WO2024053490A1 - Resin composition for dicing film substrate, dicing film substrate, and dicing film - Google Patents
Resin composition for dicing film substrate, dicing film substrate, and dicing film Download PDFInfo
- Publication number
- WO2024053490A1 WO2024053490A1 PCT/JP2023/031241 JP2023031241W WO2024053490A1 WO 2024053490 A1 WO2024053490 A1 WO 2024053490A1 JP 2023031241 W JP2023031241 W JP 2023031241W WO 2024053490 A1 WO2024053490 A1 WO 2024053490A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unsaturated carboxylic
- carboxylic acid
- dicing film
- ethylene
- ionomer
- Prior art date
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- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
Definitions
- the present invention relates to a resin composition for a dicing film base material, a dicing film base material, and a dicing film.
- a stretchable wafer processing film (herein also referred to as "dicing film”) is attached to the back side of the semiconductor wafer, and the semiconductor wafer is divided into chips using a dicing blade, laser light, etc. .
- the expansion step the dicing film is expanded to widen the distance between the chips and break the chips into small pieces.
- an expansion table placed under the dicing film is pushed up, the dicing film is expanded, and the chips are divided.
- Patent Document 1 describes a radiation-curable adhesive tape for wafer processing that includes an antistatic resin containing a polyether component and the above-mentioned ionomer.
- Patent Document 2 describes a resin composition for a dicing film base material containing the above-mentioned ionomer, ethylene, (meth)acrylic acid, and a copolymer of (meth)acrylic acid alkyl ester.
- Patent Document 3 describes an ionomer/polyamide blend containing a polyamide and an ionomer of a copolymer of ethylene and ⁇ , ⁇ -ethylenically unsaturated carboxylic acid as a resin composition used for molded parts. ing.
- the dicing film around the chips is sufficiently stretchable (hereinafter also referred to as "room-temperature stretchability"). If the dicing film is not sufficiently stretched and a plurality of chips are pushed up by the fine pins, a phenomenon may occur in which chips that are not to be picked up peel off from the dicing film. Furthermore, if the room temperature elongation of the dicing film is low, stress is applied to the chip during the pick-up process, which may cause damage within the chip. When these problems occur, the yield of products decreases and the number of product defects increases.
- Patent Document 1 does not include any description that focuses on the extensibility itself of the adhesive tape for wafer processing. Furthermore, although Patent Document 2 evaluates the heat resistance (e.g., elongation at 120° C.) of the dicing film, it does not focus on elongation at room temperature. Furthermore, since the ionomer/polyamide blend of Patent Document 3 contains a large amount of polyamide, it is difficult to form it into a film.
- the resin composition for dicing film base material is required to have modulus strength of the dicing film at room temperature and low temperature, and may also be required to have elongation at low temperature.
- the modulus strength required for division and the elongation of the film required for expansion are required.
- the film requires a modulus strength to maintain a constant chip gap after separation and a film extensibility necessary during the pick-up process as described above.
- the present invention has been made in view of the above problems.
- the purpose of the present invention is to provide a resin composition for a dicing film base material, a dicing film base material, and a dicing film that can realize a dicing film base material that has excellent elongation properties at room temperature and low temperature, and also has excellent modulus strength at room temperature and low temperature. shall be.
- the present invention provides the following resin composition for a dicing film base material.
- a resin composition for a dicing film base material comprising: [2] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is determined by the total composition of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer.
- [3] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer
- [4] The dicing film base according to any one of [1] to [3], wherein the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 10% or more and 90% or less.
- Resin composition for use Any one of [1] to [4], wherein the degree of neutralization of the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more and 90% or less.
- the resin composition for a dicing film base material as described above.
- the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is , 0.60 or more and less than 1.00, the resin composition for a dicing film base material according to any one of [1] to [6].
- the total content of the ionomer (B) of the acid/unsaturated carboxylic acid ester copolymer and the styrene elastomer (C) is more than 90% by mass and 100% by mass or less, [1] to [8]
- the resin composition for a dicing film base material according to any one of the above.
- melt flow rate measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less, [1] to [9]
- the resin composition for a dicing film base material according to any one of the above.
- the present invention provides the following dicing film base material and dicing film.
- a dicing film base material comprising at least one layer containing the resin composition for a dicing film base material according to any one of [1] to [10] above.
- the average value of the 30% modulus in the MD direction and the 30% modulus in the TD direction measured at 23°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is 8 MPa.
- the dicing film base material according to [11] which has a pressure of 17 MPa or less.
- the average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is:
- a dicing film comprising the dicing film base material according to [11] above, and an adhesive layer laminated on at least one surface of the dicing film base material.
- a dicing film base material that has excellent elongation at room temperature and low temperature, and also excellent modulus strength at room temperature and low temperature is realized.
- a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ ” as lower and upper limits.
- (meth)acrylic acid is a notation used to include both “acrylic acid” and “methacrylic acid”
- (meth)acrylate” includes both “acrylate” and “methacrylate.” This notation is used inclusively.
- the resin composition for dicing film base materials of the present invention (hereinafter also simply referred to as "resin composition”) is mainly used for the base material of dicing films.
- the use of the product is not limited to the base material of a dicing film.
- base materials for dicing films are required to have not only modulus strength at room temperature and low temperature, but also elongation at room temperature and low temperature.
- base materials for dicing films are required to have not only modulus strength at room temperature and low temperature, but also elongation at room temperature and low temperature.
- an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer and an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer It has been revealed that a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature can be obtained by using a resin composition containing the styrene elastomer (C) and styrenic elastomer (C). Although the reason is not clear, it is presumed as follows.
- the resin composition contains an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer (hereinafter also simply referred to as "binary ionomer (A)")
- the cohesive force (rigidity) of the resin composition increases.
- the low-temperature modulus of the dicing film obtained from the resin composition is improved.
- the resin composition contains an ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (hereinafter also simply referred to as "ternary ionomer (B)"), unsaturated carboxylic acid Since the acid ester is contained, the resin composition has good room temperature modulus and room temperature elongation. Furthermore, when the resin composition contains the styrene elastomer (C), the compatibility between the binary ionomer (A) and the ternary ionomer (B) improves, so that the room-temperature modulus and Good room temperature elongation.
- ternary ionomer (B) ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer
- the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) are uniformly mixed, improving compatibility and improving low-temperature elongation.
- a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature is obtained.
- the binary ionomer (A) is a copolymer of ethylene and an unsaturated carboxylic acid, that is, a copolymer of ethylene and an unsaturated carboxylic acid in which part or all of the acid has been neutralized with metal ions. It has a structure in which multiple ethylene/unsaturated carboxylic acid copolymers are crosslinked.
- the resin composition may contain only one type of the binary ionomer (A), or may contain two or more types.
- the ethylene/unsaturated carboxylic acid copolymer that forms the main skeleton of the binary ionomer (A) mainly contains ethylene and unsaturated carboxylic acid.
- structures derived from monomers other than ethylene and unsaturated carboxylic acids may be partially included, for example, all constituent units of the ethylene/unsaturated carboxylic acid copolymer. It may contain 20% by mass or less of structures derived from other monomers based on the amount of .
- those that further include a structure derived from an unsaturated carboxylic acid ester are not included in the ethylene/unsaturated carboxylic acid polymer.
- the amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid copolymer is not limited, but if the amount of ethylene-derived structural units is relative to the amount of all structural units in the ethylene/unsaturated carboxylic acid copolymer,
- the content is preferably 70% by mass or more and 99% by mass or less, more preferably 75% by mass or more and 95% by mass or less, and even more preferably 78% by mass or more and 90% by mass or less.
- the amount of structural units derived from ethylene is 70% by mass or more, blocking etc. are less likely to occur in the resulting dicing film.
- the amount of the structural unit derived from ethylene is 99% by mass or less, the amount of unsaturated carboxylic acid becomes relatively large enough, and the modulus strength and elongation tend to be good.
- the amount of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer is not limited.
- the amount of the structural unit derived from unsaturated carboxylic acid is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or more and 25% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid copolymer. is more preferable, and even more preferably 10% by mass or more and 22% by mass or less.
- the amount of structural units derived from unsaturated carboxylic acid is 1% by mass or more, the modulus strength and elongation rate tend to be good.
- the amount of structural units derived from unsaturated carboxylic acid is 30% by mass or less, blocking etc. are less likely to occur in the resulting dicing film.
- unsaturated carboxylic acids include unsaturated carboxylic acids having 4 to 8 carbon atoms such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, and maleic anhydride.
- acrylic acid or methacrylic acid is preferred from the viewpoint of reactivity and availability.
- the ethylene/unsaturated carboxylic acid copolymer may contain only one type of structural unit derived from these, or may contain two or more types.
- the ethylene/unsaturated carboxylic acid copolymer may have one or more constituent units derived from monomers other than ethylene and unsaturated carboxylic acid.
- monomers other than ethylene and unsaturated carboxylic acids include unsaturated hydrocarbons such as propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, and 1-hexene; vinyl acetate, vinyl propionate, etc. vinyl esters derived from etc.; oxides such as vinyl sulfuric acid and vinyl nitric acid; halogen compounds such as vinyl chloride and vinyl fluoride; primary amine compounds containing vinyl groups; secondary amine compounds containing vinyl groups; carbon monoxide; sulfur dioxide; etc. are included.
- the above-mentioned ethylene/unsaturated carboxylic acid copolymer may be a block copolymer or a random copolymer.
- the ethylene/unsaturated carboxylic acid copolymer may be a graft copolymer obtained by graft-polymerizing a random polymer or a block polymer with a known compound, as long as it does not impair the purpose and effects of the present invention. Good too.
- the metal ion that neutralizes the acid of the ethylene/unsaturated carboxylic acid copolymer is not particularly limited, but examples include lithium ion, sodium ion, potassium ion, rubidium ion, etc. ion, cesium ion, zinc ion, magnesium ion, manganese ion, etc.
- magnesium ion, sodium ion, or zinc ion is preferable from the viewpoint of availability, etc., sodium ion or zinc ion is more preferable, and zinc ion is even more preferable.
- the degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the binary ionomer (A) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable.
- the degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high.
- the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good.
- the degree of neutralization is the ratio of the metal ion compounding ratio to the number of moles of acid groups (for example, carboxy groups) in the binary ionomer (A) (ethylene/unsaturated carboxylic acid copolymer).
- the unit is mol%.
- the degree of neutralization can be measured by infrared absorption spectrum (IR).
- the carboxy groups in the entire resin can be quantified using this method.
- the degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
- melt flow rate (MFR) of the binary ionomer (A) measured at 190°C and a load of 2160g according to JIS K 7210:1999 (equivalent to ISO 1133:1997) is 0.2g/10min. It is preferably 20.0 g/10 minutes or more, more preferably 0.5 g/10 minutes or more and 20.0 g/10 minutes or less, and even more preferably 0.5 g/10 minutes or more and 18.0 g/10 minutes or less.
- the melt flow rate of the binary ionomer (A) is within the above range, the resin composition can be easily molded.
- the ternary ionomer (B) is a copolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic ester, that is, a part of the acid of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer. , or all of them are neutralized with metal ions, and have a structure in which a plurality of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymers are crosslinked.
- the resin composition may contain only one type of the ternary ionomer (B), or may contain two or more types.
- the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer which is the main skeleton of the ternary ionomer (B), mainly contains ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic ester.
- structures derived from monomers other than these may be partially included, for example, the entire structure of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer. It may contain 20% by mass or less of structures derived from other monomers based on the amount of units.
- the amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is not limited, but the amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is It is preferably 60% by mass or more and 94% by mass or less, more preferably 75% by mass or more and 90% by mass or less, based on the amount of all structural units of the polymer. When the amount of structural units derived from ethylene is 60% by mass or more, blocking etc. are less likely to occur in the resulting dicing film.
- the amount of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is not limited.
- the amount of the structural unit derived from unsaturated carboxylic acid is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer. % or more and 20% by mass or less is more preferable.
- the amount of structural units derived from unsaturated carboxylic acid is 1% by mass or more, the modulus strength and elongation rate tend to be good.
- the type of unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is not particularly limited; Same as carboxylic acid.
- the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may contain only one type of structural unit derived from unsaturated carboxylic acid, or may contain two or more types.
- the amount of the structural unit derived from the unsaturated carboxylic ester in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is not limited.
- the amount of the structural unit derived from the unsaturated carboxylic acid ester is preferably 1% by mass or more and 20% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and 1% by mass or more and 20% by mass or less. It is more preferably 15% by mass or more.
- the amount of structural units derived from unsaturated carboxylic ester acid is 1% by mass or more, the low-temperature elongation properties and room-temperature elongation properties of the base material for the dicing film tend to be good.
- the amount of structural units derived from unsaturated carboxylic acid esters is 20% by mass or less, it is relatively easy for the constituents derived from ethylene and unsaturated carboxylic acids to be sufficiently included, making it difficult for blocking etc. to occur in the dicing film. do.
