WO2014013884A1 - Mold release film - Google Patents
Mold release film Download PDFInfo
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- WO2014013884A1 WO2014013884A1 PCT/JP2013/068396 JP2013068396W WO2014013884A1 WO 2014013884 A1 WO2014013884 A1 WO 2014013884A1 JP 2013068396 W JP2013068396 W JP 2013068396W WO 2014013884 A1 WO2014013884 A1 WO 2014013884A1
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- release film
- release
- base layer
- layer
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
-
- 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
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- B32B7/06—Interconnection of layers permitting easy separation
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
-
- 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
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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
- B32B2307/51—Elastic
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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
- B32B2307/748—Releasability
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin 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
- C09J2425/00—Presence of styrenic polymer
- C09J2425/005—Presence of styrenic polymer in the release coating
-
- 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
- C09J2425/00—Presence of styrenic polymer
- C09J2425/006—Presence of styrenic polymer in the substrate
Definitions
- the present invention relates to a release film.
- This application claims priority on July 17, 2012 based on Japanese Patent Application No. 2012-155854 for which it applied to Japan, and uses the content here.
- a cover lay film is provided so as to cover an electrical wiring formed on the surface of an insulating base material such as a polyimide resin film, thereby insulating the electrical wiring. It is illustrated.
- This coverlay film is disposed by press laminating on an insulating substrate.
- the press laminating method is a method in which a cover lay film is pressed against an insulating substrate or electrical wiring by pressing a heating plate, but after pressing, the heating plate is easily released from the cover lay film or insulating substrate. A release film is inserted between the hot platen and the workpiece to be processed.
- the release film has a cushioning property for evenly transmitting pressure and heat to the coverlay film, and a shape-following property for suppressing the bleeding of the adhesive from the end surface of the coverlay film.
- Various characteristics such as (embeddability) are required.
- a release film As such a release film, a cushion layer containing a polyolefin resin and a polystyrene resin having a syndiotactic structure (hereinafter also referred to as SPS resin), and a mold release mainly composed of the SPS resin.
- SPS resin polystyrene resin having a syndiotactic structure
- the thing which has a layer is proposed (for example, refer patent document 1).
- the release film described in Patent Document 1 when it is attempted to sufficiently secure the embedding property of the release film, the peelability (release property) between the release film and the object to be processed decreases. As a result, workability of the press laminate may be reduced.
- An object of the present invention is to provide a release film capable of satisfying both release properties and embedding properties.
- a base layer comprising a polyolefin resin and a polystyrene resin having a syndiotactic structure
- a first release layer that is provided on at least one surface side of the base layer and is made of a resin material mainly composed of a polystyrene-based resin having a syndiotactic structure
- the tensile storage modulus E ′ measured under the measurement conditions of 1 minute and a measurement frequency of 1 Hz is 1.0 ⁇ 10 6 to 5.0 ⁇ 10 8 Pa at 120 ° C., and 1.0 ⁇ 10 7 to 170 ° C.
- a second release layer that is provided on the surface of the base layer opposite to the first release layer and is made of a resin material mainly composed of a polystyrene resin having a syndiotactic structure.
- the release film according to any one of (1) to (7) above.
- FIG. 3 is a graph showing temperature dependence of tensile storage modulus E ′ measured for release films obtained in Examples 1 to 4.
- FIG. 1 is a cross-sectional view showing an embodiment of a release film of the present invention.
- a release film 1 shown in FIG. 1 is a laminate having a base layer 2 and a first release layer 3 provided on the base layer 2.
- the base layer 2 contains a polyolefin resin and a polystyrene resin having a syndiotactic structure.
- the 1st mold release layer 3 is comprised with the resin material which has as a main component the polystyrene-type resin which has a syndiotactic structure.
- the release film 1 has a tensile storage modulus E ′ of 1.0 ⁇ 10 6 to 5.0 ⁇ 10 8 Pa at 120 ° C. measured by a method based on a test method defined in JIS K 7244. Yes, and configured to be 1.0 ⁇ 10 7 to 1.0 ⁇ 10 9 Pa at 170 ° C.
- a release film 1 press laminates a coverlay film on an insulating substrate on which an electrical wiring is formed, for example, between the heating plate and the coverlay film (in a portion where the coverlay film is interrupted, Between the board and the insulating substrate).
- the release film 1 can suppress deterioration of the release property while ensuring sufficient embedding property. That is, according to this invention, the release film 1 which can make embedding property and release property compatible is obtained.
- the base layer 2 supports the first release layer 3 and imparts cushioning properties to the release film 1.
- the constituent material of the base layer 2 is a resin mixture (resin blend) containing a polyolefin resin and a polystyrene resin having a syndiotactic structure.
- resin mixture resin blend
- polyolefin resin and the polystyrene resin having a syndiotactic structure will be sequentially described.
- Polyolefin resin Since the polyolefin-based resin has a relatively high flexibility, it contributes to improving the cushioning property of the release film 1.
- polystyrene resin examples include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 3-methyl.
- ⁇ -olefins such as 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene Homopolymers of the above, copolymers of at least two types of ⁇ -olefins, copolymers of ⁇ -olefins and other monomers, and the like. Good.
- Other monomers are those copolymerizable with ⁇ -olefins, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and unsaturated carboxylic acid esters such as acrylic acid esters and methacrylic acid esters.
- Polybasic unsaturated carboxylic acids such as maleic acid, polybasic unsaturated carboxylic acid anhydrides, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, dicyclopentadiene
- Non-conjugated dienes such as conjugated dienes, dicyclopentadiene, 1,4-hexadiene, 1,9-decadiene, cyclooctadiene, norbornadiene, methylene norbornene, ethylidene norbornene, 7-methyl-1,6-octadiene, etc. Can be mentioned.
- polyolefin resins include linear high density polyethylene, linear low density polyethylene, various polyethylenes such as high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, Examples include various polypropylenes such as random polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), and one or a mixture of two or more of ethylene-styrene copolymers. It is done.
- EVA ethylene-vinyl acetate copolymer
- EMMA ethylene-methyl methacrylate copolymer
- the polyolefin resin is preferably any one of polypropylene, ethylene-methyl methacrylate copolymer, and ethylene-styrene copolymer, and more preferably a mixture of two or more of these.
- the mechanical properties of the base layer 2 are optimized, and as a result, the tensile storage elastic modulus E ′ of the release film 1 at a predetermined temperature can be optimized.
- polypropylene examples include a propylene homopolymer and a copolymer of propylene and an ⁇ -olefin having 2 to 20 carbon atoms other than propylene.
- the polypropylene preferably has a melting point measured by a suggestive scanning calorimeter of 140 ° C. or higher, more preferably 150 to 170 ° C. Heat resistance can be imparted to the release film 1 by using such polypropylene.
- the polypropylene preferably has a melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. of 0.1 to 2 g / 10 minutes, preferably 0.3 to 1.5 g / 10 minutes. Some are more preferred.
- MFR melt flow rate
- the ethylene-methyl methacrylate copolymer preferably contains 5 to 50% by mass of units derived from methyl methacrylate, more preferably 8 to 35% by mass.
