times is preferable.
- the heat-resistant film of the present invention may be made of a similar polyester-based elastomer, a different type of elastomer, a polyester-based resin, a different kind of resin, etc. It is possible to form a layer, and it is also possible to provide another resin layer between the layers so that problems such as delamination do not occur.
- the lower limit is preferably 0.10 or more. , More preferably 0.15 or more.
- the upper limit is preferably 0.9 or less, and particularly preferably 0.5 or less because uniform expandability may not be obtained in the expanding step when applied to a dicing tape used in a semiconductor process.
- the heat-resistant film of the present invention may have a small waist feeling when the overall thickness is small, and may cause a problem in handleability when the total thickness is large.
- the overall thickness is preferably 60 ⁇ m or more, because fractures may occur due to defects generated in the cutting process and / or uniform expandability may not be obtained. More preferably, it is 80 ⁇ m or more. Further, 180 ⁇ m or less is preferable from the viewpoint of handleability.
- thermoplastic resin film of the present invention does not have stretchability when the elastic modulus is large, and the waist feeling is small when the elastic modulus is small. Therefore, 30 to 500 MPa is desirable, and 30 to 100 MPa is more preferable.
- the elongation at break may be 200 to 700%, for example, 350 to 700%.
- 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.
- the pressure-sensitive adhesive that can be used for the pressure-sensitive adhesive sheet of the present invention include (meth) acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, olefin-based pressure-sensitive adhesives, and styrene-based pressure-sensitive adhesives. It can be selected according to the object to be applied, such as a surface protective film that protects the surface condition of plastic products, glass products, ceramic products, etc. that has been subjected to conductivity and decoration. Further, among these, a (meth) acrylic pressure-sensitive adhesive that can easily adjust the adhesive strength is preferable as the dicing tape for fixing these when cutting and separating wafers and the like in a semiconductor process or the like to obtain chips. ..
- the thickness of the pressure-sensitive adhesive layer due to the above-mentioned adhesive is not particularly limited, but dicing tape for fixing these when cutting and separating wafers and the like in a semiconductor process to obtain chips, as well as plastic products, glass products, and ceramic products.
- dicing tape for fixing these when cutting and separating wafers and the like in a semiconductor process to obtain chips, as well as plastic products, glass products, and ceramic products.
- it is preferably 1 to 50 ⁇ m from the viewpoint of adhesive strength and uniformity of the thickness of the adhesive layer. It is more preferably about 30 ⁇ m.
- the evaluation method of physical properties in the examples is as follows.
- Elongation (%) (stage movement distance x 2) / frame inner diameter x 100 ⁇ : 65% or more of the predetermined elongation is reached in all directions, and the maximum difference is less than 2%. ⁇ : 65% or more of the predetermined elongation is reached in all directions, but the maximum is 2 to 5%. There is a difference ⁇ : There is a difference of up to 2 to 5% with an elongation of 50 to 65% of the predetermined elongation in some directions ⁇ : An elongation of less than 50% of the predetermined elongation in some directions There is a difference of 5% or more
- Examples 1 and 2 A preparation obtained by reacting a commercially available 1,6-hexanediol type aliphatic polycarbonate diol (molecular weight 2,000) with diphenyl carbonate at a temperature of 205 ° C. and a pressure of 130 Pa for 2 hours (number average molecular weight 10, By polycondensing PBT (polybutylene terephthalate) with respect to 000) under high temperature and reduced pressure, a resin having a mass ratio of a predetermined soft segment shown in Table 1 was obtained.
- PBT polybutylene terephthalate
- a pellet-shaped MB (masterbatch) containing 15 wt% of commercially available spherical silica (average particle size 12 ⁇ m) based on the obtained resin (for layer A) was prepared, and the spherical silica was 7 by the masterbatch.
- a resin (for layer B) adjusted to 500 ppm the film thickness of composition A becomes 10% of the total thickness, and further, it is extruded from the T die through an extruder so as to have the structure of composition A / B.
- the sheet was formed into a sheet at a temperature higher than the melting point by about 10 ° C. for about 4 to 5 hours, but no abnormal pressure of extrusion or discharge was observed.
- Table 1 shows the characteristics of the resin used and the evaluation results of the heat-resistant film and roll.