- the unsaturated carboxylic ester includes a compound in which the carboxylic acid of the above-mentioned unsaturated carboxylic acid becomes a carboxylic ester.
- unsaturated carboxylic acid esters include unsaturated carboxylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms in the alkyl group is more preferably 1 to 8, and even more preferably 1 to 4.
- alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2-ethylhexyl, isooctyl, and the like.
- the unsaturated carboxylic acid alkyl esters include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid isobutyl ester, acrylic acid n-butyl ester, acrylic acid isooctyl ester, Includes maleic acid dimethyl ester, maleic acid diethyl ester, etc.
- the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer may contain only one type of structural unit derived from an unsaturated carboxylic ester, or may contain two or more types.
- the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer has one or more constituent units derived from monomers other than ethylene, unsaturated carboxylic acid, and unsaturated carboxylic ester. It's okay. These are the same as structural units derived from other monomers that may be included in the ethylene/unsaturated carboxylic acid copolymer.
- the above-mentioned ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may be a block copolymer or a random copolymer.
- the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may be a graft copolymer obtained by further grafting a known compound to a random polymer or block polymer, within a range that does not impair the purpose and effects of the present invention. It may also be a polymer or the like.
- the metal ion that neutralizes the acid of the ethylene/unsaturated carboxylic acid copolymer is not particularly limited, but examples thereof include lithium ion, sodium ion, potassium ion, rubidium ion, etc. ion, cesium ion, zinc ion, magnesium ion, manganese ion, etc.
- magnesium ion, sodium ion, or zinc ion is preferable from the viewpoint of availability, etc., sodium ion or zinc ion is more preferable, and zinc ion is even more preferable.
- the degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the ternary ionomer (B) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable.
- the degree of neutralization of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good.
- the degree of neutralization is the ratio of the blending ratio of metal ions to the number of moles of acid groups (e.g. carboxy groups) in the ternary ionomer (B) (ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid copolymer). It is. The unit is mol%.
- the degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
- Neutralization degree (%) (1-P b1 /P b2 ) x 100
- melt flow rate (MFR) of the ternary ionomer (B) measured at 190°C and a load of 2160g according to JIS K 7210:1999 (equivalent to ISO 1133:1997) is 0.2g/10min. It is preferably 20.0 g/10 minutes or more, more preferably 0.5 g/10 minutes or more and 20.0 g/10 minutes or less, and even more preferably 0.5 g/10 minutes or more and 18.0 g/10 minutes or less.
- the melt flow rate of the ternary ionomer (B) is within the above range, the resin composition can be easily molded.
- the styrenic elastomer refers to a styrene polymer that is a rubber elastic body at room temperature.
- styrenic elastomers include block copolymers or hydrogenated products thereof, including hard segments consisting of styrene blocks (styrene polymers) and soft segments consisting of alkylene blocks; random copolymers of styrene and alkylene.
- Acid-modified styrenic elastomer which is obtained by acid-modifying the styrene-based elastomer, and the like are included.
- the styrene block in the block copolymer may be a site where two or more styrenes are polymerized, and the alkylene block may be a site where two or more alkenes are polymerized.
- the alkylene block may be a homopolymer of one type of alkene or a copolymer of two or more types of alkenes.
- block copolymers examples include styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SI), styrene-isoprene-styrene Block copolymers (SIS) are included.
- SB styrene-butadiene block copolymer
- SBS styrene-butadiene-styrene block copolymer
- SI styrene-isoprene block copolymer
- SIS styrene-isoprene-styrene Block copolymers
- the styrenic elastomer may be a hydrogenated product of the above block copolymer.
- both the styrene block and the alkylene block may be hydrogenated, or only either the styrene block or the alkylene block may be hydrogenated, and furthermore, one of the styrene block and the alkylene block may be hydrogenated. Only a portion may be hydrogenated.
- hydrogenated block copolymer examples include styrene-ethylene/butylene block copolymer (SEB), which is a hydrogenated product of styrene-butadiene block copolymer (SB), and styrene-butadiene-styrene block.
- SEB styrene-ethylene/butylene-styrene block copolymer
- SEBS Styrene-ethylene/butylene-styrene block copolymer
- SBS hydrogenated product of copolymer
- SIS styrene-isoprene-styrene block copolymer
- SEPS styrene block copolymer
- examples of styrenic elastomers also include random copolymers of styrene and alkylene.
- examples include styrene-butadiene random copolymers, styrene-isoprene random copolymers, styrene-ethylene-butylene random copolymers, styrene-ethylene-propylene random copolymers, styrene-isobutylene random copolymers, styrene -Includes ethylene-isoprene random copolymer, etc.
- the styrenic elastomer may be a hydrogenated product of the random copolymer.
- examples include hydrogenated styrene-butadiene random copolymers (HSBR) and the like.
- styrene-based elastomer that has not been acid-modified as described below
- hydrogenated substances are preferred among the above, and styrene-ethylene/butylene-styrene block copolymer (SEBS) and styrene-ethylene/propylene-styrene block copolymer ( SEPS) is more preferable, and styrene-ethylene/butylene-styrene block copolymer (SEBS) is more preferable, from the viewpoint that it can improve the low-temperature elongation properties and room-temperature elongation properties of the base material for the dicing film obtained from the resin composition. Particularly preferred.
- styrenic elastomers are acid-modified styrene elastomers in which an elastomer made of the block copolymer or random polymer, or a hydrogenated product thereof, is graft-modified with an unsaturated carboxylic acid or a derivative thereof.
- the acid-modified styrenic elastomer may be obtained by graft-modifying the block copolymer or random polymer, or a hydrogenated product thereof, with one type of unsaturated carboxylic acid or a derivative thereof, or two or more types. may be graft-modified with an unsaturated carboxylic acid or a derivative thereof.
- Examples of unsaturated carboxylic acids graft-polymerized to the above block copolymers, random copolymers, etc. include (meth)acrylic acid, 2-ethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. included.
- examples of unsaturated carboxylic acid derivatives that can be graft-polymerized to styrenic elastomers include acid anhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; acid esters such as monomethyl maleate and monoethyl maleate; and acid amides. ; acid halides; etc. are included.
- maleic acid or maleic anhydride is preferred from the viewpoint of reactivity with the styrene elastomer.
- the acid-modified styrenic elastomer can be obtained by graft polymerizing the block copolymer, random copolymer, etc. with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator.
- the radical initiator may be any one used in the graft reaction of polyolefins, and known compounds can be used.
- the acid value of the acid-modified styrenic elastomer is preferably more than 0 mg CH 3 ONa/g and less than 20 mg CH 3 ONa/g, more preferably more than 0 mg CH 3 ONa/g and less than 11 mg CH 3 ONa/g, and more preferably 0.5 mg CH 3 ONa/g. More preferably, the amount is from 11 mg CH 3 ONa/g to 11 mg CH 3 ONa/g.
- the acid value of the acid-modified styrene elastomer is within this range, it tends to have good elongation properties at low temperatures and room temperatures.
- the melt plate of the styrene elastomer (C) is preferably 0.1 g/10 minutes to 100 g/10 minutes, more preferably 0.5 g/10 minutes to 90 g/10 minutes, and 1.0 g/10 minutes to 80 g/10 minutes. minutes, more preferably 2.0 g/10 minutes to 75 g/10 minutes.
- the above melt flow rate is a value measured at 230° C. and a load of 2160 g in accordance with JIS K 7210:1999 (corresponding to ISO 1133:1997).
- the Tan ⁇ peak temperature of the styrene elastomer (C) is preferably -60°C or higher, more preferably -55°C or higher, from the viewpoint of improving the low-temperature elongation properties and room-temperature elongation properties of the obtained base material for the dicing film. , -50°C or higher is more preferred.
- the Tan ⁇ peak temperature is a temperature at which a peak value is obtained in a dynamic viscoelasticity test (temperature dependent measurement 10 Hz) in accordance with JIS K 6394 (corresponding to ISO 4664-1:2005).
- the resin composition may contain various additives, antistatic agents, ultraviolet absorbers, fillers, other polymers, etc., as necessary, within a range that does not impair the effects of the present invention.
- additives examples include antioxidants, heat stabilizers, light stabilizers, pigments, dyes, lubricants, antiblocking agents, fungicides, antibacterial agents, flame retardants, flame retardant aids, crosslinking agents, and crosslinking aids.
- the content of the additive is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, when the total mass of the resin components contained in the resin composition is 100 parts by mass.
- examples of the antistatic agent include a low molecular weight antistatic agent and a polymer type antistatic agent, and a polymer type antistatic agent is preferable.
- a polymer type antistatic agent refers to conductive sites (e.g., polyether-derived structural sites, quaternary ammonium base sites, etc.) and non-conductive sites (e.g., polyamide-derived structural sites, polyethylene, etc.). It is a copolymer having a molecular weight of 300 or more (preferably 1000 to 10000). The molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC. Note that conductivity means that the surface resistivity measured based on ASTM D257 is 10 10 ⁇ / ⁇ or less.
- polymer type antistatic agent examples include vinyl copolymers having sulfonate salts in the molecule, alkyl sulfonate salts, alkylbenzene sulfonate salts, betaine, and the like.
- polymer type antistatic agent examples include polyether amide, polyether ester amide, an inorganic protonic acid salt of polyether amide, or an inorganic protonic acid salt of polyether ester amide.
- Salts of inorganic protic acids include alkali metal salts, alkaline earth metal salts, zinc salts, or ammonium salts.
- ultraviolet absorbers examples include benzophenone-based, benzoate-based, benzotriazole-based, cyanoacrylate-based, hindered amine-based, and the like.
- fillers examples include silica, clay, calcium carbonate, barium sulfate, glass beads, talc, etc.
- additives are appropriately selected depending on their types.
- polystyrene resin examples include polyolefins such as polyethylene and polypropylene, and polyamides.
- the amount of polyamide is preferably less than 5 parts by mass when the total mass of the resin components contained in the resin composition is 100 parts by mass. It is preferable that the resin composition does not contain polyamide as other polymers.
- the amount of the binary ionomer (A) is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, based on the total amount of the resin composition.
- the amount of the ternary ionomer (B) is preferably 10% by mass or more and 80% by mass or less, more preferably 12% by mass or more and 75% by mass or less, based on the total amount of the resin composition.
- the amount of the styrene elastomer (C) is preferably 5% by mass or more and 35% by mass or less, more preferably 7% by mass or more and 32% by mass or less, based on the total amount of the resin composition.
- the mass of the binary ionomer (A) is 0.10 or more and 0.95
- 0.15 or more and 0.90 or less are more preferable
- 0.20 or more and 0.85 or less are still more preferable.
- the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) is 1, the binary ionomer (A) and the ternary ionomer (B)
- the total mass is preferably 0.60 or more and less than 1.00, more preferably 0.65 or more and 0.95 or less.
- the total mass of the resin components contained in the resin composition is 100% by mass
- the total content of the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) is , preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, even more preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. It is more preferably not more than 90% by mass and not more than 100% by mass, even more preferably not less than 95% by mass and not more than 100% by mass, and more than 95% by mass and not more than 100% by mass. It is more preferably at least 98% by mass and at most 100% by mass, even more preferably at least 99% by mass and at most 100% by mass.
- the "amount (mass) of the structural unit derived from the unsaturated carboxylic acid in the binary ionomer (A)" relative to the total mass of the resin components ) and the amount (mass) of the unsaturated carboxylic acid-derived structural units in the ternary ionomer (B)" adjust the amount of each component so that the ratio is 5% by mass or more and 20% by mass or less. It is preferable to adjust the amount of each component so that it is 7% by mass or more and 15% by mass or less, and it is more preferable to adjust the amount of each component so that it is 9% by mass or more and 13% by mass or less. preferable.
- the amount of the structural unit derived from unsaturated carboxylic acid in the resin composition is within the above range, low-temperature modulus properties tend to be good.
- the "amount of structural units derived from the unsaturated carboxylic acid ester in the ternary ionomer (B)" relative to the total mass of the resin components It is preferable to adjust the amount of each component so that the ratio of "mass)" is 0.5% by mass or more and 10% by mass or less, and the amount of each component is adjusted so that the ratio of "mass)” is 1% by mass or more and 8% by mass or less. It is more preferable.
- the amount of the structural unit derived from the unsaturated carboxylic acid ester in the resin composition is within the above range, the elongation properties at room temperature and low temperature tend to be good.
- the degree of neutralization of the carboxylic acid in the resin composition is preferably 40% or more and 90% or less, more preferably 45% or more and 85% or less, further preferably 50% or more and 80% or less, further preferably 55% or more and 75% or less, and even more preferably 60% or more and 70% or less.
- the above degree of neutralization is, for example, when the degree of neutralization of the unsaturated carboxylic acid in the binary ionomer (A) and the degree of neutralization of the unsaturated carboxylic acid in the ternary ionomer (B) are known.