- the ethylene-methyl methacrylate copolymer preferably has a melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 190 ° C. of 0.25 to 50 g / 10 minutes, preferably 0.5 to What is 10 g / 10min is more preferable.
- MFR melt flow rate
- the ethylene-styrene copolymer may be any copolymer as long as it is a copolymer of a polyethylene structural unit and a polystyrene structural unit.
- a copolymer By using such a copolymer, the affinity with the polystyrene resin having the syndiotactic structure contained in the base layer 2 and the polystyrene resin having the syndiotactic structure contained in the first release layer 3 is improved. To do. As a result, the mechanical strength of the base layer 2 can be improved and the adhesion between the base layer 2 and the first release layer 3 can be improved.
- the ethylene-styrene copolymer is preferably a copolymer having a main chain composed of polyethylene structural units and a side chain composed of polystyrene structural units.
- Such an ethylene-styrene copolymer has a polystyrene structural unit in the side chain, so that the above effect becomes more remarkable.
- ethylene-styrene copolymer a copolymer having a polystyrene structural unit mass ratio of 5 to 15% by mass is preferably used.
- a copolymer having a polystyrene structural unit mass ratio of 5 to 15% by mass is preferably used.
- the mechanical strength of the base layer 2 and the adhesion between the base layer 2 and the first release layer 3 can be further enhanced.
- the mass ratio of the polystyrene structural unit is lower than the lower limit, the affinity between the ethylene-styrene copolymer and the polystyrene resin having a syndiotactic structure is lowered. Therefore, the mechanical strength of the base layer 2 may be reduced, or the adhesion between the base layer 2 and the first release layer 3 may be reduced.
- the mass ratio of the polystyrene structural unit in the ethylene-styrene copolymer can be calculated based on, for example, a peak integral value in a 1 H-NMR spectrum obtained by NMR analysis.
- the NMR analyzer for example, a JNM-ECA400 superconducting FT-NMR apparatus manufactured by JEOL Ltd. is used.
- the measurement nucleus is 1 H, 13 C
- the measurement temperature is 125 ° C.
- the measurement solvent is deuterated 1,2-dichlorobenzene
- the number of integration is 16 for 1 H, 16384 for 13 C
- the repetition waiting time is 1 H can be 5 seconds and 13 C can be 2 seconds.
- the reference peak can be set to the peak of the measurement solvent
- 1 H can be set to 7.40 ppm as an internal reference
- 13 C can be set to 127.70 ppm as an internal reference.
- a polystyrene-based resin (SPS resin) having a syndiotactic structure has a stereoregular structure (syndi) in which phenyl groups and substituted phenyl groups as side chains are alternately located in opposite directions with respect to the main chain composed of carbon-carbon sigma bonds. It is a resin having an tactic structure.
- SPS resin used for the base layer 2 examples include those described in JP-A No. 2000-038461. Specifically, 75% or more, preferably 85% or more of racemic dyad, or 30% or more, preferably 50% or more of syndiotacticity of racemic pentad, polystyrene, poly (alkylstyrene), poly ( Aryl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), hydrogenated polymers thereof and mixtures thereof, or these as main components And the like.
- poly (alkyl styrene) examples include poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene), and the like.
- poly (aryl styrene) examples include poly (phenyl styrene), poly (vinyl naphthalene), and poly (vinyl styrene).
- poly (halogenated styrene) examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like.
- poly (halogenated alkylstyrene) examples include poly (chloromethylstyrene).
- poly (alkoxystyrene) examples include poly (methoxystyrene) and poly (ethoxystyrene).
- polystyrene poly (p-methylstyrene), poly (m-methylstyrene), poly (pt-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene) are particularly preferable.
- Poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units are preferably used.
- Examples of other resins include various elastomer resins, polyester resins, polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins, and the like, and one or a mixture of two or more of these are used.
- elastomer resin for example, those described in JP 2011-161749 A are preferably used.
- polyester-based resin examples include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and the like.
- examples of the polyamide-based resin include nylon 6, nylon 66, and the like.
- additives include an antiblocking agent, an antioxidant, a nucleating agent, an antistatic agent, a process oil, a plasticizer, a release agent, a flame retardant, and the like as described in JP-A-2011-161749.
- flame retardant aids, pigments, etc. and one or a mixture of two or more of these is used.
- antiblocking agent for example, those described in JP 2011-161749 A are preferably used.
- antioxidants examples include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.
- nucleating agent examples include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate); metal salts of phosphoric acid such as methylene bis (2,4-di-tert-butylphenol) acid phosphate sodium.
- Polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (dimethylbenzylidene) sorbitol; N, N ′, N ′′ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ', N "-tricyclohexyl 1,3,5-benzenetricarboximide, N, N'-dicyclohexyl-naphthalenedicarboxamide, 1,3,5- Of tri (dimethylisopropoylamino) benzene Una amide compound; talc, phthalocyanine derivatives and the like, and these can be used singly or in combination of two or more of them.
- plasticizer examples include polyethylene glycol, polyamide oligomer, ethylene bisstearoamide, phthalate ester, polystyrene oligomer, polyethylene wax, silicone oil, etc., and one or more of these are combined. Can be used.
- examples of the release agent include polyethylene wax, silicone oil, long chain carboxylic acid, long chain carboxylic acid metal salt, and the like, and one or more of them can be used in combination.
- examples of the process oil include paraffinic oil, naphthenic oil, and aroma oil.
- the amount of each of these additives is not particularly limited, but is preferably about 0.01 to 15 parts by mass, and 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the polyolefin resin and the SPS resin. More preferably, it is about a part.
- First release layer For example, when the coverlay film is press-laminated on an insulating substrate on which electrical wiring is formed, the first release layer 3 prevents adhesion between the release film 1 and the object to be processed and provides good release properties.
- the constituent material of the first release layer 3 is a resin material mainly composed of the SPS resin described above.
- the SPS resin included in the first release layer 3 and the SPS resin included in the base layer 2 may have different compositions, but are preferably configured to include the same composition. Thereby, the adhesiveness of the base layer 2 and the 1st mold release layer 3 can be improved. As a result, it is possible to prevent delamination between the base layer 2 and the first release layer 3 when the release film 1 is peeled after press lamination.
- the average thickness of the first release layer 3 is not particularly limited, but is preferably 5 to 100 ⁇ m, and more preferably 10 to 80 ⁇ m. By making the thickness of the first release layer 3 within the above range, sufficient embedding property can be imparted to the release film 1 while ensuring the adhesion between the base layer 2 and the first release layer 3. it can.
- the ratio of the SPS resin in the first release layer 3 is preferably 70% by mass or more, and more preferably 80% by mass or more. By setting the ratio of the SPS resin in the first release layer 3 within the above range, the release film 1 has good release properties.
- FIG. 2 is a cross-sectional view showing another embodiment of the release film of the present invention.
- the release film 1 shown in FIG. 2 will be described.
- differences from FIG. 1 will be mainly described, and description of similar matters will be omitted.
- the release film 1 shown in FIG. 2 has the second release layer 4 provided on the surface opposite to the surface on which the first release layer 3 of the base layer 2 is provided, except for the release film shown in FIG. The same as film 1.