- Comparative Example 1 and Comparative Example 2 films were produced in the same manner as in Example 1 except that the resins under the conditions shown in Table 1 were used. Table 1 shows the physical characteristics of the obtained film.
- Examples 3 to 4> A preparation obtained by reacting a commercially available 1,6-hexanediol type aliphatic polycarbonate diol (molecular weight 2000) with diphenyl carbonate at a temperature of 205 ° C. and a pressure of 130 Pa for 2 hours (number average molecular weight 10,000).
- a resin was obtained in the same manner as in Example 1 described above, except that PBN (polybutylene naphthalate) was used.
- the film thickness of the configuration A is 10% of the total thickness, and a film is formed so as to have the structure of the configuration A / B, the total film thickness is 100 ⁇ m, the width is 650 mm, and the winding length.
- a roll of a heat resistant film of 1,000 m was obtained.
- the sheet was formed into a sheet at a temperature higher than the melting point by about 10 ° C. for about 4 to 5 hours, but no abnormal pressure of extrusion or discharge was observed.
- Table 1 shows the characteristics of the resin used and the evaluation results of the heat-resistant film and roll.
- the polyester-based elastomer is a combination of a hard segment made of polyester composed of aromatic dicarboxylic acid, an aliphatic diol or an alicyclic diol, and a soft segment mainly made of aliphatic polycarbonate. It is a heat-resistant film that uses polycarbonate, and in the examples, it is easy to adjust the tension when applying the adhesive. Curl becomes smaller. Further, in terms of expandability, uniform elongation can be obtained even with high elongation, and in addition, the high heat resistance characteristic of polyester elastomers is maintained.
- Examples 5 to 12 A preparation obtained by reacting a mixture of a commercially available 1,6-hexanediol type aliphatic polycarbonate diol (molecular weight 2000) described in Examples 1 to 4 with diphenyl carbonate at a temperature of 205 ° C. and a pressure of 130 Pa for 2 hours.
- PBT polybutylene terephthalate
- PBN polybutylene naphthalate
- a resin (for layer B) adjusted to 7,500 ppm a carbodiimide compound (“carbodilite LA-1”) is supplied in a predetermined amount as a side feed when the resin for layer A and the resin for layer B are extruded.
- a heat-resistant film was produced in the same manner as in Example 1 except for the above.
- the film thickness of the configuration A becomes 10% of the total thickness
- the extrusion is performed from the T die through an extruder so as to have the structure of the configuration A / B, and then pressed against a cooling roll with an air knife.
- a roll having a width of 650 mm and a winding length of 1,000 m was obtained as a heat-resistant film having a total thickness of 100 ⁇ m according to Examples 5 to 12.
- Table 2 shows the characteristics of the resin in Examples 5 to 12 and the evaluation results of the sheet-like material and the roll of the resin.
- the polyester-based elastomer is a combination of a hard segment made of polyester composed of an aromatic dicarboxylic acid, an aliphatic diol or an alicyclic diol, and a soft segment mainly made of an aliphatic polycarbonate. It is a heat-resistant film that uses a resin.
- the addition of the polycarbodiimide compound improves the expandability and increases the reduced viscosity corresponding to the molecular weight, which gives an opportunity to whiten with a cooling roll when obtaining a heat-resistant film. Is reduced, and the temperature of the cooling roll can be easily controlled.
- the pressure-sensitive adhesive sheet of the present invention is a heat-resistant film made of a polyester-based elastomer, and has high heat resistance, which is a feature thereof. Further, by setting an appropriate amount of a predetermined soft segment applied to the polyester-based elastomer, it is stable in a processing process such as coating, and uniform elongation can be obtained even in a high elongation in terms of expandability. Therefore, it is suitable as a surface protective film that protects the surface condition of plastic products, glass products, ceramic products, etc. that has been subjected to conductivity, decoration, etc., and is particularly suitable as a surface protective film or dicing tape in a semiconductor process. Suitable.