- the degree of neutralization of the unsaturated carboxylic acid in the entire resin composition is 40% or more, when the resin composition is used as a base material for a dicing film, the modulus strength of the base film at room temperature and low temperature becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good.
- the method for producing the resin composition of the present invention is not particularly limited, and includes a binary ionomer (A), a ternary ionomer (B), and a styrene elastomer (C), and if necessary, other polymers and additives.
- A binary ionomer
- B ternary ionomer
- C styrene elastomer
- the shape of the resin composition after the kneading is not particularly limited, and may be, for example, in the form of pellets, or may be processed into a long or single sheet.
- the melt flow rate of the resin composition measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less. is preferable, 0.2 g/10 minutes or more and 20 g/10 minutes or less, more preferably 0.3 g/10 minutes or more and 10 g/10 minutes or less, even more preferably 0.4 g/10 minutes or more and 5 g/10 minutes or less. , more preferably 0.5 g/10 minutes or more and 3 g/10 minutes or less.
- the melt flow rate of the resin composition is within this range, the modulus strength at room temperature and low temperature and the elongation property at room temperature and low temperature of the base material obtained from the resin composition tend to be good.
- the dicing base material may be any base material as long as it has at least one layer containing the above-mentioned resin composition. Since the dicing film base material has a layer containing the above-mentioned resin composition, it exhibits excellent modulus strength and elongation at room temperature and low temperature.
- the dicing film base material is suitably used as a base material for a dicing film, but is not limited to this use.
- the structure of the dicing film base material is not particularly limited, and may have only one layer containing the above-mentioned resin composition, or may have two or more layers containing the above-mentioned resin composition. Furthermore, other resin layers may be laminated as necessary.
- the dicing film base material examples include a laminate with a one-layer structure consisting only of a layer containing the above-mentioned resin composition; a laminate with a two-layer structure consisting of a layer containing the above-mentioned resin composition and another resin layer. body; a laminate having a three-layer structure consisting of three layers: a layer containing the above-mentioned resin composition/another resin layer/a layer containing the above-mentioned resin composition; and the like.
- the dicing film base material may further contain a layer containing an adhesive, an adhesive sheet, etc. in addition to the above.
- the layer containing the above-mentioned resin composition may be a layer consisting only of the above-mentioned resin composition, or may include the above-mentioned resin composition and other components within the range that does not impair the purpose and effects of the present invention.
- a layer consisting essentially of the above-mentioned resin composition is preferable from the viewpoint of the extensibility and modulus strength of the dicing film base material.
- the thickness of the layer containing the above resin composition is not particularly limited, but from the viewpoint of improving the strength, modulus strength, elongation, etc. of the dicing film base material, it is preferably 50 ⁇ m or more and 200 ⁇ m or less, and 60 ⁇ m or more and 180 ⁇ m or less. More preferred.
- the average value of the 30% modulus in the MD direction (Machine Direction) and the 30% modulus in the TD direction (Transverse Direction) measured at 23° C. of the layer containing the resin composition is preferably 8 MPa or more and 17 MPa or less, and 10 MPa or more and 15 MPa or less. The following are more preferred.
- the average value of the 30% modulus at 23° C. is within this range, the extensibility of the dicing film base material at room temperature tends to be good.
- the above 30% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 ⁇ m, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The distance between chucks is 100 mm, and the test speed is 300 mm/min.
- the average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15° C. of the layer containing the resin composition is preferably 20 MPa or more, more preferably 24 MPa or more.
- the dicing film base material tends to have good separability and elongation at low temperatures.
- the above 10% modulus is determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 ⁇ m, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The distance between the chucks is 100 mm, and the test speed is 1000 mm/min.
- the layer containing the resin composition can measure both the 200% modulus in the MD direction and the 200% modulus in the TD direction at 23°C. If both the 200% modulus in the MD direction at 23° C. and the 200% modulus in the TD direction at 23° C. can be measured, stress is less likely to be applied to the chip in the pick-up process, and damage within the chip is less likely to occur.
- the above 200% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 ⁇ m, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm, and the film was determined according to JIS K 7127:1999 (ISO 527). -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The test speed is 300 mm/min.
- the layer containing the resin composition can measure both the 200% modulus in the MD direction and the 200% modulus in the TD direction at -15°C. If both the 200% modulus in the MD direction at -15°C and the 200% modulus in the TD direction at -15°C can be measured, it is possible to measure both the 200% modulus in the MD direction at -15°C and the 200% modulus in the TD direction at -15°C. Easy to perform expansion.
- the above 200% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 ⁇ m, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The test speed is 1000 mm/min.
- examples of other resin layers include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene/ ⁇ -olefin copolymer, polypropylene, ethylene/unsaturated carboxylic acid copolymer or its ionomer.
- LLDPE linear low density polyethylene
- LDPE low density polyethylene
- ethylene/ ⁇ -olefin copolymer polypropylene
- ethylene/unsaturated carboxylic acid copolymer or its ionomer ethylene/unsaturated carboxylic acid copolymer or its ionomer.
- ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid alkyl ester terpolymer or its ionomer ethylene/unsaturated carboxylic acid alkyl ester copolymer, ethylene/vinyl ester copolymer, ethylene/unsaturated alkyl carboxylate
- a layer containing an ester/carbon monoxide copolymer, an unsaturated carboxylic acid graft product thereof, polyvinyl chloride, etc. is included.
- the other resin layer may contain only one type of the above resin, or may contain two or more types of the above resin.
- the thickness of the other resin layer is not particularly limited, but from the viewpoint of not impairing the modulus strength and elongation of the layer containing the resin composition, it is preferably 10 ⁇ m or more and 100 ⁇ m or less, and more preferably 15 ⁇ m or more and 80 ⁇ m or less.
- the thickness of the entire dicing film base material is preferably 50 ⁇ m or more from the viewpoint of frame retention during dicing and 200 ⁇ m or less from the viewpoint of expandability, considering that it is used as a component of the dicing film.
- the surface of the dicing film base material may be subjected to various treatments, such as corona treatment. Furthermore, electron beam irradiation may be performed.
- the manufacturing method of the above-mentioned dicing film base material is not particularly limited, and it can be manufactured by a known molding method.
- a dicing film base material consisting only of a layer containing the above-mentioned resin composition
- the above resin composition etc. may be molded.
- the dicing film base material is a laminate of a layer containing the above-mentioned resin composition and another resin layer
- the above-mentioned resin composition and other resin are combined by a coextrusion lamination method, etc. It can be formed by Alternatively, a layer containing the above-mentioned resin composition and another resin layer may be produced separately, and then bonded together using an adhesive, an adhesive sheet, or the like.
- materials for adhesives and adhesive sheets include various ethylene copolymers and unsaturated carboxylic acid grafts thereof.
- the dicing film base material is a laminate of a layer containing the above-mentioned resin composition and another resin layer
- one of the layer containing the above-mentioned resin composition and the other resin layer is The first layer may be formed first, and then the other layer may be formed on the one layer using a T-die film molding machine, an extrusion coating molding machine, etc., and then laminated.
- the dicing film of the present invention only needs to include the above-described dicing film base material and an adhesive layer laminated on at least one surface thereof, and may include other configurations as necessary. .
- the above-mentioned dicing film base material consists of multiple layers, it is preferable that the layer containing the resin composition in the dicing film base material and the adhesive layer are laminated.
- the adhesive constituting the adhesive layer can be an adhesive for the adhesive layer of a general dicing film.
- the adhesive include rubber-based, acrylic-based, silicone-based, and polyvinyl ether-based adhesives; radiation-curable adhesives; heat-foaming adhesives, and the like.
- the adhesive layer preferably contains a radiation-curable adhesive, and more preferably contains an ultraviolet-curable adhesive.
- UV-curable adhesives usually contain a radically polymerizable compound (which can be a monomer, oligomer, or polymer) and a photopolymerization initiator, and optionally a crosslinker, tackifier, and filler. Contains additives such as anti-aging agents, anti-aging agents, and coloring agents.
- radically polymerizable compounds examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and (meth)acrylate.
- Monomers or oligomers of alkyl (meth)acrylates such as isononyl acid; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, etc.
- photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; aromatic ketones such as ⁇ -hydroxycyclohexylphenyl ketone; aromatic ketals such as benzyl dimethyl ketal. ; Includes thioxanthone such as polyvinylbenzophenone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone.
- crosslinking agents examples include polyisocyanate compounds, melamine resins, urea resins, polyamines, carboxyl group-containing polymers, and the like.
- the thickness of the adhesive layer is appropriately selected depending on the type of adhesive, and is preferably 3 to 100 ⁇ m, more preferably 3 to 50 ⁇ m.
- the adhesive layer of the dicing film may be protected by a separator.
- the surface of the adhesive layer can be kept smooth.
- the dicing film can be easily handled and transported, and it is also possible to process a label on the separator.
- the separator is peeled off when using the dicing film.
- the separator may be paper or a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, etc. Furthermore, the surface of the separator that comes into contact with the adhesive layer may be subjected to a release treatment such as silicone treatment or fluorine treatment, as necessary, in order to improve the releasability from the adhesive layer.
- the thickness of the separator is usually about 10 to 200 ⁇ m, preferably about 25 to 100 ⁇ m.
- the method for producing the dicing film is not particularly limited, and for example, the dicing film may be produced by applying an adhesive onto the dicing base material using a known method.
- the adhesive can be applied using a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, or the like.
- an adhesive layer may be formed by applying an adhesive on a release sheet, and the adhesive layer may be transferred to a dicing film base material to laminate the dicing film base material and the adhesive layer.
- the dicing film base material and the adhesive layer may be formed simultaneously by coextrusion or the like.
- IO1 Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 85% by mass, content of structural units derived from methacrylic acid: 15% by mass, degree of neutralization: 59% zinc, JIS MFR: 8.9 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
- IO2 Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 20% by mass, degree of neutralization: 40% zinc, JIS MFR: 8.0 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
- IO3 Ionomer of ethylene/methacrylic acid/butyl acrylate copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 10% by mass, butyl acrylate) Content of structural units derived from: 10% by mass, degree of neutralization: 70% zinc, MFR measured at 190°C and 2160g load according to JIS K 7210:1999 (equivalent to ISO 1133:1997): 1g /10 minutes)
- Examples 1 to 11 and Comparative Examples 1 to 5 In the proportions (mass ratio) shown in Table 1, the ionomer (A) of ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene-based The elastomer (C) was dry blended. Next, the dry blended mixture was charged into a resin inlet of a 30 mm ⁇ twin screw extruder and melt-kneaded at a die temperature of 230° C. to obtain a resin composition for a dicing film base material. Regarding the obtained resin composition for a dicing film base material, MFR was measured at 190° C. and a load of 2160 g in accordance with JIS K 7210:1999 (corresponding to ISO 1133:1997). The results are shown in Table 1.
- the obtained resin composition for a dicing film base material was molded using a 40 mm ⁇ T-die film molding machine at a processing temperature of 230° C. to produce a 100 ⁇ m thick T-die film.
- the obtained T-die film was used as a dicing film base material and evaluated by the following method.
- the total amount of structural units derived from unsaturated carboxylic acids is determined by "content ratio of binary ionomer (A) x amount of structural units derived from carboxylic acid in binary ionomer (A)” and “amount of structural units derived from carboxylic acid in ternary ionomer (A)” It was calculated from the sum of the content ratio of (B) x the amount of structural units derived from carboxylic acid in the ternary ionomer (B).
- the total amount of structural units derived from unsaturated carboxylic acid esters was calculated from "content ratio of ternary ionomer (B) x amount of structural units derived from carboxylic acid esters in ternary ionomer (B)".
- the degree of neutralization (mol%) is calculated as follows: "Degree of neutralization of the binary ionomer (A) x (of the binary ionomer (A) relative to the total amount of the binary ionomer (A) and the ternary ionomer (B)”) "Amount ratio)" + "Neutralization degree of ternary ionomer (B) x (Ratio of amount of ternary ionomer (B) to the total amount of binary ionomer (A) and ternary ionomer (B) )”. Furthermore, “total amount of structural units derived from unsaturated carboxylic acid x degree of neutralization/100” was also calculated. The results are shown in Table 1.
- the 30% modulus in the MD direction and the 30% modulus in the TD direction obtained in the above test were averaged, and the room temperature modulus strength of the dicing film base material was evaluated according to the following criteria.
- the 10% modulus in the MD direction and the 10% modulus in the TD direction obtained in the above test were averaged, and the low-temperature modulus strength of the dicing film base material was evaluated based on the following criteria.
- the room temperature elongation of the dicing film base material was evaluated based on the following criteria.
- the low temperature elongation of the dicing film base material was evaluated based on the following criteria.
- Comparative Example 1 which does not contain the ternary ionomer (B) and the styrene elastomer (C), has low room temperature modulus strength, room temperature elongation, and low temperature elongation, and Modulus strength and room temperature elongation were low.