- the second release layer 4 for example, when the coverlay film is press-laminated on the insulating substrate on which the electrical wiring is formed, the releasability between the hot platen and the coverlay film can be improved.
- the intermediate member is interposed between the hot platen and the cover lay film, the releasability between the intermediate member and the cover lay film can be enhanced. As a result, adhesion between the hot platen or the intermediate member and the release film 1 can be suppressed, and the workability of press lamination can be further improved.
- the total thickness (average thickness) of the release film 1 is preferably about 20 to 300 ⁇ m, and more preferably about 20 to 200 ⁇ m.
- the release film 1 having the above layer structure has an appropriate cushioning property.
- This cushioning property influences the embedding property and releasing property of the release film 1, and is an important characteristic for the release film 1 to perform its function. Specifically, for example, when the release film 1 is subjected to press lamination, it is heated to a predetermined temperature. The release film 1 is softened with heating, and easily follows the surface shape of the object to be processed for press lamination. This phenomenon imparts embedding property to the release film 1, while causing the release property to deteriorate.
- embedding property and releasability are characteristics that can be contradicted in principle. Therefore, it has been insufficient so far to achieve both of these characteristics, particularly when a press laminate is applied to a workpiece having a complicated surface shape.
- the present inventor has intensively studied the conditions for achieving both embeddability and releasability.
- the tensile storage elastic modulus E ′ of the release film 1 on the low temperature side is 1.0 ⁇ 10 6 to 5.0 ⁇ 10.
- the tensile storage elastic modulus E ′ of the release film 1 on the high temperature side (170 ° C.) is 1.0 ⁇ 10 7 to 1.0 ⁇ 10 9 Pa at 8 Pa, the release film 1 is embedded.
- the present invention has been completed by finding that the properties and releasability can be highly compatible.
- the release film 1 satisfying such conditions is optimized for cushioning from the low temperature side to the high temperature side in the temperature rising process in the press laminating process and the like, and can be highly compatible with embedding property and mold release property. . Therefore, for example, when the coverlay film is press-laminated on the insulating substrate on which the electrical wiring is formed, it is possible to improve the release workability while suppressing the bleeding of the adhesive from the end face of the coverlay film. As a result, a high-quality FPC can be efficiently manufactured.
- the tensile storage elastic modulus E ′ of the release film 1 is measured by a method based on the test method specified in JIS K 7244.
- the measurement conditions were as follows: test piece length 40 mm, test piece width 4 mm, test piece length 20 mm between clamps for fixing the test piece, measurement start temperature 25 ° C., measurement end temperature 250 ° C., heating rate 5
- the measurement frequency is 1 ° C./min.
- the tensile storage elastic modulus E ′ at 120 ° C. is set to the above-described value on the low temperature side
- the tensile storage elastic modulus E ′ at 170 ° C. is set to the above-described value on the high temperature side.
- the tensile storage elastic modulus E ′ of the release film 1 at 120 ° C. is preferably 3.0 ⁇ 10 6 to 3.0 ⁇ 10 8 Pa, more preferably 7.0 ⁇ 10 6 to 7.0 ⁇ . 10 7 Pa.
- the tensile storage elastic modulus E ′ of the release film 1 at 170 ° C. is preferably 2.0 ⁇ 10 7 to 5.0 ⁇ 10 8 Pa, more preferably 3.0 ⁇ 10 7 to 3.0 ⁇ . 10 8 Pa.
- the tensile storage elastic modulus E ′ of the release film 1 is preferably 1.0 ⁇ 10 6 to 5.0 ⁇ 10 8 Pa in the temperature range of 120 to 145 ° C., and preferably 3.0 ⁇ 10 6 to 3.0 ⁇ 10 8 Pa is more preferable, and 5.0 ⁇ 10 6 to 7.0 ⁇ 10 7 Pa is even more preferable.
- the tensile storage modulus E ′ of the release film 1 at 185 ° C. which is higher than 170 ° C., is preferably 8.0 ⁇ 10 6 to 5.0 ⁇ 10 8 Pa, more preferably 1. 5 ⁇ 10 7 to 5.0 ⁇ 10 8 Pa, more preferably 2.0 ⁇ 10 7 to 3.0 ⁇ 10 8 Pa. If the tensile storage elastic modulus E ′ of the release film 1 at 185 ° C. is within the above range, the embedding property of the release film can be further improved. Therefore, the embedding property and the releasability can be made highly compatible. For example, even when the height difference of the surface of the FPC is large, it is possible to manufacture a high-quality FPC and prevent the workability of the press laminate from being lowered. .
- the average thickness of the base layer 2 is not particularly limited, but is preferably about 10 to 200 ⁇ m, more preferably about 15 to 150 ⁇ m, and further preferably about 20 to 120 ⁇ m. By making the thickness of the base layer 2 within the above range, it is possible to suppress the deterioration of the mold release property while ensuring the sufficient embedding property of the mold release film 1. In addition, when the average thickness of the base layer 2 is less than the said lower limit, the adhesive force of the base layer 2 with respect to the 1st release layer 3 will fall.
- the release film 1 when the release film 1 is peeled after press laminating a coverlay film on an insulating substrate on which electrical wiring is formed, there is a possibility that delamination may occur between the base layer 2 and the first release layer 3. is there. Moreover, when the average thickness of the base layer 2 is less than the said lower limit, there exists a possibility that the embedding property of the release film 1 may fall. On the other hand, when the average thickness of the base layer 2 exceeds the upper limit, the embedding property of the release film 1 becomes excessive, and the release property of the release film 1 may be lowered.
- the average thickness of the base layer 2 is preferably 1.5 times or more, more preferably 2 to 10 times, more preferably 2.5 to 7 times the average thickness of the first release layer 3. Is more preferable.
- the ratio of the SPS resin in the base layer 2 is preferably smaller than the ratio of the polyolefin resin. Specifically, it is preferably about 2 to 40% by mass, more preferably about 3 to 35% by mass. Thereby, sufficient embedding property can be imparted to the release film 1 while ensuring the adhesion between the base layer 2 and the first release layer 3.
- the ratio of the polyolefin-based resin is preferably about 60 to 98% by mass, and more preferably about 65 to 97% by mass.
- the ethylene-styrene copolymer is preferably set to be larger.
- the mass ratio of the ethylene-styrene copolymer is preferably about 1.05 to 2.5 times the mass ratio of polypropylene, more preferably about 1.1 to 2 times.
- the amount of the ethylene-methyl methacrylate copolymer is preferably increased.
- the mass ratio of the ethylene-methyl methacrylate copolymer is preferably about 1.05 to 2.5 times, more preferably about 1.1 to 2 times the mass ratio of polypropylene.
- the ethylene-styrene copolymer and the ethylene-methyl methacrylate copolymer are each preferably set to be larger than the SPS resin.
- the mass ratio of the ethylene-styrene copolymer and the ethylene-methyl methacrylate copolymer is preferably about 1.05 to 2.5 times the mass ratio of the SPS resin. More preferably, it is about double.
- the cushioning property of the base layer 2 is optimized, so that the embedding property and the releasability of the release film 1 can be made more highly compatible.