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Abstract
Description
また、ガラス転移温度が-100~0℃と0~100℃のポリエステル系樹脂を積層する方法が開示されている。しかし、基本的に融点、あるいは、軟化点が低い層を含むため、高温になる処理が行なわれると、シワや押圧痕などの欠陥が生じる、ウエハの重量でたわみが生じるなどの問題がある(特許文献2~3)。
該ハードセグメントは、芳香族ジカルボン酸と、脂肪族ジオール、又は、脂環族ジオールから構成されたポリエステル単位を有し、
該ソフトセグメントは、主として脂肪族ポリカーボネートから構成され、
該ポリエステル系エラストマーに含まれる該ハードセグメントの重量比が50%を超え、
該熱可塑性樹脂からなるフィルムは、弾性率が30~500MPa、破断伸度が200~700%、伸度25%における応力F25に対する伸度50%における応力F50の比F50/F25が1.05以上である耐熱性フィルム。
[2]ポリエステル系エラストマーのハードセグメントがポリブチレンテレフタレート単位よりなり、かつ、ポリエステル系エラストマーの融点が195~220℃であることを特徴とする上記耐熱性フィルム。
[3]ポリエステル系エラストマーのハードセグメントがポリブチレンナフタレート単位よりなり、かつ、ポリエステル系エラストマーの融点が210~240℃であることを特徴とする上記耐熱性フィルム。
[4]保護フィルム用途に用いられる、上記の耐熱性フィルム。
[5]上記の耐熱性フィルムの少なくとも一方の面に、粘着剤を有する粘着シート。
本発明の耐熱性フィルムに用いるポリエステル系エラストマーは、芳香族ジカルボン酸と、脂肪族ジオール、又は、脂環族ジオールとから構成されたポリエステルからなるハードセグメントと、主として脂肪族ポリカーボネートからなるソフトセグメントが結合されてなる。
その他の酸成分としては、ジフェニルジカルボン酸、イソフタル酸、5-ナトリウムスルホイソフタル酸などの芳香族ジカルボン酸、シクロヘキサンジカルボン酸、テトラヒドロ無水フタル酸などの脂環族ジカルボン酸、これにコハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカン二酸、ダイマー酸、水添ダイマー酸などの脂肪族ジカルボン酸などを付与したものが挙げられる。なお、これの脂肪族ジカルボン酸は樹脂の融点を大きく低下させない範囲で用いられ、その量は全酸成分の30モル%未満、好ましくは20モル%未満である。
ハードセグメントのポリエステルを構成する脂肪族ジオール、又は、脂環族ジオールは、特に限定されないが、炭素数2~8のアルキレングリコール類であることが好ましい。具体的にはエチレングリコール、1,3-プロピレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,4-シクロヘキサンジメタノールなどが挙げられ、1,4-ブタンジオール、及び、1,4-シクロヘキサンジメタノールが最も好ましい。また、これら化合物を、本発明に係るジオールの主成分として含むことができる。
従って、ハードセグメントのポリエステルとしては、主として、ブチレンテレフタレート単位、あるいは、ブチレンナフタレート単位よりなるものが物性、成形性、コストパフォーマンスの点より望ましい。
これらの脂肪族ポリカーボネートジオールは、他のグリコール、ジカルボン酸、エステル化合物やエーテル化合物などを少量共重合したものでもよく、共重合成分の例として、ダイマージオール、水添ダイマージオール、及び、これらの変性体などのグリコール、ダイマー酸、水添ダイマー酸などのジカルボン酸、脂肪族、芳香族、又は、脂環族のジカルボン酸とグリコールとからなるポリエステル、又は、オリゴエステル、ε-カプロラクトンなどからなるポリエステル、又は、オリゴエステル、ポリテトラメチレングリコール、ポリオキシエチレングリコールなどのポリアルキレングリコール、又は、オリゴアルキレングリコールなどが挙げられ、実質的に脂肪族ポリカーボネートセグメントの効果を消失させない程度に用いることができる。また、エチレングリコール、1,3-プロピレングリコール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,8-オクタンジオール、2,2-ジメチル-1,3-プロパンジオール、3-メチル-1,5-ペンタンジオール、2,4-ジエチル-1,5-ペンタンジオール、1,9-ノナンジオール、2-メチル-1,8-オクタンジオールなどの主として炭素数2~12の脂肪族ジオール残基からなるもので、特に、炭素数5~12の脂肪族ジオールが耐熱性や伸張性の点から好ましく、これらの成分は単独で用いてもよいし、必要に応じて2種以上を併用してもよい。