- Comparative Example 3 which did not contain the binary ionomer (A) and the styrene elastomer (C), the low-temperature elongation properties were low. Furthermore, in Comparative Example 4, which did not contain the styrene elastomer (C), low-temperature elongation was low. Furthermore, in Comparative Example 5, which did not contain the ternary ionomer (B), low-temperature elongation was low.
- a dicing film base material that has excellent elongation at room temperature and low temperature, and also excellent modulus strength at room temperature and low temperature is realized. Therefore, it is very useful in the field of manufacturing semiconductor devices.
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Abstract
The present invention addresses the problem of providing a resin composition for a dicing film substrate, the resin composition being capable of forming a dicing film substrate having excellent elongation at room temperature and at low temperatures and having excellent modulus strength at room temperature and at low temperatures. The above-mentioned problem is solved by a resin composition for a dicing film substrate, the resin composition comprising an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer, an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and a styrene-based elastomer (C).
Description
本発明は、ダイシングフィルム基材用樹脂組成物、ダイシングフィルム基材、およびダイシングフィルムに関する。
The present invention relates to a resin composition for a dicing film base material, a dicing film base material, and a dicing film.
ＩＣ（集積回路）等の半導体装置の製造過程では、回路パターンを形成した半導体ウエハを薄膜化した後、半導体ウエハをチップ単位に分断するダイシング工程を行うことが一般的である。ダイシング工程では、半導体ウエハの裏面に伸縮性を有するウエハ加工用フィルム（本明細書では、「ダイシングフィルム」とも称する）を貼着し、ダイシングブレードやレーザー光等によって半導体ウエハをチップ単位に分断する。そして拡張工程によって、ダイシングフィルムを拡張することにより、チップどうしの間隔を広げ、チップを小片化する。当該拡張工程では、例えばダイシングフィルムの下に配置した拡張テーブルを押し上げ、ダイシングフィルムを拡張し、チップを分割する。
In the manufacturing process of semiconductor devices such as ICs (integrated circuits), it is common to thin a semiconductor wafer on which a circuit pattern is formed, and then perform a dicing process to cut the semiconductor wafer into chips. In the dicing process, a stretchable wafer processing film (herein also referred to as "dicing film") is attached to the back side of the semiconductor wafer, and the semiconductor wafer is divided into chips using a dicing blade, laser light, etc. . Then, in the expansion step, the dicing film is expanded to widen the distance between the chips and break the chips into small pieces. In the expansion step, for example, an expansion table placed under the dicing film is pushed up, the dicing film is expanded, and the chips are divided.
その後、ピックアップ工程において、所望のチップのみをダイシングフィルムからピックアップして所望の用途に使用する。当該ピックアップ工程では、ダイシングフィルム側から、所望のチップのみを微細ピンで突き上げて、ピックアップすることが一般的である。
Thereafter, in the pick-up process, only the desired chips are picked up from the dicing film and used for the desired purpose. In the pick-up process, it is common to pick up only desired chips from the dicing film side by pushing them up with fine pins.
ここで、ダイシングフィルムを構成する材料として、エチレン・（メタ）アクリル酸共重合体を金属イオンで架橋したアイオノマーが知られている。例えば特許文献１には、ポリエーテル成分を含む帯電防止樹脂と、上記アイオノマーと、を含む放射線硬化型ウエハ加工用粘着テープが記載されている。特許文献２には、上記アイオノマーと、エチレンと、（メタ）アクリル酸と、（メタ）アクリル酸アルキルエステルの共重合体と、を含むダイシングフィルム基材用樹脂組成物が記載されている。
Here, an ionomer made by crosslinking an ethylene/(meth)acrylic acid copolymer with metal ions is known as a material constituting the dicing film. For example, Patent Document 1 describes a radiation-curable adhesive tape for wafer processing that includes an antistatic resin containing a polyether component and the above-mentioned ionomer. Patent Document 2 describes a resin composition for a dicing film base material containing the above-mentioned ionomer, ethylene, (meth)acrylic acid, and a copolymer of (meth)acrylic acid alkyl ester.
また、成型部品等に使用する樹脂組成物として、エチレンおよびα，β－エチレン性不飽和カルボン酸の共重合体のアイオノマーと、ポリアミドと、を含むアイオノマー／ポリアミド配合物が特許文献３に記載されている。
Furthermore, Patent Document 3 describes an ionomer/polyamide blend containing a polyamide and an ionomer of a copolymer of ethylene and α,β-ethylenically unsaturated carboxylic acid as a resin composition used for molded parts. ing.
ここで、上述のピックアップ工程で、所望のチップのみを適切にピックアップするためには、チップの周囲のダイシングフィルムが十分に伸びること（以下、「常温伸び性」とも称する）が重要である。ダイシングフィルムが十分に伸びずに、微細ピンによって複数のチップが突き上げられてしまうと、ピックアップ対象ではないチップがダイシングフィルムから剥離する現象が生じることがある。また、ダイシングフィルムの常温伸び性が低いと、ピックアップ工程において、チップに応力が掛かり、チップ内の破損が起こることもある。これらの問題が生じると、製品の歩留まりが低下したり、製品不良が増加したりする。
Here, in order to appropriately pick up only the desired chips in the above-mentioned pick-up process, it is important that the dicing film around the chips is sufficiently stretchable (hereinafter also referred to as "room-temperature stretchability"). If the dicing film is not sufficiently stretched and a plurality of chips are pushed up by the fine pins, a phenomenon may occur in which chips that are not to be picked up peel off from the dicing film. Furthermore, if the room temperature elongation of the dicing film is low, stress is applied to the chip during the pick-up process, which may cause damage within the chip. When these problems occur, the yield of products decreases and the number of product defects increases.
しかしながら、特許文献１には、ウエハ加工用粘着テープの伸び性自体に着目した記載がない。さらに、特許文献２では、ダイシングフィルムの耐熱性（例えば、１２０℃における伸び性）を評価しているものの、常温での伸び性には着目していない。さらに、特許文献３のアイオノマー／ポリアミド配合物は、ポリアミドを多量に含むことから、これをフィルム状に成形することが困難である。
However, Patent Document 1 does not include any description that focuses on the extensibility itself of the adhesive tape for wafer processing. Furthermore, although Patent Document 2 evaluates the heat resistance (e.g., elongation at 120° C.) of the dicing film, it does not focus on elongation at room temperature. Furthermore, since the ionomer/polyamide blend of Patent Document 3 contains a large amount of polyamide, it is difficult to form it into a film.
また、ダイシングフィルム基材用樹脂組成物には、前記の常温伸び性に加えて、常温や低温におけるダイシングフィルムのモジュラス強度が求められ、さらに低温における伸び性も求められることもある。具体的には、ダイシング・ダイボンド一体型フィルムの場合、低温でチップとダイボンドフィルムの分断と拡張（エキスパンド）を行う工程があり、分断に必要なモジュラス強度とエキスパンドに必要なフィルムの伸び性とが要求される。また、常温時には、分断後のチップ間隙を一定に維持するためのモジュラス強度と前記のとおりピックアップ工程時に必要なフィルム伸び性が求められる。しかしながら、従来、常温や低温でのモジュラス強度および常温および低温での伸び性を両立させることは試みられていなかった。
In addition to the above-mentioned room temperature elongation, the resin composition for dicing film base material is required to have modulus strength of the dicing film at room temperature and low temperature, and may also be required to have elongation at low temperature. Specifically, in the case of a dicing/die bond integrated film, there is a process of dividing and expanding the chip and die bond film at low temperatures, and the modulus strength required for division and the elongation of the film required for expansion are required. Furthermore, at room temperature, the film requires a modulus strength to maintain a constant chip gap after separation and a film extensibility necessary during the pick-up process as described above. However, no attempt has been made to achieve both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature.
本発明は上記課題を鑑みてなされたものである。常温および低温における伸び性に優れ、さらには常温および低温におけるモジュラス強度にも優れたダイシングフィルム基材を実現可能なダイシングフィルム基材用樹脂組成物、ダイシングフィルム基材、およびダイシングフィルムの提供を目的とする。
The present invention has been made in view of the above problems. The purpose of the present invention is to provide a resin composition for a dicing film base material, a dicing film base material, and a dicing film that can realize a dicing film base material that has excellent elongation properties at room temperature and low temperature, and also has excellent modulus strength at room temperature and low temperature. shall be.
すなわち、本発明は、以下のダイシングフィルム基材用樹脂組成物を提供する。
［１］エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）と、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）と、スチレン系エラストマー（Ｃ）と、を含むダイシングフィルム基材用樹脂組成物。
［２］前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）中の不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の全構成単位の量に対して、１質量％以上３０質量％以下である、［１］に記載のダイシングフィルム基材用樹脂組成物。
［３］前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）中の、不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の全構成単位の量に対して、１質量％以上３０質量％以下である、［１］または［２］に記載のダイシングフィルム基材用樹脂組成物。
［４］前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の中和度が、１０％以上９０％以下である、［１］～［３］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［５］前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の中和度が、１０％以上９０％以下である、［１］～［４］のいずれかに記載のダイシングフィルム基材用樹脂組成物。 That is, the present invention provides the following resin composition for a dicing film base material.
[1] An ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer, an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and a styrene elastomer (C). A resin composition for a dicing film base material comprising:
[2] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is determined by the total composition of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer. The resin composition for a dicing film base material according to [1], which is 1% by mass or more and 30% by mass or less based on the amount of units.
[3] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer The resin composition for a dicing film base material according to [1] or [2], wherein the resin composition is 1% by mass or more and 30% by mass or less based on the amount of all structural units of the ionomer (B) of the acid ester copolymer.
[4] The dicing film base according to any one of [1] to [3], wherein the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 10% or more and 90% or less. Resin composition for use.
[5] Any one of [1] to [4], wherein the degree of neutralization of the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more and 90% or less. The resin composition for a dicing film base material as described above.
［１］エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）と、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）と、スチレン系エラストマー（Ｃ）と、を含むダイシングフィルム基材用樹脂組成物。
［２］前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）中の不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の全構成単位の量に対して、１質量％以上３０質量％以下である、［１］に記載のダイシングフィルム基材用樹脂組成物。
［３］前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）中の、不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の全構成単位の量に対して、１質量％以上３０質量％以下である、［１］または［２］に記載のダイシングフィルム基材用樹脂組成物。
［４］前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の中和度が、１０％以上９０％以下である、［１］～［３］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［５］前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の中和度が、１０％以上９０％以下である、［１］～［４］のいずれかに記載のダイシングフィルム基材用樹脂組成物。 That is, the present invention provides the following resin composition for a dicing film base material.
[1] An ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer, an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and a styrene elastomer (C). A resin composition for a dicing film base material comprising:
[2] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is determined by the total composition of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer. The resin composition for a dicing film base material according to [1], which is 1% by mass or more and 30% by mass or less based on the amount of units.
[3] The amount of structural units derived from unsaturated carboxylic acid in the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer The resin composition for a dicing film base material according to [1] or [2], wherein the resin composition is 1% by mass or more and 30% by mass or less based on the amount of all structural units of the ionomer (B) of the acid ester copolymer.
[4] The dicing film base according to any one of [1] to [3], wherein the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 10% or more and 90% or less. Resin composition for use.
[5] Any one of [1] to [4], wherein the degree of neutralization of the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more and 90% or less. The resin composition for a dicing film base material as described above.
［６］前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）および前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の合計質量を１とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の質量が、０．１０以上０．９５以下である、［１］～［５］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
[７]前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量を１とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）および前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の合計質量が、０．６０以上１．００未満である、［１］～［６］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［８］ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量の割合が、５０質量％以上１００質量％以下である、［１］～［７］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［９］ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計含有率が、９０質量％を超えて１００質量％以下である、［１］～［８］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［１０］ＪＩＳ Ｋ ７２１０：１９９９に準拠して、１９０℃、荷重２１６０ｇにて測定されるメルトフローレートが、０．１ｇ／１０分以上３０ｇ／１０分以下である、［１］～［９］のいずれかに記載のダイシングフィルム基材用樹脂組成物。 [6] When the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 1, The resin composition for a dicing film base material according to any one of [1] to [5], wherein the mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.10 or more and 0.95 or less. thing.
[7] The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene elastomer (C). When the total mass is 1, the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is , 0.60 or more and less than 1.00, the resin composition for a dicing film base material according to any one of [1] to [6].
[8] When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid copolymer [1] to [7], wherein the ratio of the total mass of the ionomer (B) of the acid/unsaturated carboxylic acid ester copolymer and the styrene elastomer (C) is 50% by mass or more and 100% by mass or less Any resin composition for a dicing film base material.
[9] When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid copolymer The total content of the ionomer (B) of the acid/unsaturated carboxylic acid ester copolymer and the styrene elastomer (C) is more than 90% by mass and 100% by mass or less, [1] to [8] The resin composition for a dicing film base material according to any one of the above.