- the base layer 2 contains, for example, SPS resin, polypropylene, ethylene-methyl methacrylate copolymer (EMMA) and ethylene-styrene copolymer
- the ratio of SPS resin is 2 to 40 parts by mass
- the ratio of polypropylene is 3 to It is preferable to set 40 parts by mass, the ratio of ethylene-methyl methacrylate copolymer to 10 to 50 parts by mass, and the ratio of ethylene-styrene copolymer to 10 to 50 parts by mass, respectively.
- the release film 1 shown in FIG. 1 can be produced by a coextrusion method or an extrusion lamination method.
- FIG. 3 is a diagram for explaining an example of a method for producing the release film 1.
- the release film 1 is manufactured by extruding the raw material of the base layer 2 and the raw material of the first release layer 3 simultaneously using a feed block and a multi-manifold die.
- the raw material of the base layer 2 and the raw material of the first release layer 3 are each melt-kneaded by a known method, and granulated or pulverized as necessary to obtain a melt.
- a blender such as a V blender, a ribbon blender, a Henschel hexar, or a tumbler blender, a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like is used.
- the melt that is the raw material of the base layer 2 and the melt that is the raw material of the first release layer 3 are simultaneously extruded in layers from the die 210.
- a single screw extruder, a twin screw extruder, or the like is used for this extrusion.
- the extruded melt M is guided between the first roll 230 and the touch roll 220, and until the melt M is separated from the first roll 230, the melt M is pushed by the touch roll 220 and the first roll 230. To be cooled. Thereby, the release film 1 is obtained.
- the manufactured release film 1 is sent to the downstream side in the film feeding direction (see the arrow in FIG. 3) by the second roll 240 and is finally taken up by a take-up roll (not shown).
- the temperature of the first roll 230 is preferably about 30 to 100 ° C.
- the temperature of the touch roll 220 is preferably about 50 to 120 ° C.
- the temperature of the second roll 240 relative to the first roll 230 is The peripheral speed ratio is preferably about 0.990 to 0.998.
- the release film 1 is manufactured by extruding the raw material of the base layer 2 and the raw material of the first release layer 3 and then laminating them.
- the temperature of the extruder cylinder is set to 270 to 300 ° C., and the melt as the raw material of the first release layer 3 is extruded in layers, and as shown in FIG. 3, the first roll 230 and the touch roll Lead to 220.
- the induced melt M is cooled by the touch roll 220 and the first roll 230 until the melt M is separated from the first roll 230. Thereby, the release layer film 30 is obtained.
- the melt which is the raw material of the base layer 2
- the release layer film 30 (not shown).
- the release film 1 is obtained by cooling this.
- the manufactured release film 1 is finally wound up on a winding roll (not shown).
- the tensile storage elastic modulus E ′ of the release film 1 can be appropriately adjusted by changing the cooling rate of the melt that is the raw material of the base layer 2 and the first release layer 3.
- the cooling rate is appropriately set according to the composition and thickness of the base layer 2, the composition and thickness of the first release layer 3, the layer configuration of the release film 1, and the like. For example, it is preferably set to about 0.1 to 20 ° C./second, more preferably about 0.3 to 15 ° C./second.
- the crystallinity of the crystalline resin eg, SPS resin, polypropylene, etc.
- the crystallinity of the crystalline resin eg, SPS resin, polypropylene, etc.
- the crystallinity of the crystalline resin contained in the base layer 2 and the first release layer 3 is reduced, or the crystal size is reduced, and the mold release
- the tensile storage elastic modulus E ′ of the film 1 is lowered.
- the crystallinity of the crystalline resin contained in the base layer 2 and the first release layer 3 is increased, or the crystal size is increased, and the tensile storage modulus E of the release film 1 is increased. 'Will rise.
- the crystallinity of the constituent material of the base layer 2 and the first release layer 3 is preferably 5 to 50%, more preferably 10 to 40%, as measured by a differential scanning calorimeter (DSC). preferable.
- DSC differential scanning calorimeter
- the tensile storage elastic modulus E ′ of the release film 1 on the low temperature side (120 ° C.) and the tensile storage elastic modulus E ′ of the release film 1 on the high temperature side (170 ° C.) are respectively the base layer 2 and the first release layer. It can adjust suitably by changing the composition of 3.
- the ratio of resins having a softening point (melting point or glass transition point) close to 170 ° C. hereinafter referred to as “high softening point resin” is increased and the softening point is close to 120 ° C.
- the tensile storage modulus E ′ of the release film 1 By lowering the ratio of the resin (hereinafter referred to as “low softening point resin”), the characteristics occupied by the high softening point resin in the tensile storage modulus E ′ of the release film 1 become more obvious. As a result, the tensile storage modulus E ′ on the high temperature side can be selectively adjusted. Similarly, the tensile storage modulus E ′ on the low temperature side can be selectively adjusted by decreasing the ratio of the high softening point resin and increasing the ratio of the low softening point resin. In this way, the release film 1 having the tensile storage elastic modulus E ′ on the low temperature side and the high temperature side within the above ranges can be produced.
- the tensile storage elastic modulus E ′ can also be adjusted by adding the above-described additives to the base layer 2 and the first release layer 3.
- a step of adjusting the crystallinity of the SPS resin or polyolefin resin of the release film 1 obtained as described above may be provided.
- the crystallinity can be adjusted, for example, by subjecting the release film 1 to heat treatment. Specifically, a method of heat-setting the release film 1 in a drier using a tenter device or a method of heat-treating at about 50 to 220 ° C. using a heat treatment roll can be mentioned.
- the manufacturing method of the release film 1 is not limited to the above-mentioned thing, Other methods may be used.
- FIG. 4 is a diagram for explaining an example of use of the release film 1.
- the release film 1 according to the present invention is, for example, when a coverlay film is press-laminated on a surface having an elevation difference of an insulating substrate on which electric wiring is formed (between a hot platen and a coverlay film). In the interrupted portion, it is inserted between the hot platen and the insulating substrate) and used to ensure the release property after press lamination.
- an unbonded body 340 having a coverlay film temporarily fixed on an insulating substrate on which electrical wiring is formed is sandwiched between two release films 1. Further, these are sandwiched between two fluororesin sheets 330, two rubber cushions 320, and two stainless steel plates 310. And these are pressed with the hot platen 300 as shown by the arrow in FIG.
- FIG. 5 is a diagram showing an example of a temperature profile in press lamination. Note that the origin of the horizontal axis of the temperature profile corresponds to the time when the object to be processed is started to be pressed by the heating plate 300.
- the temperature of the hot platen 300 is rapidly raised from room temperature to 185 ° C. within 10 seconds after starting to pressurize the workpiece, and then maintained at that temperature for 60 seconds. Thereafter, when pressurization of the object to be processed by the hot platen 300 is finished, press lamination is completed.
- the press pressure of the object to be processed by the hot platen 300 is preferably set to about 5 to 15 MPa.
- the release film 1 In press laminating, the release film 1 is deformed so as to be embedded along the end face of the coverlay film, so that bleeding of the adhesive from the end face of the coverlay film is suppressed.