また、発明の効果が消失しない程度に、ソフトセグメントとして、例えばポリエチレングリコール、ポリオキシテトラメチレングリコールなどのポリアルキレングリコール、ポリカプロラクトン、ポリブチレンアジペートなどのポリエステルなどの共重合成分が導入されていてもよい。
特に、ジシクロヘキシルメタンジイソシアネートやイソホロンジイソシアネートに由来するポリカルボジイミドであって、イソシアネート基含有率が0.5~4質量%のものが好ましく、さらにイソシアネート基含有率が1~3質量%のものがより好ましい。なお、イソシアネート基含有率は常法(アミンで溶解して塩酸で逆滴定を行う方法)を用いて測定が可能である。
このようなイソシアネート基含有率が0.5~4質量%であり、カルボジイミド基数が2~50であるポリカルボジイミド化合物を用いることで、JIS K 7210「プラスチック−熱可塑性プラスチックのメルトマスフローレイト(MFR)及びメルトボリュームフローレイト(MVR)の求め方」に準拠したMFRを1~10g/10min分に調整し、製膜などの溶融押出で吐出ムラなどの発生を抑制することが可能となる。
ここで、本発明の耐熱性フィルムは、伸度25%における応力F25に対する伸度50%における応力F50の比F50/F25が1.05以上であり、例えば、2.0以下である。一態様において、F50/F25は、1.05以上1.6以下であってよい。
F50/F25がこのような範囲内であることにより、一方向、あるいは、多方向に伸張する場合、シワやゆがみなどの異常が発生しにくくなる。
本発明の耐熱性フィルムは、芳香族ジカルボン酸と脂肪族ジオール、又は、脂環族ジオールとから構成されたポリエステルからなるハードセグメントと、主として脂肪族ポリカーボネートからなるソフトセグメントが結合されてなるポリエステル系エラストマーを溶融押出などによるシート化で得られる。
本発明の耐熱性フィルムは、類似したポリエステル系エラストマー、異種のエラストマー、ポリエステル系樹脂、異種の樹脂などによって、A:単層、A/B、A/B/A、A/B/Cなどの層構成が可能で、更に、層間剥離などの問題が生じないように、更に、層間に、別の樹脂層を設けることも可能である。
本発明の耐熱性フィルムは、使用法によるが、全体の厚さが小さい場合、腰感が小さく、大きいと取扱性に問題が生じることがある。特に、半導体工程に供するダイシングテープに適用する場合、切断工程で生じる欠損により、破断が生じるおそれ及び/又は均一なエキスパンド性が得られないことがあるので、全体の厚さは60μm以上が好ましく、80μm以上がより好ましい。また、180μm以下が取り扱い性の観点から好ましい。
一実施態様において、本発明に係る耐熱性フィルムの少なくとも一方の面に、粘着剤を有する粘着シートが提供される。本発明の粘着シートに使用できる粘着剤は、(メタ)アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、オレフィン系粘着剤、スチレン系粘着剤等が挙げられる。プラスチック製品、ガラス製品、セラミック製品などにおける導電、加飾などを施した表面状態を保護する表面保護フィルムなど、適用する対象に応じて、選択が可能である。また、半導体工程などでウエハなどを切断、分離してチップを得る際に、これらを固定するダイシングテープには、これらの中でも、接着力の調整を容易にできる(メタ)アクリル系粘着剤が好ましい。
重水素化クロロホルム(CDCl3 )に脂肪族ポリカーボネートジオールサンプルを溶解させ、H-NMRを測定することにより末端基を算出し、下記の式で求めた。
数平均分子量=1,000,000/((末端基量(当量/トン))/2)
JIS K 7367-5:1998「プラスチック―毛細管形粘度計を用いたポリマー希釈溶液の粘度の求め方―」に準拠し、フェノール/テトラクロロエタン=60/40