[10] In accordance with JIS K 7210:1999, the melt flow rate measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less, [1] to [9] The resin composition for a dicing film base material according to any one of the above.
[７]前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量を１とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）および前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の合計質量が、０．６０以上１．００未満である、［１］～［６］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［８］ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量の割合が、５０質量％以上１００質量％以下である、［１］～［７］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［９］ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計含有率が、９０質量％を超えて１００質量％以下である、［１］～［８］のいずれかに記載のダイシングフィルム基材用樹脂組成物。
［１０］ＪＩＳ Ｋ ７２１０：１９９９に準拠して、１９０℃、荷重２１６０ｇにて測定されるメルトフローレートが、０．１ｇ／１０分以上３０ｇ／１０分以下である、［１］～［９］のいずれかに記載のダイシングフィルム基材用樹脂組成物。 [6] When the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 1, The resin composition for a dicing film base material according to any one of [1] to [5], wherein the mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.10 or more and 0.95 or less. thing.
[7] The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene elastomer (C). When the total mass is 1, the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is , 0.60 or more and less than 1.00, the resin composition for a dicing film base material according to any one of [1] to [6].
[8] When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid copolymer [1] to [7], wherein the ratio of the total mass of the ionomer (B) of the acid/unsaturated carboxylic acid ester copolymer and the styrene elastomer (C) is 50% by mass or more and 100% by mass or less Any resin composition for a dicing film base material.
[9] When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid copolymer The total content of the ionomer (B) of the acid/unsaturated carboxylic acid ester copolymer and the styrene elastomer (C) is more than 90% by mass and 100% by mass or less, [1] to [8] The resin composition for a dicing film base material according to any one of the above.
[10] In accordance with JIS K 7210:1999, the melt flow rate measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less, [1] to [9] The resin composition for a dicing film base material according to any one of the above.
本発明は、以下のダイシングフィルム基材およびダイシングフィルムを提供する。
［１１］上記［１］～［１０］のいずれかに記載のダイシングフィルム基材用樹脂組成物を含む層を、少なくとも一層有する、ダイシングフィルム基材。
［１２］前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して２３℃で測定したＭＤ方向の３０％モジュラスおよびＴＤ方向の３０％モジュラスの平均値が、８ＭＰａ以上１７ＭＰａ以下である、［１１］に記載のダイシングフィルム基材。
［１３］前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して－１５℃で測定したＭＤ方向の１０％モジュラスおよびＴＤ方向の１０％モジュラスの平均値が、２０ＭＰａ以上である、［１１］または［１２］に記載のダイシングフィルム基材。
［１４］上記［１１］に記載のダイシングフィルム基材と、前記ダイシングフィルム基材の少なくとも一方の面に積層された粘着層と、を有する、ダイシングフィルム。 The present invention provides the following dicing film base material and dicing film.
[11] A dicing film base material, comprising at least one layer containing the resin composition for a dicing film base material according to any one of [1] to [10] above.
[12] The average value of the 30% modulus in the MD direction and the 30% modulus in the TD direction measured at 23°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is 8 MPa. The dicing film base material according to [11], which has a pressure of 17 MPa or less.
[13] The average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is: The dicing film base material according to [11] or [12], which has a pressure of 20 MPa or more.
[14] A dicing film comprising the dicing film base material according to [11] above, and an adhesive layer laminated on at least one surface of the dicing film base material.
［１１］上記［１］～［１０］のいずれかに記載のダイシングフィルム基材用樹脂組成物を含む層を、少なくとも一層有する、ダイシングフィルム基材。
［１２］前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して２３℃で測定したＭＤ方向の３０％モジュラスおよびＴＤ方向の３０％モジュラスの平均値が、８ＭＰａ以上１７ＭＰａ以下である、［１１］に記載のダイシングフィルム基材。
［１３］前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して－１５℃で測定したＭＤ方向の１０％モジュラスおよびＴＤ方向の１０％モジュラスの平均値が、２０ＭＰａ以上である、［１１］または［１２］に記載のダイシングフィルム基材。
［１４］上記［１１］に記載のダイシングフィルム基材と、前記ダイシングフィルム基材の少なくとも一方の面に積層された粘着層と、を有する、ダイシングフィルム。 The present invention provides the following dicing film base material and dicing film.
[11] A dicing film base material, comprising at least one layer containing the resin composition for a dicing film base material according to any one of [1] to [10] above.
[12] The average value of the 30% modulus in the MD direction and the 30% modulus in the TD direction measured at 23°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is 8 MPa. The dicing film base material according to [11], which has a pressure of 17 MPa or less.
[13] The average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is: The dicing film base material according to [11] or [12], which has a pressure of 20 MPa or more.
[14] A dicing film comprising the dicing film base material according to [11] above, and an adhesive layer laminated on at least one surface of the dicing film base material.
本発明のダイシングフィルム基材用樹脂組成物によれば、常温および低温での伸び性に優れ、さらには常温および低温でのモジュラス強度にも優れるダイシングフィルム基材が実現される。
According to the resin composition for a dicing film base material of the present invention, a dicing film base material that has excellent elongation at room temperature and low temperature, and also excellent modulus strength at room temperature and low temperature is realized.
本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。また、「(メタ）アクリル酸」は、「アクリル酸」および「メタクリル酸」の双方を包含して用いられる表記であり、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方を包含して用いられる表記である。
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits. In addition, "(meth)acrylic acid" is a notation used to include both "acrylic acid" and "methacrylic acid," and "(meth)acrylate" includes both "acrylate" and "methacrylate." This notation is used inclusively.
１．ダイシングフィルム基材用樹脂組成物について
本発明のダイシングフィルム基材用樹脂組成物（以下、単に「樹脂組成物」とも称する）は、主にダイシングフィルムの基材に使用されるが、当該樹脂組成物の用途は、ダイシングフィルムの基材に限定されない。 1. About the resin composition for dicing film base materials The resin composition for dicing film base materials of the present invention (hereinafter also simply referred to as "resin composition") is mainly used for the base material of dicing films. The use of the product is not limited to the base material of a dicing film.
本発明のダイシングフィルム基材用樹脂組成物（以下、単に「樹脂組成物」とも称する）は、主にダイシングフィルムの基材に使用されるが、当該樹脂組成物の用途は、ダイシングフィルムの基材に限定されない。 1. About the resin composition for dicing film base materials The resin composition for dicing film base materials of the present invention (hereinafter also simply referred to as "resin composition") is mainly used for the base material of dicing films. The use of the product is not limited to the base material of a dicing film.
前述のように、ダイシングフィルム用の基材には、常温および低温におけるモジュラス強度だけでなく、常温および低温における伸び性も求められている。しかしながら、従来、これらを両立させることは試みられていなかった。
As mentioned above, base materials for dicing films are required to have not only modulus strength at room temperature and low temperature, but also elongation at room temperature and low temperature. However, conventionally, no attempt has been made to achieve both of these requirements.
これに対し、本発明者らが鋭意検討したところ、エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）と、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）と、スチレン系エラストマー（Ｃ）と、を含む樹脂組成物によれば、常温および低温におけるモジュラス強度と、常温および低温における伸び性とを兼ね備えるダイシングフィルム基材が得られることが明らかとなった。その理由は明確ではないが、以下のように推定される。例えば、樹脂組成物が、エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）（以下、単に「２元系アイオノマー（Ａ）」とも称する）を含むと、樹脂組成物の凝集力（剛性）が向上するため、樹脂組成物から得られるダイシングフィルムの低温モジュラス性が良好になる。また、樹脂組成物が、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）（以下、単に「３元系アイオノマー（Ｂ）」とも称する）を含むと、不飽和カルボン酸エステルが含有されるため、樹脂組成物から得られる常温モジュラス性および常温伸び性が良好になる。さらに、樹脂組成物がスチレン系エラストマー（Ｃ）を含むと、２元系アイオノマー（Ａ）と３元系アイオノマー（Ｂ）との相溶性が向上するため、樹脂組成物から得られる常温モジュラス性および常温伸び性が良好になる。一方で、これらを単独で含む場合には、ダイシングフィルムの低温伸び性が良好になり難い。しかしながら、これらを組み合わせると、２元系アイオノマー（Ａ）と３元系アイオノマー（Ｂ）とスチレン系エラストマー（Ｃ）とが均一に混合され、相溶性が向上することで、低温伸び性も良好になり、常温および低温におけるモジュラス強度と、常温および低温における伸び性とを兼ね備えるダイシングフィルム基材が得られる。
以下、樹脂組成物が含む各成分について説明し、その後、樹脂組成物の物性について説明する。 On the other hand, the present inventors conducted extensive studies and found that an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer and an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer It has been revealed that a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature can be obtained by using a resin composition containing the styrene elastomer (C) and styrenic elastomer (C). Although the reason is not clear, it is presumed as follows. For example, when the resin composition contains an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer (hereinafter also simply referred to as "binary ionomer (A)"), the cohesive force (rigidity) of the resin composition increases. As a result, the low-temperature modulus of the dicing film obtained from the resin composition is improved. In addition, when the resin composition contains an ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (hereinafter also simply referred to as "ternary ionomer (B)"), unsaturated carboxylic acid Since the acid ester is contained, the resin composition has good room temperature modulus and room temperature elongation. Furthermore, when the resin composition contains the styrene elastomer (C), the compatibility between the binary ionomer (A) and the ternary ionomer (B) improves, so that the room-temperature modulus and Good room temperature elongation. On the other hand, when these are contained alone, it is difficult for the dicing film to have good low-temperature elongation properties. However, when these are combined, the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) are uniformly mixed, improving compatibility and improving low-temperature elongation. Thus, a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature is obtained.
Each component contained in the resin composition will be explained below, and then the physical properties of the resin composition will be explained.
以下、樹脂組成物が含む各成分について説明し、その後、樹脂組成物の物性について説明する。 On the other hand, the present inventors conducted extensive studies and found that an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer and an ionomer (B) of an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer It has been revealed that a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature can be obtained by using a resin composition containing the styrene elastomer (C) and styrenic elastomer (C). Although the reason is not clear, it is presumed as follows. For example, when the resin composition contains an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer (hereinafter also simply referred to as "binary ionomer (A)"), the cohesive force (rigidity) of the resin composition increases. As a result, the low-temperature modulus of the dicing film obtained from the resin composition is improved. In addition, when the resin composition contains an ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (hereinafter also simply referred to as "ternary ionomer (B)"), unsaturated carboxylic acid Since the acid ester is contained, the resin composition has good room temperature modulus and room temperature elongation. Furthermore, when the resin composition contains the styrene elastomer (C), the compatibility between the binary ionomer (A) and the ternary ionomer (B) improves, so that the room-temperature modulus and Good room temperature elongation. On the other hand, when these are contained alone, it is difficult for the dicing film to have good low-temperature elongation properties. However, when these are combined, the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) are uniformly mixed, improving compatibility and improving low-temperature elongation. Thus, a dicing film base material having both modulus strength at room temperature and low temperature and extensibility at room temperature and low temperature is obtained.
Each component contained in the resin composition will be explained below, and then the physical properties of the resin composition will be explained.
＜エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）＞
２元系アイオノマー（Ａ）は、エチレンと、不飽和カルボン酸との共重合体、すなわちエチレン・不飽和カルボン酸共重合体の酸の一部、または全てが金属イオンで中和されたものであり、複数のエチレン・不飽和カルボン酸共重合体が架橋した構造を有する。樹脂組成物は、当該２元系アイオノマー（Ａ）を一種のみ含んでいてもよく、二種以上含んでいてもよい。 <Ionomer of ethylene/unsaturated carboxylic acid copolymer (A)>
The binary ionomer (A) is a copolymer of ethylene and an unsaturated carboxylic acid, that is, a copolymer of ethylene and an unsaturated carboxylic acid in which part or all of the acid has been neutralized with metal ions. It has a structure in which multiple ethylene/unsaturated carboxylic acid copolymers are crosslinked. The resin composition may contain only one type of the binary ionomer (A), or may contain two or more types.
２元系アイオノマー（Ａ）は、エチレンと、不飽和カルボン酸との共重合体、すなわちエチレン・不飽和カルボン酸共重合体の酸の一部、または全てが金属イオンで中和されたものであり、複数のエチレン・不飽和カルボン酸共重合体が架橋した構造を有する。樹脂組成物は、当該２元系アイオノマー（Ａ）を一種のみ含んでいてもよく、二種以上含んでいてもよい。 <Ionomer of ethylene/unsaturated carboxylic acid copolymer (A)>
The binary ionomer (A) is a copolymer of ethylene and an unsaturated carboxylic acid, that is, a copolymer of ethylene and an unsaturated carboxylic acid in which part or all of the acid has been neutralized with metal ions. It has a structure in which multiple ethylene/unsaturated carboxylic acid copolymers are crosslinked. The resin composition may contain only one type of the binary ionomer (A), or may contain two or more types.