- the base layer 2 since the base layer 2 has appropriate mechanical properties, the release film 1 is quickly separated from the end face of the coverlay film when the applied pressure is released after press lamination. Thereby, the embedding property and release property of the release film 1 in the press laminate can be made compatible, and the workability of the press laminate can be improved.
- the bleeding of the adhesive is prevented at the portion where the cover lay film is interrupted, the electrical wiring can be surely exposed at the portion to achieve electrical connection.
- the fluororesin sheet 330, the rubber cushion 320, and the stainless steel plate 310 may be omitted.
- the release film 1 may be used for the purpose of separating the molding die and the member so as not to adhere to each other when the member is molded, in addition to the above-described use examples.
- release film for FRP (Fiber Reinforced Plastics) and CFRP (Carbon Fiber Reinforced Plastics) molding release film for advanced composite materials (ACM: Advanced Composites Material), release film for rubber sheet curing, epoxy and phenolic It can be used as a release film for semiconductor sealing materials such as, a release film for special adhesive tape, and the like.
- the present invention is intermediate between the base layer 2 and the first release layer 3 and between the base layer 2 and the second release layer 4. You may make it interpose a layer.
- the intermediate layer is used, for example, for the purpose of increasing the adhesion between the layers, and specifically includes an anchor layer, a primer layer, and the like.
- Example 1 Production of release film (Example 1) (1) Raw materials for first release layer and second release layer First, SPS resins (Zarek S104 manufactured by Idemitsu Kosan Co., Ltd.) were prepared as raw materials for the first release layer and the second release layer.
- SPS resins Zarek S104 manufactured by Idemitsu Kosan Co., Ltd.
- Base layer raw materials The following resins were prepared as base layer raw materials.
- the polyolefin resin is a mixture of a plurality of resins, and the breakdown is as follows.
- the ethylene-methyl methacrylate copolymer is represented as EMMA, the ethylene-styrene copolymer as AD, and the polypropylene as PP.
- EMMA Suditomo Chemical Co., Ltd. ACLIFT WD106
- AD Mitsubishi Chemical Co., Ltd. Modic F502
- PP Part 1 of PP
- the methyl methacrylate derived unit content in EMMA is 5% by mass, and the melt flow rate is 2 g / 10 min.
- the polyethylene structural unit content rate in AD is 91.4 mass%
- the polystyrene structural unit content rate is 8.6 mass%
- the melt flow rate is 1 g / 10 min.
- the melt flow rate of PP is 0.5 g / 10 minutes.
- the raw materials were simultaneously extruded so that the first release layer, the base layer, and the second release layer were laminated to produce a release film.
- the temperature of the raw material melt was 285 ° C., respectively.
- the apparatus shown in FIG. 3 is used, the temperature of the first roll 230 is 30 ° C., the temperature of the touch roll 220 is 70 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230. was set to 0.990.
- the peripheral speed etc. of each roll were adjusted so that the cooling rate of a release film might be 5 degree-C / sec.
- the total thickness (average thickness) of the produced release film was 120 ⁇ m.
- the average thickness of the base layer was 70 ⁇ m, and the average thickness of the first release layer and the second release layer was 25 ⁇ m.
- Example 2 A release film was produced in the same manner as in Example 1 except that the layer configuration and production conditions of the release film were changed as shown in Table 1.
- N, N ′, N ′′ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide was used as the nucleating agent.
- FIG. 6 is a graph showing the temperature dependence of the tensile storage modulus E ′ measured for the release films obtained in Examples 1 to 4.
- a coverlay film was formed on an insulating substrate (FPC) on which an electrical wiring having an L / S of 150/150 ⁇ m was formed. Press laminated.
- press lamination stainless steel plate, rubber cushion, fluororesin sheet, release film, coverlay film, FPC, release film, fluororesin sheet, rubber cushion, stainless steel are stacked in this order, and this is a one-stage press Pressed by machine.
- pressing the temperature was raised to 185 ° C. at a rate of temperature rise of 10 ° C./min while being pressurized at a pressure of 10 MPa, then held for 1 minute, and then cooled to room temperature. This obtained the sample which carried out the press lamination of the coverlay film on FPC.
- the embedding property of the coverlay film was evaluated for the obtained sample.
- the extent of the coverlay film adhesive exuding from the end face is determined by “7.5. Of JPCA Standard, Single-sided and Double-sided Flexible Printed Circuit Board JPCA-DG02 issued by the Japan Electronic Circuits Association.
- the evaluation was made based on the following evaluation criteria.
- the release film obtained in each example can achieve both embedding and release properties when the cover lay film is press-laminated on the insulating substrate.
- the release film obtained in each example by optimizing the layer structure of the base layer, even when press laminating a coverlay film on a rough surface, according to the release film obtained in each example, embedding and releasing properties It was recognized that the above can be made highly compatible.
- the present invention it is possible to obtain a release film that can achieve both release properties and embedding properties by optimizing the structure of the base layer. Therefore, the present invention can be suitably used for a release film and is extremely important in industry.
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Abstract
Description
本願は、2012年7月17日に、日本に出願された特願2012-158584号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a release film.
This application claims priority on July 17, 2012 based on Japanese Patent Application No. 2012-155854 for which it applied to Japan, and uses the content here.
プレスラミネート法は、熱盤を押し当てることにより、カバーレイフィルムを絶縁基材や電気配線に圧着する方法であるが、圧着後、熱盤をカバーレイフィルムや絶縁基材から容易に離型することができるよう、熱盤と被処理物との間に離型フィルムが介挿される。したがって離型フィルムには、上記離型性に加え、カバーレイフィルムに対して圧力や熱を均等に伝えるためのクッション性、カバーレイフィルム端面からの接着剤の染み出しを抑えるための形状追従性(埋め込み性)等の各種特性が求められることとなる。 For example, in a flexible printed circuit board (hereinafter also referred to as FPC), a cover lay film is provided so as to cover an electrical wiring formed on the surface of an insulating base material such as a polyimide resin film, thereby insulating the electrical wiring. It is illustrated. This coverlay film is disposed by press laminating on an insulating substrate.
The press laminating method is a method in which a cover lay film is pressed against an insulating substrate or electrical wiring by pressing a heating plate, but after pressing, the heating plate is easily released from the cover lay film or insulating substrate. A release film is inserted between the hot platen and the workpiece to be processed. Therefore, in addition to the above releasability, the release film has a cushioning property for evenly transmitting pressure and heat to the coverlay film, and a shape-following property for suppressing the bleeding of the adhesive from the end surface of the coverlay film. Various characteristics such as (embeddability) are required.
しかしながら、特許文献1に記載の離型フィルムでは、離型フィルムの埋め込み性を十分に確保しようとしたとき、離型フィルムと被処理物との間の剥離性(離型性)が低下する。これによりプレスラミネートの作業性が低下することがあった。 As such a release film, a cushion layer containing a polyolefin resin and a polystyrene resin having a syndiotactic structure (hereinafter also referred to as SPS resin), and a mold release mainly composed of the SPS resin. The thing which has a layer is proposed (for example, refer patent document 1).