(質量%)の混合溶媒を使用し、オストワルド粘度計を用いた測定より得た粘度数を還元粘度とした。
JIS K 7121:1987「プラスチックの転移温度測定方法」に準拠し、DSC(視差走査熱量測定)で得た曲線における融解ピーク温度を用いた。
フーリエ変換核磁気共鳴装置(ドイツ国BRUKER社製AVANCE-NEO500)を用いて、溶媒(重水素化クロロホルム/トリフルオロ酢酸=85/15容積%)中に、3〜5体積%の濃度に溶解した後、25℃でプロトンNMR測定を行ない、分子構造中の各種酸素に隣接するメチレンピークのシグナル強度比からハードセグメントとソフトセグメントの質量比を求めて、算出した。
JIS K 7130:1999「プラスチックフィルム及びシートの厚さ測定方法(A法)」に準拠して求めた。
JIS K 7127:1999「プラスチック-引張特性の試験方法-」に準拠し、引張強さ、引張破壊伸び、引張弾性率より強度、伸度、弾性率を求め、規定ひずみとして25%と50%を設定し、その引張応力をF25とF50とした。なお、拡張性の指標は、上述の規定ひずみにおける応力の比F50/F25で示す。
アクリル酸ブチル/アクリル酸=90/10をトルエン溶液中で常法により共重合させたアクリル系共重合体(重量平均分子量500,000)を含有する溶液に、市販のジペンタエリスリトールヘキサアクリレート「カラヤットDPHA:日本火薬製」を80重量部、光重合開始剤「Omnirad184:IGM Resins R.V.製」5重量部、ポリイソシアネート化合物「コロネートL:東ソー製」5重量部を加えた粘着剤溶液を市販の離型フィルム「E7002:東洋紡製」に粘着剤厚が約10μmに塗工した後、本発明に係る耐熱性フィルム(実施例)又は汎用フィルム(比較例)と貼り合わせを行ない、粘着シートを得た。得られた粘着シートを下記の項目で判定した。
◎ 粘着シートの枚葉品でカールがない
○ 粘着シートの枚葉品でカールは発生するが、シート状物の張力調整で対応が可能
△ 粘着シートの枚葉品でカールが発生し、シート状物の張力調整で対応が困難
× 貼り合わせでのシート状物の張力調整が困難で、枚葉品の粘着剤厚にムラがでる
粘着シートを6インチのダイシングフレームに両面テープで固定し、中心点とこれに対して直径50mmと直径100mmの同心円を描いた上で、ダイシングフレームの内径に対して所定の伸度となるようにエキスパンダー(ステージ:温度30℃、上昇速度50mm/min、保持60sec)で拡張を行ない、同心円に対する45degピッチで測定した伸度から、下記の評価を行なった。なお、所定の伸度は次式で求める。
伸度(%)=(ステージの移動距離×2)/フレーム内径×100
◎: 全方向で所定の伸度の65%以上に到達し、最大の差が2%未満である
○: 全方向で所定の伸度の65%以上に到達するが、最大2~5%の差がある
△: 一部の方向で所定の伸度の50~65%の伸度で、最大2~5%の差がある
×: 一部の方向に所定の伸度の50%未満の伸度、または、最大5%以上の差がある
JIS K 7206:1999「プラスチック-熱可塑性プラスチック-ビカット軟化温度の求め方(A120法)」に準拠し、下記の実施例、ならびに、比較例で得た樹脂よりプレス機で得た板厚3mmの試料に対して、下記の評価を行なった。
◎: ビカット軟化点が180℃以上である
△: ビカット軟化点が170~180℃である
△: ビカット軟化点が160~170℃である
×: ビカット軟化点が160℃以下である
市販の1,6-ヘキサンジオールタイプの脂肪族ポリカーボネートジオール(分子量2,000)と、ジフェニルカーボネートとの混合物を温度205℃、圧力130Pa、2時間の反応で得た調製物(数平均分子量10,000)に対して、PBT(ポリブチレンテレフタレート)とを昇温減圧下で縮重合させることで、表1に記載する所定のソフトセグメントの質量比を有する樹脂を得た。
得られた樹脂(層A向け)と、同じ樹脂をベースに市販の球状シリカ(平均粒径12μm)を15wt%含有したペレット状のMB(マスターバッチ)を作製し、マスターバッチにより球状シリカが7,500ppmになるようにした樹脂(層B向け)とを用い、構成Aの膜厚が、全厚の10%となり、更に、構成A/Bの構造を有するように押出機を通してTダイから押出を行ない、エアーナイフで冷却ロールに押さえつけた後、工程内で耳部のトリミングにより、実施例1~2の全膜厚100μmの耐熱性フィルムであって、幅650mm、巻長1,000mのロールを得た。