２元系アイオノマー（Ａ）の主骨格となるエチレン・不飽和カルボン酸共重合体は、エチレンと、不飽和カルボン酸とを主に含む。本発明の目的および効果を損なわない範囲で、エチレンおよび不飽和カルボン酸以外の単量体由来の構造を一部に含んでいてもよく、例えばエチレン・不飽和カルボン酸共重合体の全構成単位の量に対して、他の単量体由来の構造を２０質量％以下含んでいてもよい。ただし、本明細書において、不飽和カルボン酸エステル由来の構造をさらに含むものは、エチレン・不飽和カルボン酸重合体に含まない。
The ethylene/unsaturated carboxylic acid copolymer that forms the main skeleton of the binary ionomer (A) mainly contains ethylene and unsaturated carboxylic acid. As long as the objects and effects of the present invention are not impaired, structures derived from monomers other than ethylene and unsaturated carboxylic acids may be partially included, for example, all constituent units of the ethylene/unsaturated carboxylic acid copolymer. It may contain 20% by mass or less of structures derived from other monomers based on the amount of . However, in this specification, those that further include a structure derived from an unsaturated carboxylic acid ester are not included in the ethylene/unsaturated carboxylic acid polymer.
エチレン・不飽和カルボン酸共重合体におけるエチレン由来の構成単位の量は制限されないが、エチレン由来の構成単位の量が、エチレン・不飽和カルボン酸共重合体の全構成単位の量に対して、７０質量％以上９９質量％以下が好ましく、７５質量％以上９５質量％以下がより好ましく、７８質量％以上９０質量％以下がさらに好ましい。エチレン由来の構成単位量が７０質量％以上であると、得られるダイシングフィルムにブロッキング等が生じ難くなる。一方、エチレン由来の構成単位の量が９９質量％以下であると、相対的に不飽和カルボン酸の量が十分に多くなり、モジュラス強度や伸びが良好になりやすい。
The amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid copolymer is not limited, but if the amount of ethylene-derived structural units is relative to the amount of all structural units in the ethylene/unsaturated carboxylic acid copolymer, The content is preferably 70% by mass or more and 99% by mass or less, more preferably 75% by mass or more and 95% by mass or less, and even more preferably 78% by mass or more and 90% by mass or less. When the amount of structural units derived from ethylene is 70% by mass or more, blocking etc. are less likely to occur in the resulting dicing film. On the other hand, when the amount of the structural unit derived from ethylene is 99% by mass or less, the amount of unsaturated carboxylic acid becomes relatively large enough, and the modulus strength and elongation tend to be good.
一方、エチレン・不飽和カルボン酸共重合体における不飽和カルボン酸由来の構成単位の量は制限されない。不飽和カルボン酸由来の構成単位の量は、エチレン・不飽和カルボン酸共重合体の全構成単位の量に対して、１質量％以上３０質量％以下が好ましく、５質量％以上２５質量％以下がより好ましく、１０質量％以上２２質量％以下がさらに好ましい。不飽和カルボン酸由来の構成単位量が１質量％以上であると、モジュラス強度や伸び率が良好になりやすい。一方、不飽和カルボン酸由来の構成単位量が３０質量％以下であると、得られるダイシングフィルムにブロッキング等が生じ難くなる。
On the other hand, the amount of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer is not limited. The amount of the structural unit derived from unsaturated carboxylic acid is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or more and 25% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid copolymer. is more preferable, and even more preferably 10% by mass or more and 22% by mass or less. When the amount of structural units derived from unsaturated carboxylic acid is 1% by mass or more, the modulus strength and elongation rate tend to be good. On the other hand, when the amount of structural units derived from unsaturated carboxylic acid is 30% by mass or less, blocking etc. are less likely to occur in the resulting dicing film.
不飽和カルボン酸の例には、アクリル酸、メタクリル酸、エタクリル酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸、マレイン酸、無水マレイン酸等の炭素数４～８の不飽和カルボン酸が含まれ、これらの中でも反応性や入手容易性等の観点で、アクリル酸またはメタクリル酸が好ましい。エチレン・不飽和カルボン酸共重合体は、これら由来の構成単位を一種のみ含んでいてもよく、二種以上含んでいてもよい。
Examples of unsaturated carboxylic acids include unsaturated carboxylic acids having 4 to 8 carbon atoms such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, and maleic anhydride. Among these, acrylic acid or methacrylic acid is preferred from the viewpoint of reactivity and availability. The ethylene/unsaturated carboxylic acid copolymer may contain only one type of structural unit derived from these, or may contain two or more types.
上述のように、エチレン・不飽和カルボン酸共重合体は、エチレンおよび不飽和カルボン酸以外の単量体由来の構成単位一種、または二種以上有していてもよい。エチレンおよび不飽和カルボン酸以外の単量体の例には、プロピレン、ブテン、１，３－ブタジエン、ペンテン、１，３－ペンタジエン、１－ヘキセン等の不飽和炭化水素；酢酸ビニル、プロピオン酸ビニル等由来のビニルエステル；ビニル硫酸やビニル硝酸等の酸化物；塩化ビニル、フッ化ビニル等のハロゲン化合物；ビニル基含有１級アミン化合物；ビニル基含有２級アミン化合物；一酸化炭素；二酸化硫黄；等が含まれる。
As mentioned above, the ethylene/unsaturated carboxylic acid copolymer may have one or more constituent units derived from monomers other than ethylene and unsaturated carboxylic acid. Examples of monomers other than ethylene and unsaturated carboxylic acids include unsaturated hydrocarbons such as propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, and 1-hexene; vinyl acetate, vinyl propionate, etc. vinyl esters derived from etc.; oxides such as vinyl sulfuric acid and vinyl nitric acid; halogen compounds such as vinyl chloride and vinyl fluoride; primary amine compounds containing vinyl groups; secondary amine compounds containing vinyl groups; carbon monoxide; sulfur dioxide; etc. are included.
上記エチレン・不飽和カルボン酸共重合体は、ブロック共重合体であってもよく、ランダム共重合体であってもよい。また、エチレン・不飽和カルボン酸共重合体は、本発明の目的および効果を損なわない範囲で、ランダム重合体やブロック重合体に、さらに公知の化合物がグラフト重合したグラフト共重合体等であってもよい。
The above-mentioned ethylene/unsaturated carboxylic acid copolymer may be a block copolymer or a random copolymer. In addition, the ethylene/unsaturated carboxylic acid copolymer may be a graft copolymer obtained by graft-polymerizing a random polymer or a block polymer with a known compound, as long as it does not impair the purpose and effects of the present invention. Good too.
また、２元系アイオノマー（Ａ）において、上記エチレン・不飽和カルボン酸共重合体の酸を中和する金属イオンは特に制限されないが、その例には、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオン、亜鉛イオン、マグネシウムイオン、マンガンイオン等が含まれる。これらの中でも、入手容易性等の観点でマグネシウムイオン、ナトリウムイオン、または亜鉛イオンが好ましく、ナトリウムイオンまたは亜鉛イオンがより好ましく、亜鉛イオンがさらに好ましい。
In addition, in the binary ionomer (A), the metal ion that neutralizes the acid of the ethylene/unsaturated carboxylic acid copolymer is not particularly limited, but examples include lithium ion, sodium ion, potassium ion, rubidium ion, etc. ion, cesium ion, zinc ion, magnesium ion, manganese ion, etc. Among these, magnesium ion, sodium ion, or zinc ion is preferable from the viewpoint of availability, etc., sodium ion or zinc ion is more preferable, and zinc ion is even more preferable.
２元系アイオノマー（Ａ）におけるエチレン・不飽和カルボン酸共重合体の中和度は、１０％以上９０％以下が好ましく、１０％以上８５％以下がより好ましく、１５％以上８２％以下がさらに好ましい。エチレン・不飽和カルボン酸共重合体の中和度が１０％以上であると、樹脂組成物をダイシングフィルムの基材としたとき、基材表面の硬度が高くなる。一方、中和度が９０％以下であると、樹脂組成物の加工性や成形性が良好になる。中和度とは、２元系アイオノマー（Ａ）（エチレン・不飽和カルボン酸共重合体）中の酸基（例えばカルボキシ基）のモル数に対する、金属イオンの配合比率の割合である。単位はモル％である。当該中和度は、赤外吸収スペクトル（ＩＲ）によって測定可能である。赤外吸収スペクトルによって、樹脂のＣ＝Ｏ伸縮吸収ピークを測定することでイオン化していないカルボキシ基を定量でき、塩酸処理した２元系アイオノマー（Ａ）のＣ＝Ｏ伸縮吸収ピークを測定することで、樹脂全体のカルボキシ基を定量できる。両者を測定することで中和度が求められ、具体的には、以下の式で算出できる。
中和度（％）＝（１－Ｐａ１／Ｐａ２）×１００
Ｐａ１：２元系アイオノマー（Ａ）のＣ＝Ｏ伸縮吸収ピーク高さ
Ｐａ２：塩酸処理したエチレン・不飽和カルボン酸共重合体のＣ＝Ｏ伸縮吸収ピーク高さ The degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the binary ionomer (A) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable. When the degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good. The degree of neutralization is the ratio of the metal ion compounding ratio to the number of moles of acid groups (for example, carboxy groups) in the binary ionomer (A) (ethylene/unsaturated carboxylic acid copolymer). The unit is mol%. The degree of neutralization can be measured by infrared absorption spectrum (IR). Unionized carboxy groups can be quantified by measuring the C=O stretching absorption peak of the resin using an infrared absorption spectrum, and by measuring the C=O stretching absorption peak of the binary ionomer (A) treated with hydrochloric acid. The carboxy groups in the entire resin can be quantified using this method. The degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
Degree of neutralization (%) = (1-P a1 /P a2 ) x 100
P a1 : C=O stretching absorption peak height of the binary ionomer (A) P a2 : C=O stretching absorption peak height of the hydrochloric acid-treated ethylene/unsaturated carboxylic acid copolymer
中和度（％）＝（１－Ｐａ１／Ｐａ２）×１００
Ｐａ１：２元系アイオノマー（Ａ）のＣ＝Ｏ伸縮吸収ピーク高さ
Ｐａ２：塩酸処理したエチレン・不飽和カルボン酸共重合体のＣ＝Ｏ伸縮吸収ピーク高さ The degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the binary ionomer (A) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable. When the degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good. The degree of neutralization is the ratio of the metal ion compounding ratio to the number of moles of acid groups (for example, carboxy groups) in the binary ionomer (A) (ethylene/unsaturated carboxylic acid copolymer). The unit is mol%. The degree of neutralization can be measured by infrared absorption spectrum (IR). Unionized carboxy groups can be quantified by measuring the C=O stretching absorption peak of the resin using an infrared absorption spectrum, and by measuring the C=O stretching absorption peak of the binary ionomer (A) treated with hydrochloric acid. The carboxy groups in the entire resin can be quantified using this method. The degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
Degree of neutralization (%) = (1-P a1 /P a2 ) x 100
P a1 : C=O stretching absorption peak height of the binary ionomer (A) P a2 : C=O stretching absorption peak height of the hydrochloric acid-treated ethylene/unsaturated carboxylic acid copolymer
また、２元系アイオノマー（Ａ）のＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるメルトフローレート（ＭＦＲ）は、０．２ｇ／１０分以上２０．０ｇ／１０分以下が好ましく、０．５ｇ／１０分以上２０．０ｇ／１０分以下がより好ましく、０．５ｇ／１０分以上１８．０ｇ／１０分以下がさらに好ましい。２元系アイオノマー（Ａ）のメルトフローレートが前記範囲内であると、樹脂組成物を成形しやすくなる。
In addition, the melt flow rate (MFR) of the binary ionomer (A) measured at 190°C and a load of 2160g according to JIS K 7210:1999 (equivalent to ISO 1133:1997) is 0.2g/10min. It is preferably 20.0 g/10 minutes or more, more preferably 0.5 g/10 minutes or more and 20.0 g/10 minutes or less, and even more preferably 0.5 g/10 minutes or more and 18.0 g/10 minutes or less. When the melt flow rate of the binary ionomer (A) is within the above range, the resin composition can be easily molded.
＜エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）＞
３元系アイオノマー（Ｂ）は、エチレンと、不飽和カルボン酸と、不飽和カルボン酸エステルとの共重合体、すなわちエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の酸の一部、または全てが金属イオンで中和されたものであり、複数のエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体が架橋した構造を有する。樹脂組成物は、当該３元系アイオノマー（Ｂ）を一種のみ含んでいてもよく、二種以上含んでいてもよい。 <Ionomer of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (B)>
The ternary ionomer (B) is a copolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic ester, that is, a part of the acid of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer. , or all of them are neutralized with metal ions, and have a structure in which a plurality of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymers are crosslinked. The resin composition may contain only one type of the ternary ionomer (B), or may contain two or more types.