However, in the release film described in
(1) ポリオレフィン系樹脂と、シンジオタクチック構造を有するポリスチレン系樹脂と、を含む基層と、
前記基層の少なくとも一方の面側に設けられ、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂材料で構成される第1離型層と、
を有し、
JIS K 7244に規定の試験方法に準拠し、試験片の長さ40mm、幅4mm、クランプ間の試験片の長さ20mm、測定開始温度25℃、測定終了温度250℃、昇温速度5℃/分、測定周波数1Hzの測定条件で測定された引張貯蔵弾性率E’が、120℃において1.0×106~5.0×108Paであり、170℃において1.0×107~1.0×109Paであることを特徴とする離型フィルム。 Such an object is achieved by the present inventions (1) to (8) below.
(1) a base layer comprising a polyolefin resin and a polystyrene resin having a syndiotactic structure;
A first release layer that is provided on at least one surface side of the base layer and is made of a resin material mainly composed of a polystyrene-based resin having a syndiotactic structure;
Have
In accordance with the test method specified in JIS K 7244, the length of the test piece is 40 mm, the width is 4 mm, the length of the test piece between the clamps is 20 mm, the measurement start temperature is 25 ° C., the measurement end temperature is 250 ° C., and the heating rate is 5 ° C. / The tensile storage modulus E ′ measured under the measurement conditions of 1 minute and a measurement frequency of 1 Hz is 1.0 × 10 6 to 5.0 × 10 8 Pa at 120 ° C., and 1.0 × 10 7 to 170 ° C. A release film characterized by being 1.0 × 10 9 Pa.
図1は、本発明の離型フィルムの実施形態を示す断面図である。 Hereinafter, it demonstrates in detail based on suitable embodiment of the release film of this invention.
FIG. 1 is a cross-sectional view showing an embodiment of a release film of the present invention.
<基層>
基層2は、第1離型層3を支持するとともに、離型フィルム1にクッション性を付与する。 Hereinafter, each part of the
<Base layer>
The
ポリオレフィン系樹脂は、比較的柔軟性が高いことから、離型フィルム1のクッション性の向上に寄与する。 (Polyolefin resin)
Since the polyolefin-based resin has a relatively high flexibility, it contributes to improving the cushioning property of the
シンジオタクチック構造を有するポリスチレン系樹脂(SPS樹脂)は、炭素-炭素シグマ結合からなる主鎖に対して側鎖であるフェニル基や置換フェニル基が交互に反対方向に位置する立体規則構造(シンジオタクチック構造)を有する樹脂である。 (Polystyrene resin with syndiotactic structure)
A polystyrene-based resin (SPS resin) having a syndiotactic structure has a stereoregular structure (syndi) in which phenyl groups and substituted phenyl groups as side chains are alternately located in opposite directions with respect to the main chain composed of carbon-carbon sigma bonds. It is a resin having an tactic structure.
基層2には、上記の樹脂の他に、その他の樹脂や各種添加剤等が添加されていてもよい。 (Other resins, etc.)
In addition to the above resins, other resins, various additives, and the like may be added to the
第1離型層3は、例えば電気配線が形成された絶縁基板上にカバーレイフィルムをプレスラミネートする際、離型フィルム1と被処理物との密着を防ぎ、良好な離型性をもたらす。 <First release layer>
For example, when the coverlay film is press-laminated on an insulating substrate on which electrical wiring is formed, the
第1離型層3に含まれるSPS樹脂と基層2に含まれるSPS樹脂とは、互いに異なる組成のものでもよいが、好ましくは互いに同じ組成のものが含まれるように構成される。これにより、基層2と第1離型層3との密着性を高めることができる。その結果、プレスラミネート後に離型フィルム1を剥離する際、基層2と第1離型層3との間で層間剥離が生じるのを防止することができる。 The constituent material of the
The SPS resin included in the
図2は、本発明の離型フィルムの他の実施形態を示す断面図である。以下、図2に示す離型フィルム1について説明するが、以下の説明では図1との相違点を中心に説明し、同様の事項についてはその説明を省略する。 <Second release layer>
FIG. 2 is a cross-sectional view showing another embodiment of the release film of the present invention. Hereinafter, the
以上のような層構成を有する離型フィルム1は、適度なクッション性を有している。このクッション性は、離型フィルム1の埋め込み性および離型性を左右するため、離型フィルム1がその機能を果たすために重要な特性である。具体的には、例えば離型フィルム1がプレスラミネートに供されたとき、所定の温度まで加熱される。加熱に伴って離型フィルム1が柔軟化し、プレスラミネートの被処理物の表面形状に追従し易くなる。この現象が、離型フィルム1に埋め込み性を付与し、一方、離型性を低下させる原因となる。このように、埋め込み性と離型性は、原理上相反し得る特性である。よって、特に複雑な表面形状を有する被処理物に対してプレスラミネートを施す場合において、これらの特性を両立させることはこれまで不十分であった。 <Characteristics of release film>
The
図1に示す離型フィルム1は、共押出法や押出ラミネート法により製造することができる。
図3は、離型フィルム1を製造する方法の一例を説明するための図である。 <Method for producing release film>
The
FIG. 3 is a diagram for explaining an example of a method for producing the
図4は、離型フィルム1の使用例を説明するための図である。 <Usage example of release film>
FIG. 4 is a diagram for explaining an example of use of the
1.離型フィルムの製造
(実施例1)
(1)第1離型層および第2離型層の原材料
まず、第1離型層および第2離型層の原材料としてそれぞれSPS樹脂(出光興産(株)製ザレックS104)を用意した。 Next, specific examples of the present invention will be described.
1. Production of release film (Example 1)
(1) Raw materials for first release layer and second release layer First, SPS resins (Zarek S104 manufactured by Idemitsu Kosan Co., Ltd.) were prepared as raw materials for the first release layer and the second release layer.
また、基層の原材料として以下の樹脂を用意した。 (2) Base layer raw materials The following resins were prepared as base layer raw materials.
・ポリオレフィン系樹脂 80質量部 ・ 20 parts by mass of SPS resin (Zarek S104 manufactured by Idemitsu Kosan Co., Ltd.)
AD(三菱化学(株)製モディックF502) 30質量部
PP(住友化学(株)製ノーブレンFH1016) 20質量部 EMMA (Sumitomo Chemical Co., Ltd. ACLIFT WD106) 30 parts by mass AD (Mitsubishi Chemical Co., Ltd. Modic F502) 30 parts by mass PP (Sumitomo Chemical Co., Ltd. Nobrene FH1016) 20 parts by mass
共押出法を利用して基層の表裏に同一の離型層(第1離型層および第2離型層)を有する積層フィルムを作製した。 (3) Film formation A laminated film having the same release layer (first release layer and second release layer) on the front and back of the base layer was prepared using a coextrusion method.
離型フィルムの層構成および製造条件を表1に示すように変更した以外は、それぞれ実施例1と同様にして離型フィルムを製造した。なお、一部の実施例では、核剤としてN,N’,N”-トリス[2-メチルシクロヘキシル]-1,2,3-プロパントリカルボキサミドを用いた。 (Examples 2 to 9)
A release film was produced in the same manner as in Example 1 except that the layer configuration and production conditions of the release film were changed as shown in Table 1. In some examples, N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide was used as the nucleating agent.