上記の実施例では、融点に対して、約10℃高い温度で約4~5時間のシート化を行なったが、押出や吐出の圧力異常は認めなかった。用いた樹脂の特性、耐熱性フィルムとロールの評価結果を表1に示す。
比較例1、及び、比較例2は、表1で示す条件の樹脂を用いたこと以外は、実施例1と同様にフィルムを作製した。また、得られたフィルムの物性を表1に示す。
市販の1,6-ヘキサンジオールタイプの脂肪族ポリカーボネートジオール(分子量2000)と、ジフェニルカーボネートとの混合物を温度205℃、圧力130Pa、2時間の反応で得た調製物(数平均分子量10,000)に対して、PBN(ポリブチレンナフタレート)を使用すること以外は、上述の実施例1と同様にして樹脂を得た。
更に、実施例1と同様に、構成Aの膜厚が、全厚の10%となり、更に、構成A/Bの構造を有するようにフィルムを形成し、全膜厚100μm、幅650mm、巻長1,000mの耐熱性フィルムのロールを得た。
上記の実施例では、融点に対して、約10℃高い温度で約4~5時間のシート化を行なったが、押出や吐出の圧力異常は認めなかった。用いた樹脂の特性、耐熱性フィルムとロールの評価結果を表1に示す。
比較例3、及び、比較例4は、表1で示す条件の樹脂を用いたこと以外は、実施例3と同様にフィルムを作製した。また、得られたフィルムの物性を表1に示す。
実施例1~4に記載する市販の1,6-ヘキサンジオールタイプの脂肪族ポリカーボネートジオール(分子量2000)と、ジフェニルカーボネートとの混合物を温度205℃、圧力130Pa、2時間の反応で得た調製物(数平均分子量10,000)に対して、PBT(ポリブチレンテレフタレート)、又は、PBN(ポリブチレンナフタレート)とを昇温減圧下で縮重合させることで、所定のソフトセグメントの質量比にした樹脂を得た。
得られた樹脂(層A向け樹脂)と、同じ樹脂をベースに市販の球状シリカ(平均粒径12μm)を15wt%含有したペレット状のMB(マスターバッチ)を作製し、マスターバッチにより球状シリカが7,500ppmになるようにした樹脂(層B向け)とを用い、カルボジイミド化合物(「カルボジライトLA-1」)を、層A向け樹脂及び層B向け樹脂の押出時に所定の量、サイドフィード供給すること以外は実施例1と同様にして耐熱性フィルムを作製した。具体的には、構成Aの膜厚が、全厚の10%となり、更に、構成A/Bの構造を有するように押出機を通してTダイから押出を行ない、エアーナイフで冷却ロールに押さえつけた後、工程内で耳部のトリミングにより、実施例5~12の全膜厚100μmの耐熱性フィルムであって、幅650mm、巻長1,000mのロールを得た。
Claims (5)
- 熱可塑性樹脂からなる耐熱性フィルムであって、該熱可塑性樹脂は、ハードセグメントとソフトセグメントが結合されてなるポリエステル系エラストマーであり、
該ハードセグメントは、芳香族ジカルボン酸と、脂肪族ジオール、又は、脂環族ジオールから構成されたポリエステル単位を有し、
該ソフトセグメントは、主として脂肪族ポリカーボネートから構成され、
該ポリエステル系エラストマーに含まれる該ハードセグメントの重量比が50%を超え、
該熱可塑性樹脂からなるフィルムは、弾性率が30~500MPa、破断伸度が200~700%、伸度25%における応力F25に対する伸度50%における応力F50の比F50/F25が1.05以上である耐熱性フィルム。 - 該ポリエステル系エラストマーのハードセグメントがポリブチレンテレフタレート単位よりなり、かつ、ポリエステル系エラストマーの融点が195~220℃であることを特徴とする請求項1に記載の耐熱性フィルム。
- 該ポリエステル系エラストマーのハードセグメントがポリブチレンナフタレート単位よりなり、かつ、ポリエステル系エラストマーの融点が210~240℃であることを特徴とする請求項1に記載の耐熱性フィルム。
- 保護フィルム用途に用いられる、請求項1~3のいずれか1項に記載の耐熱性フィルム。
- 請求項1~3のいずれか1項に記載の耐熱性フィルムの少なくとも一方の面に、粘着剤を有する粘着シート。
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