３元系アイオノマー（Ｂ）は、エチレンと、不飽和カルボン酸と、不飽和カルボン酸エステルとの共重合体、すなわちエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の酸の一部、または全てが金属イオンで中和されたものであり、複数のエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体が架橋した構造を有する。樹脂組成物は、当該３元系アイオノマー（Ｂ）を一種のみ含んでいてもよく、二種以上含んでいてもよい。 <Ionomer of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (B)>
The ternary ionomer (B) is a copolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic ester, that is, a part of the acid of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer. , or all of them are neutralized with metal ions, and have a structure in which a plurality of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymers are crosslinked. The resin composition may contain only one type of the ternary ionomer (B), or may contain two or more types.
３元系アイオノマー（Ｂ）の主骨格となるエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、エチレンと、不飽和カルボン酸、不飽和カルボン酸エステルとを主に含む。本発明の目的および効果を損なわない範囲で、これら以外の単量体由来の構造を一部に含んでいてもよく、例えばエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の全構成単位の量に対して、他の単量体由来の構造を２０質量％以下含んでいてもよい。
The ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer, which is the main skeleton of the ternary ionomer (B), mainly contains ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic ester. As long as the objects and effects of the present invention are not impaired, structures derived from monomers other than these may be partially included, for example, the entire structure of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer. It may contain 20% by mass or less of structures derived from other monomers based on the amount of units.
エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体におけるエチレン由来の構成単位の量は制限されないが、エチレン由来の構成単位の量が、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の全構成単位の量に対して、６０質量％以上９４質量％以下が好ましく、７５質量％以上９０質量％以下がより好ましい。エチレン由来の構成単位量が６０質量％以上であると、得られるダイシングフィルムにブロッキング等が生じ難くなる。一方、エチレン由来の構成単位の量が９４質量％以下であると、相対的に不飽和カルボン酸や不飽和カルボン酸エステルの量が十分に多くなり、モジュラス強度や伸びが良好になりやすい。
The amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is not limited, but the amount of ethylene-derived structural units in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is It is preferably 60% by mass or more and 94% by mass or less, more preferably 75% by mass or more and 90% by mass or less, based on the amount of all structural units of the polymer. When the amount of structural units derived from ethylene is 60% by mass or more, blocking etc. are less likely to occur in the resulting dicing film. On the other hand, when the amount of structural units derived from ethylene is 94% by mass or less, the amount of unsaturated carboxylic acid or unsaturated carboxylic acid ester becomes relatively large enough, and the modulus strength and elongation tend to be good.
一方、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体における不飽和カルボン酸由来の構成単位の量は制限されない。不飽和カルボン酸由来の構成単位の量は、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の全構成単位の量に対して、１質量％以上３０質量％以下が好ましく、５質量％以上２０質量％以下がより好ましい。不飽和カルボン酸由来の構成単位量が１質量％以上であると、モジュラス強度や伸び率が良好になりやすい。一方、不飽和カルボン酸由来の構成単位量が３０質量％以下であると、相対的にエチレンや不飽和カルボン酸エステル由来の構成単位が十分に含まれやすく、ダイシングフィルムにブロッキング等が生じ難くなったりする。
On the other hand, the amount of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is not limited. The amount of the structural unit derived from unsaturated carboxylic acid is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer. % or more and 20% by mass or less is more preferable. When the amount of structural units derived from unsaturated carboxylic acid is 1% by mass or more, the modulus strength and elongation rate tend to be good. On the other hand, when the amount of structural units derived from unsaturated carboxylic acids is 30% by mass or less, it is relatively easy for sufficient structural units derived from ethylene and unsaturated carboxylic acid esters to be included, making it difficult for blocking etc. to occur in the dicing film. or
ここで、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体における不飽和カルボン酸の種類は特に制限されず、上述の２元系モノマーのエチレン・不飽和カルボン酸共重合体の不飽和カルボン酸と同様である。エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、不飽和カルボン酸由来の構成単位を一種のみ含んでいてもよく、二種以上含んでいてもよい。
Here, the type of unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is not particularly limited; Same as carboxylic acid. The ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may contain only one type of structural unit derived from unsaturated carboxylic acid, or may contain two or more types.
エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体における不飽和カルボン酸エステル由来の構成単位の量は制限されない。不飽和カルボン酸エステル由来の構成単位の量は、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の全構成単位の量に対して、１質量％以上２０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましい。不飽和カルボンエステル酸由来の構成単位量が１質量％以上であると、ダイシングフィルム用の基材の低温伸び性や常温伸び性が良好になりやすい。一方、不飽和カルボン酸エステル由来の構成単位量が２０質量％以下であると、相対的にエチレンや不飽和カルボン酸由来の構成が十分に含まれやすく、ダイシングフィルムにブロッキング等が生じ難くなったりする。
The amount of the structural unit derived from the unsaturated carboxylic ester in the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is not limited. The amount of the structural unit derived from the unsaturated carboxylic acid ester is preferably 1% by mass or more and 20% by mass or less, based on the amount of all the structural units of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and 1% by mass or more and 20% by mass or less. It is more preferably 15% by mass or more. When the amount of structural units derived from unsaturated carboxylic ester acid is 1% by mass or more, the low-temperature elongation properties and room-temperature elongation properties of the base material for the dicing film tend to be good. On the other hand, if the amount of structural units derived from unsaturated carboxylic acid esters is 20% by mass or less, it is relatively easy for the constituents derived from ethylene and unsaturated carboxylic acids to be sufficiently included, making it difficult for blocking etc. to occur in the dicing film. do.
上記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体における、不飽和カルボン酸エステルは、上述の不飽和カルボン酸のカルボン酸が、カルボンエステルになった化合物が含まれる。不飽和カルボン酸エステルの例には、炭素数が１～１２のアルキル基不飽和カルボン酸アルキルエステルが含まれる。アルキル基の炭素数は、１～８がより好ましく、１～４がさらに好ましい。アルキル基の例には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、セカンダリーブチル基、２－エチルヘキシル基、イソオクチル基等が含まれる。
In the above-mentioned ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, the unsaturated carboxylic ester includes a compound in which the carboxylic acid of the above-mentioned unsaturated carboxylic acid becomes a carboxylic ester. Examples of unsaturated carboxylic acid esters include unsaturated carboxylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms in the alkyl group is more preferably 1 to 8, and even more preferably 1 to 4. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2-ethylhexyl, isooctyl, and the like.
上記不飽和カルボン酸アルキルエステルの具体例には、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸イソブチルエステル、アクリル酸ｎ－ブチルエステル、アクリル酸イソオクチルエステル、マレイン酸ジメチルエステル、マレイン酸ジエチルエステル等が含まれる。エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、不飽和カルボン酸エステル由来の構成単位を一種のみ含んでいてもよく、二種以上含んでいてもよい。
Specific examples of the unsaturated carboxylic acid alkyl esters include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid isobutyl ester, acrylic acid n-butyl ester, acrylic acid isooctyl ester, Includes maleic acid dimethyl ester, maleic acid diethyl ester, etc. The ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer may contain only one type of structural unit derived from an unsaturated carboxylic ester, or may contain two or more types.
また、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、エチレン、不飽和カルボン酸、および不飽和カルボン酸エステル以外の単量体由来の構成単位を一種または二種以上有していてもよい。これらは、エチレン・不飽和カルボン酸共重合体が含んでもよい他の単量体由来の構成単位と同様である。
In addition, the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer has one or more constituent units derived from monomers other than ethylene, unsaturated carboxylic acid, and unsaturated carboxylic ester. It's okay. These are the same as structural units derived from other monomers that may be included in the ethylene/unsaturated carboxylic acid copolymer.
上記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、ブロック共重合体であってもよく、ランダム共重合体であってもよい。また、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体は、本発明の目的および効果を損なわない範囲で、ランダム重合体やブロック重合体に、さらに公知の化合物がグラフト重合したグラフト共重合体等であってもよい。
The above-mentioned ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may be a block copolymer or a random copolymer. In addition, the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer may be a graft copolymer obtained by further grafting a known compound to a random polymer or block polymer, within a range that does not impair the purpose and effects of the present invention. It may also be a polymer or the like.
さらに、３元系アイオノマー（Ｂ）において、上記エチレン・不飽和カルボン酸共重合体の酸を中和する金属イオンは特に制限されないが、その例には、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオン、亜鉛イオン、マグネシウムイオン、マンガンイオン等が含まれる。これらの中でも、入手容易性等の観点でマグネシウムイオン、ナトリウムイオン、または亜鉛イオンが好ましく、ナトリウムイオンまたは亜鉛イオンがより好ましく、亜鉛イオンがさらに好ましい。
Further, in the ternary ionomer (B), the metal ion that neutralizes the acid of the ethylene/unsaturated carboxylic acid copolymer is not particularly limited, but examples thereof include lithium ion, sodium ion, potassium ion, rubidium ion, etc. ion, cesium ion, zinc ion, magnesium ion, manganese ion, etc. Among these, magnesium ion, sodium ion, or zinc ion is preferable from the viewpoint of availability, etc., sodium ion or zinc ion is more preferable, and zinc ion is even more preferable.
３元系アイオノマー（Ｂ）におけるエチレン・不飽和カルボン酸共重合体の中和度は、１０％以上９０％以下が好ましく、１０％以上８５％以下がより好ましく、１５％以上８２％以下がさらに好ましい。エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体の中和度が１０％以上であると、樹脂組成物をダイシングフィルムの基材としたとき、基材表面の硬度が高くなる。一方、中和度が９０％以下であると、樹脂組成物の加工性や成形性が良好になる。中和度とは、３元系アイオノマー（Ｂ）（エチレン・不飽和カルボン酸・不飽和カルボン酸共重合体）中の酸基（例えばカルボキシ基）のモル数に対する、金属イオンの配合比率の割合である。単位はモル％である。当該中和度は、赤外吸収スペクトル（ＩＲ）によって測定可能である。赤外吸収スペクトルによって、樹脂のＣ＝Ｏ伸縮吸収ピークを測定することでイオン化していないカルボキシ基を定量でき、塩酸処理した３元系アイオノマー（Ｂ）のＣ＝Ｏ伸縮吸収ピークを測定することで、樹脂全体のカルボキシ基を定量できる。両者を測定することで中和度が求められ、具体的には、以下の式で算出できる。
中和度（％）＝（１－Ｐｂ１／Ｐｂ２）×１００
Ｐｂ１：３元系アイオノマー（Ｂ）のＣ＝Ｏ伸縮吸収ピーク高さ
Ｐｂ２：塩酸処理したエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のＣ＝Ｏ伸縮吸収ピーク高さ The degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the ternary ionomer (B) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable. When the degree of neutralization of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good. The degree of neutralization is the ratio of the blending ratio of metal ions to the number of moles of acid groups (e.g. carboxy groups) in the ternary ionomer (B) (ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid copolymer). It is. The unit is mol%. The degree of neutralization can be measured by infrared absorption spectrum (IR). By measuring the C=O stretching absorption peak of the resin using an infrared absorption spectrum, unionized carboxy groups can be quantified, and by measuring the C=O stretching absorption peak of the ternary ionomer (B) treated with hydrochloric acid. The carboxy groups in the entire resin can be quantified using this method. The degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
Neutralization degree (%) = (1-P b1 /P b2 ) x 100
P b1 : C=O stretching absorption peak height of the ternary ionomer (B) P b2 : C=O stretching absorption peak height of the hydrochloric acid-treated ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer
中和度（％）＝（１－Ｐｂ１／Ｐｂ２）×１００
Ｐｂ１：３元系アイオノマー（Ｂ）のＣ＝Ｏ伸縮吸収ピーク高さ
Ｐｂ２：塩酸処理したエチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のＣ＝Ｏ伸縮吸収ピーク高さ The degree of neutralization of the ethylene/unsaturated carboxylic acid copolymer in the ternary ionomer (B) is preferably 10% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 15% or more and 82% or less. preferable. When the degree of neutralization of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more, when the resin composition is used as a base material for a dicing film, the hardness of the surface of the base material becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good. The degree of neutralization is the ratio of the blending ratio of metal ions to the number of moles of acid groups (e.g. carboxy groups) in the ternary ionomer (B) (ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid copolymer). It is. The unit is mol%. The degree of neutralization can be measured by infrared absorption spectrum (IR). By measuring the C=O stretching absorption peak of the resin using an infrared absorption spectrum, unionized carboxy groups can be quantified, and by measuring the C=O stretching absorption peak of the ternary ionomer (B) treated with hydrochloric acid. The carboxy groups in the entire resin can be quantified using this method. The degree of neutralization is determined by measuring both, and specifically, it can be calculated using the following formula.