離型フィルムの層構成および製造条件を表2に示すように変更した以外は、それぞれ実施例1と同様にして離型フィルムを製造した。 (Comparative Examples 1 to 9)
A release film was produced in the same manner as in Example 1 except that the layer structure and production conditions of the release film were changed as shown in Table 2.
2.1 引張貯蔵弾性率E’の測定
各実施例および各比較例で得られた離型フィルムについてJIS K 7244に規定の試験方法に準拠した方法により、引張貯蔵弾性率E’を測定した。なお、引張貯蔵弾性率E’としては、120℃、170℃および185℃における値、および、120~145℃の範囲における最大値、最小値をそれぞれ得た。また、測定条件は以下に示す通りである。 2. 2. Evaluation of Release Film 2.1 Measurement of Tensile Storage Elastic Modulus E ′ Tensile storage elastic modulus E by a method based on the test method defined in JIS K 7244 for the release films obtained in each Example and each Comparative Example. 'Measured. As the tensile storage elastic modulus E ′, values at 120 ° C., 170 ° C. and 185 ° C., and a maximum value and a minimum value in the range of 120 to 145 ° C. were obtained, respectively. The measurement conditions are as shown below.
・試験片の長さ :40mm
・試験片の幅 : 4mm
・試験片を固定するクランプ間における試験片の長さ:20mm
・測定開始温度 :25℃
・測定終了温度 :250℃
・昇温速度 :5℃/分
・測定周波数 :1Hz <Measurement conditions of tensile storage modulus E '>
-Test piece length: 40 mm
-Test piece width: 4 mm
-Test piece length between clamps for fixing the test piece: 20 mm
-Measurement start temperature: 25 ° C
-Measurement end temperature: 250 ° C
・ Rise rate: 5 ℃ / min ・ Measurement frequency: 1Hz
各実施例および各比較例で得られた離型フィルムを用いて、L/Sが150/150μmの電気配線が形成された絶縁基板(FPC)上にカバーレイフィルムをプレスラミネートした。プレスラミネートでは、ステンレス鋼板、ゴムクッション、フッ素樹脂シート、離型フィルム、カバーレイフィルム、FPC、離型フィルム、フッ素樹脂シート、ゴムクッション、ステンレス鋼の順で各部材を重ね、これを一段型プレス機によりプレスした。プレスにあたっては、10MPaの圧力で加圧しながら10℃/分の昇温速度で185℃まで昇温させ、次いで1分間保持した後、常温まで冷却した。これにより、FPC上にカバーレイフィルムをプレスラミネートしたサンプルを得た。 2.2 Evaluation of embeddability Using a release film obtained in each example and each comparative example, a coverlay film was formed on an insulating substrate (FPC) on which an electrical wiring having an L / S of 150/150 μm was formed. Press laminated. In press lamination, stainless steel plate, rubber cushion, fluororesin sheet, release film, coverlay film, FPC, release film, fluororesin sheet, rubber cushion, stainless steel are stacked in this order, and this is a one-stage press Pressed by machine. In pressing, the temperature was raised to 185 ° C. at a rate of temperature rise of 10 ° C./min while being pressurized at a pressure of 10 MPa, then held for 1 minute, and then cooled to room temperature. This obtained the sample which carried out the press lamination of the coverlay film on FPC.
◎:接着剤の流れの最大値が0.2mm以下である
○:接着剤の流れの最大値が0.2mm超0.3mm以下である
×:接着剤の流れの最大値が0.3mm超である <Evaluation criteria for embedding>
A: The maximum value of the adhesive flow is 0.2 mm or less. ○: The maximum value of the adhesive flow is more than 0.2 mm and less than 0.3 mm. X: The maximum value of the adhesive flow is more than 0.3 mm. Is
2.2で得られたサンプルについて観察することにより、プレスラミネートにおける離型フィルムの離型性を評価した。この評価は、離型フィルムの剥離後、カバーレイフィルムの端部の浮き上がりや剥離有無を、JPCA規格、片面及び両面フレキシブルプリント配線板JPCA-DG02の「7.5.2.3 浮き上がり及びはく離」に準拠し、以下の評価基準に基づいて評価した。なお、この評価は、100個のサンプルについての観察に基づいて行った。 2.3 Evaluation of
By observing the sample obtained in 2.2, the release property of the release film in the press laminate was evaluated. In this evaluation, after peeling of the release film, the end of the cover lay film is lifted up or peeled off, as described in “7.5.2.3 Lifting and peeling” of the JPCA standard, single-sided and double-sided flexible printed wiring board JPCA-DG02. And evaluated based on the following evaluation criteria. In addition, this evaluation was performed based on observation about 100 samples.
◎:浮き上がりおよび剥離の発生率が3%未満である
○:浮き上がりおよび剥離の発生率が3%以上5%未満である
×:浮き上がりまたは剥離の発生率が5%以上である <Evaluation criteria for releasability>
A: The occurrence rate of lifting and peeling is less than 3%. O: The occurrence rate of lifting and peeling is 3% or more and less than 5%. X: The occurrence rate of lifting or peeling is 5% or more.
2.2で得られたサンプルを製造するのに使用した離型フィルムについて観察することにより、プレスラミネートにおける離型フィルムの離型性を評価した。この評価は、離型フィルムの剥離後、離型フィルムの破れ有無を、JPCA規格、片面及び両面フレキシブルプリント配線板JPCA-DG02の「7.5.6.1 表面の付着物」に準拠し、以下の評価基準に基づいて評価した。なお、この評価は、100個のサンプルを製造するのに使用した100枚の離型フィルムについての観察に基づいて行った。 2.4 Evaluation of
By observing the release film used to produce the sample obtained in 2.2, the release property of the release film in the press laminate was evaluated. This evaluation is based on “7.5.6.1 Surface deposits” of the JPCA standard, single-sided and double-sided flexible printed wiring board JPCA-DG02, whether the release film is torn or not after the release film is peeled off. Evaluation was made based on the following evaluation criteria. In addition, this evaluation was performed based on observation about 100 mold release films used for manufacturing 100 samples.
◎:破れ発生率が3%未満である
〇:破れ発生率が3%以上5%未満である
×:破れ発生率が5%以上である <Evaluation criteria for releasability>
◎: Breakage rate is less than 3% ◯: Breakage rate is 3% or more and less than 5% ×: Breakage rate is 5% or more
各実施例および各比較例で得られた離型フィルムを用いて、電気配線が形成された絶縁基板(FPC)上にカバーレイフィルムをプレスラミネートした。これにより、FPC上にカバーレイフィルムを密着させたサンプルを得た。なお、使用したFPCは、カバーレイフィルムをプレスラミネートする面の表面粗さが2.2~2.4で使用したFPCよりも粗いものである。 2.5 Evaluation of Correspondence to Rough Surface Using a release film obtained in each example and each comparative example, a coverlay film was press-laminated on an insulating substrate (FPC) on which electrical wiring was formed. As a result, a sample was obtained in which a cover lay film was adhered to the FPC. The FPC used is rougher than the FPC used when the surface of the coverlay film to be press-laminated has a surface roughness of 2.2 to 2.4.
以上、評価結果を表1、2に示す。 Next, the obtained sample was evaluated for embedding property and releasability of the release film in the same manner as in 2.2 to 2.4, thereby evaluating the compatibility with FPC having a rough surface roughness.
The evaluation results are shown in Tables 1 and 2.
2 基層
210 ダイス
220 タッチロール
230 第1ロール
240 第2ロール
3 第1離型層
30 離型層フィルム
300 熱盤
310 ステンレス鋼板
320 ゴムクッション
330 フッ素樹脂シート
340 未接合体
4 第2離型層
M 融解物 DESCRIPTION OF
Claims (8)
- ポリオレフィン系樹脂と、シンジオタクチック構造を有するポリスチレン系樹脂と、を含む基層と、
前記基層の少なくとも一方の面側に設けられ、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂材料で構成される第1離型層と、
を有し、
JIS K 7244に規定の試験方法に準拠し、試験片の長さ40mm、幅4mm、クランプ間の試験片の長さ20mm、測定開始温度25℃、測定終了温度250℃、昇温速度5℃/分、測定周波数1Hzの測定条件で測定された引張貯蔵弾性率E’が、120℃において1.0×106~5.0×108Paであり、170℃において1.0×107~1.0×109Paであることを特徴とする離型フィルム。 A base layer comprising a polyolefin resin and a polystyrene resin having a syndiotactic structure;
A first release layer that is provided on at least one surface side of the base layer and is made of a resin material mainly composed of a polystyrene-based resin having a syndiotactic structure;
Have
In accordance with the test method specified in JIS K 7244, the length of the test piece is 40 mm, the width is 4 mm, the length of the test piece between the clamps is 20 mm, the measurement start temperature is 25 ° C., the measurement end temperature is 250 ° C., and the heating rate is 5 ° C. / The tensile storage modulus E ′ measured under the measurement conditions of 1 minute and a measurement frequency of 1 Hz is 1.0 × 10 6 to 5.0 × 10 8 Pa at 120 ° C., and 1.0 × 10 7 to 170 ° C. A release film characterized by being 1.0 × 10 9 Pa. - 前記測定条件で測定された引張貯蔵弾性率E’が、185℃において8.0×106~5.0×108Paである請求項1に記載の離型フィルム。 The release film according to claim 1, wherein the tensile storage modulus E ′ measured under the measurement conditions is 8.0 × 10 6 to 5.0 × 10 8 Pa at 185 ° C.
- 前記測定条件で測定された引張貯蔵弾性率E’が、120~145℃の温度域において1.0×106~5.0×108Paである請求項1または2に記載の離型フィルム。 3. The release film according to claim 1, wherein the tensile storage elastic modulus E ′ measured under the measurement conditions is 1.0 × 10 6 to 5.0 × 10 8 Pa in a temperature range of 120 to 145 ° C. .
- 前記ポリオレフィン系樹脂は、ポリプロピレンを含むものである請求項1ないし3のいずれか一項に記載の離型フィルム。 The mold release film according to any one of claims 1 to 3, wherein the polyolefin-based resin contains polypropylene.
- 前記ポリオレフィン系樹脂は、ポリエチレン構造単位とポリスチレン構造単位との共重合体を含むものである請求項4に記載の離型フィルム。 The release film according to claim 4, wherein the polyolefin resin contains a copolymer of a polyethylene structural unit and a polystyrene structural unit.
- 前記共重合体は、ポリエチレン構造単位からなる主鎖と、ポリスチレン構造単位からなる側鎖と、を有するものである請求項5に記載の離型フィルム。 The release film according to claim 5, wherein the copolymer has a main chain composed of polyethylene structural units and a side chain composed of polystyrene structural units.
- 前記ポリオレフィン系樹脂は、エチレン-メタクリル酸メチル共重合体を含むものである請求項4ないし6のいずれか一項に記載の離型フィルム。 The release film according to any one of claims 4 to 6, wherein the polyolefin resin contains an ethylene-methyl methacrylate copolymer.
- さらに、前記基層の前記第1離型層とは反対の面側に設けられ、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂材料で構成される第2離型層を有する請求項1ないし7のいずれか一項に記載の離型フィルム。 Furthermore, it has a 2nd mold release layer comprised by the resin material which has a syndiotactic structure as a main component and is provided in the surface opposite to the said 1st mold release layer of the said base layer. The release film as described in any one of 1 thru | or 7.
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CN201380037570.1A CN104507680B (en) | 2012-07-17 | 2013-07-04 | Mold release film |
KR20147034756A KR20150035596A (en) | 2012-07-17 | 2013-07-04 | Mold release film |
PH12015500100A PH12015500100A1 (en) | 2012-07-17 | 2015-01-14 | Mold release film |
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KR (1) | KR20150035596A (en) |
CN (1) | CN104507680B (en) |
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JP6398221B2 (en) * | 2014-02-26 | 2018-10-03 | 住友ベークライト株式会社 | Release film for producing resin-encapsulated semiconductor device, method for producing release film for producing resin-encapsulated semiconductor device, and method for producing resin-encapsulated semiconductor device |
JP6303727B2 (en) * | 2014-03-31 | 2018-04-04 | 住友ベークライト株式会社 | Release film |
JP6467800B2 (en) * | 2014-07-30 | 2019-02-13 | 住友ベークライト株式会社 | Release film |
JP6648400B2 (en) * | 2014-11-10 | 2020-02-14 | 凸版印刷株式会社 | Terminal resin film, tab and power storage device using the same |
CN110461594B (en) * | 2017-03-22 | 2021-02-12 | 住友电木株式会社 | Release film and method for manufacturing flexible printed circuit board |
EP3904090A4 (en) * | 2018-12-28 | 2022-09-14 | Kuraray Co., Ltd. | Base film for decorative film and decorative film including same |
JP7281381B2 (en) * | 2019-10-04 | 2023-05-25 | 出光興産株式会社 | Resin laminate for low dielectric materials |
CN114080866B (en) * | 2020-10-21 | 2022-09-16 | 住友电木株式会社 | Release film and method for producing molded article |
CN113924825B (en) * | 2020-10-21 | 2022-10-25 | 住友电木株式会社 | Release film and method for producing molded article |
JP6870775B1 (en) * | 2020-10-21 | 2021-05-12 | 住友ベークライト株式会社 | Manufacturing method of release film and molded product |
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JP2004082502A (en) * | 2002-08-27 | 2004-03-18 | Mitsubishi Plastics Ind Ltd | Release film |
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2013
- 2013-07-04 WO PCT/JP2013/068396 patent/WO2014013884A1/en active Application Filing
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KR20150035596A (en) | 2015-04-06 |
JP5895755B2 (en) | 2016-03-30 |
PH12015500100A1 (en) | 2015-03-02 |
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CN104507680A (en) | 2015-04-08 |
CN104507680B (en) | 2016-10-19 |
TWI554375B (en) | 2016-10-21 |
JP2014019017A (en) | 2014-02-03 |
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