Neutralization degree (%) = (1-P b1 /P b2 ) x 100
P b1 : C=O stretching absorption peak height of the ternary ionomer (B) P b2 : C=O stretching absorption peak height of the hydrochloric acid-treated ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer
また、３元系アイオノマー（Ｂ）のＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるメルトフローレート（ＭＦＲ）は、０．２ｇ／１０分以上２０．０ｇ／１０分以下が好ましく、０．５ｇ／１０分以上２０．０ｇ／１０分以下がより好ましく、０．５ｇ／１０分以上１８．０ｇ／１０分以下がさらに好ましい。３元系アイオノマー（Ｂ）のメルトフローレートが前記範囲内であると、樹脂組成物を成形しやすくなる。
In addition, the melt flow rate (MFR) of the ternary ionomer (B) measured at 190°C and a load of 2160g according to JIS K 7210:1999 (equivalent to ISO 1133:1997) is 0.2g/10min. It is preferably 20.0 g/10 minutes or more, more preferably 0.5 g/10 minutes or more and 20.0 g/10 minutes or less, and even more preferably 0.5 g/10 minutes or more and 18.0 g/10 minutes or less. When the melt flow rate of the ternary ionomer (B) is within the above range, the resin composition can be easily molded.
＜スチレン系エラストマー（Ｃ）＞
スチレン系エラストマーとは、室温でゴム弾性体であるスチレン系重合体をいう。スチレン系エラストマーの例には、スチレンブロック（スチレン重合体）からなるハードセグメントと、アルキレンブロックからなるソフトセグメントとを含む、ブロック共重合体、またはその水素添加物；スチレンとアルキレンとのランダム共重合体、またはその水素添加物；あるいは当該スチレン系エラストマーを酸変性した酸変性スチレン系エラストマー等が含まれる。 <Styrenic elastomer (C)>
The styrenic elastomer refers to a styrene polymer that is a rubber elastic body at room temperature. Examples of styrenic elastomers include block copolymers or hydrogenated products thereof, including hard segments consisting of styrene blocks (styrene polymers) and soft segments consisting of alkylene blocks; random copolymers of styrene and alkylene. Acid-modified styrenic elastomer, which is obtained by acid-modifying the styrene-based elastomer, and the like are included.
スチレン系エラストマーとは、室温でゴム弾性体であるスチレン系重合体をいう。スチレン系エラストマーの例には、スチレンブロック（スチレン重合体）からなるハードセグメントと、アルキレンブロックからなるソフトセグメントとを含む、ブロック共重合体、またはその水素添加物；スチレンとアルキレンとのランダム共重合体、またはその水素添加物；あるいは当該スチレン系エラストマーを酸変性した酸変性スチレン系エラストマー等が含まれる。 <Styrenic elastomer (C)>
The styrenic elastomer refers to a styrene polymer that is a rubber elastic body at room temperature. Examples of styrenic elastomers include block copolymers or hydrogenated products thereof, including hard segments consisting of styrene blocks (styrene polymers) and soft segments consisting of alkylene blocks; random copolymers of styrene and alkylene. Acid-modified styrenic elastomer, which is obtained by acid-modifying the styrene-based elastomer, and the like are included.
上記ブロック共重合体におけるスチレンブロックとは、２つ以上のスチレン重合した部位であればよく、アルキレンブロックとは、２つ以上のアルケンが重合した部位であればよい。アルキレンブロックは、一種のアルケンの単独重合体であってもよく、二種以上のアルケンの共重合体であってもよい。
The styrene block in the block copolymer may be a site where two or more styrenes are polymerized, and the alkylene block may be a site where two or more alkenes are polymerized. The alkylene block may be a homopolymer of one type of alkene or a copolymer of two or more types of alkenes.
上記ブロック共重合体の例には、スチレン－ブタジエンブロック共重合体（ＳＢ）、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレンブロック共重合体（ＳＩ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）が含まれる。
Examples of the above block copolymers include styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SI), styrene-isoprene-styrene Block copolymers (SIS) are included.
上述のように、スチレン系エラストマーは、上記ブロック共重合体の水素添加物であってもよい。当該水素添加物では、スチレンブロックおよびアルキレンブロックの両方が水素添加されていてもよく、スチレンブロックまたはアルキレンブロックのいずれか一方のみが水素添加されていてもよく、さらに、スチレンブロックおよびアルキレンブロックの一部のみが水素添加されていてもよい。
As mentioned above, the styrenic elastomer may be a hydrogenated product of the above block copolymer. In the hydrogenated product, both the styrene block and the alkylene block may be hydrogenated, or only either the styrene block or the alkylene block may be hydrogenated, and furthermore, one of the styrene block and the alkylene block may be hydrogenated. Only a portion may be hydrogenated.
上記ブロック共重合体の水素添加物の具体例には、スチレン－ブタジエンブロック共重合体（ＳＢ）の水素添加物であるスチレン－エチレン・ブチレンブロック共重合体（ＳＥＢ）、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）の水素添加物であるスチレン－エチレン・ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）の水素添加物であるスチレン－エチレン・プロピレン－スチレンブロック共重合体（ＳＥＰＳ）等が含まれる。
Specific examples of the hydrogenated block copolymer include styrene-ethylene/butylene block copolymer (SEB), which is a hydrogenated product of styrene-butadiene block copolymer (SB), and styrene-butadiene-styrene block. Styrene-ethylene/butylene-styrene block copolymer (SEBS), which is a hydrogenated product of copolymer (SBS), and styrene-ethylene/propylene, which is a hydrogenated product of styrene-isoprene-styrene block copolymer (SIS). -Includes styrene block copolymer (SEPS), etc.
上述のように、スチレン系エラストマーの例には、スチレンとアルキレンとのランダム共重合体も含まれる。その例には、スチレン－ブタジエンランダム共重合体、スチレン－イソプレンランダム共重合体、スチレン－エチレン－ブチレンランダム共重合体、スチレン－エチレン－プロピレンランダム共重合体、スチレン－イソブチレンランダム共重合体、スチレン－エチレン－イソプレンランダム共重合体等が含まれる。
As mentioned above, examples of styrenic elastomers also include random copolymers of styrene and alkylene. Examples include styrene-butadiene random copolymers, styrene-isoprene random copolymers, styrene-ethylene-butylene random copolymers, styrene-ethylene-propylene random copolymers, styrene-isobutylene random copolymers, styrene -Includes ethylene-isoprene random copolymer, etc.
上述のように、スチレン系エラストマーは、上記ランダム共重合体の水素添加物であってもよい。その例には、スチレン－ブタジエンランダム共重合体の水素添加物（ＨＳＢＲ）等が含まれる。
As mentioned above, the styrenic elastomer may be a hydrogenated product of the random copolymer. Examples include hydrogenated styrene-butadiene random copolymers (HSBR) and the like.
後述の酸変性がなされていないスチレン系エラストマーにおいては、上記の中でも水素添加物が好ましく、スチレン－エチレン・ブチレン－スチレンブロック共重合体（ＳＥＢＳ）およびスチレン－エチレン・プロピレン－スチレンブロック共重合体（ＳＥＰＳ）がより好ましく、スチレン－エチレン・ブチレン－スチレンブロック共重合体（ＳＥＢＳ）が、樹脂組成物から得られるダイシングフィルム用の基材の低温伸び性や常温伸び性を良好にできるとの観点で特に好ましい。
In the styrene-based elastomer that has not been acid-modified as described below, hydrogenated substances are preferred among the above, and styrene-ethylene/butylene-styrene block copolymer (SEBS) and styrene-ethylene/propylene-styrene block copolymer ( SEPS) is more preferable, and styrene-ethylene/butylene-styrene block copolymer (SEBS) is more preferable, from the viewpoint that it can improve the low-temperature elongation properties and room-temperature elongation properties of the base material for the dicing film obtained from the resin composition. Particularly preferred.
一方、スチレン系エラストマーは、上述のように、上記ブロック共重合体またはランダム重合体、もしくはこれらの水素添化物からなるエラストマーが不飽和カルボン酸やその誘導体によってグラフト変性された酸変性スチレン系エラストマーであってもよい。当該酸変性スチレン系エラストマーは、上記ブロック共重合体またはランダム重合体、もしくはこれらの水素添化物が、一種の不飽和カルボン酸またはその誘導体によってグラフト変性されたものであってもよく、二種以上の不飽和カルボン酸またはその誘導体によってグラフト変性されたものであってもよい。
On the other hand, as mentioned above, styrenic elastomers are acid-modified styrene elastomers in which an elastomer made of the block copolymer or random polymer, or a hydrogenated product thereof, is graft-modified with an unsaturated carboxylic acid or a derivative thereof. There may be. The acid-modified styrenic elastomer may be obtained by graft-modifying the block copolymer or random polymer, or a hydrogenated product thereof, with one type of unsaturated carboxylic acid or a derivative thereof, or two or more types. may be graft-modified with an unsaturated carboxylic acid or a derivative thereof.
上記ブロック共重合体やランダム共重合体等にグラフト重合する不飽和カルボン酸の例には、（メタ）アクリル酸や、２－エチルアクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸等が含まれる。一方、スチレン系エラストマーにグラフト重合する不飽和カルボン酸誘導体の例には、無水マレイン酸、無水フタル酸、無水イタコン酸等の酸無水物；マレイン酸モノメチル、マレイン酸モノエチル等の酸エステル；酸アミド；酸ハロゲン化物；等が含まれる。これらの中でも、マレイン酸または無水マレイン酸がスチレン系エラストマーとの反応性の観点等で好ましい。
Examples of unsaturated carboxylic acids graft-polymerized to the above block copolymers, random copolymers, etc. include (meth)acrylic acid, 2-ethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. included. On the other hand, examples of unsaturated carboxylic acid derivatives that can be graft-polymerized to styrenic elastomers include acid anhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; acid esters such as monomethyl maleate and monoethyl maleate; and acid amides. ; acid halides; etc. are included. Among these, maleic acid or maleic anhydride is preferred from the viewpoint of reactivity with the styrene elastomer.
上記酸変性スチレン系エラストマーは、上記ブロック共重合体やランダム共重合体等をラジカル開始剤の存在下で、不飽和カルボン酸またはその誘導体をグラフト重合させることで得られる。ラジカル開始剤は、ポリオレフィンのグラフト反応に用いられるものであればよく、公知の化合物を使用できる。
The acid-modified styrenic elastomer can be obtained by graft polymerizing the block copolymer, random copolymer, etc. with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator. The radical initiator may be any one used in the graft reaction of polyolefins, and known compounds can be used.
上記酸変性スチレン系エラストマーの酸価は、０ｍｇＣＨ３ＯＮａ／ｇ超、２０ｍｇＣＨ３ＯＮａ／ｇ未満が好ましく、０ｍｇＣＨ３ＯＮａ／ｇ超、１１ｍｇＣＨ３ＯＮａ／ｇ未満がより好ましく、０．５ｍｇＣＨ３ＯＮａ／ｇ以上１１ｍｇＣＨ３ＯＮａ／ｇ以下がさらに好ましい。酸変性スチレン系エラストマーの酸価が当該範囲であると、低温、常温時の伸び性が良好になりやすい。
The acid value of the acid-modified styrenic elastomer is preferably more than 0 mg CH 3 ONa/g and less than 20 mg CH 3 ONa/g, more preferably more than 0 mg CH 3 ONa/g and less than 11 mg CH 3 ONa/g, and more preferably 0.5 mg CH 3 ONa/g. More preferably, the amount is from 11 mg CH 3 ONa/g to 11 mg CH 3 ONa/g. When the acid value of the acid-modified styrene elastomer is within this range, it tends to have good elongation properties at low temperatures and room temperatures.
スチレン系エラストマー（Ｃ）のメルトフレートは、０．１ｇ／１０分～１００ｇ／１０分が好ましく、０．５ｇ／１０分～９０ｇ／１０分がより好ましく、１．０ｇ／１０分～８０ｇ／１０分がさらに好ましく、２．０ｇ／１０分～７５ｇ／１０分がさらに好ましい。上記メルトフローレートは、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定される値である。
The melt plate of the styrene elastomer (C) is preferably 0.1 g/10 minutes to 100 g/10 minutes, more preferably 0.5 g/10 minutes to 90 g/10 minutes, and 1.0 g/10 minutes to 80 g/10 minutes. minutes, more preferably 2.0 g/10 minutes to 75 g/10 minutes. The above melt flow rate is a value measured at 230° C. and a load of 2160 g in accordance with JIS K 7210:1999 (corresponding to ISO 1133:1997).
スチレン系エラストマー（Ｃ）のＴａｎδピーク温度は、得られるダイシングフィルム用の基材の低温伸び性や常温伸び性を良好にできるとの観点から－６０℃以上が好ましく、－５５℃以上がより好ましく、－５０℃以上がさらに好ましい。上記Ｔａｎδピーク温度は、ＪＩＳ Ｋ ６３９４（ＩＳＯ ４６６４－１：２００５に相当）に準拠した動的粘弾性試験（温度依存測定１０Ｈｚ）において、ピーク値を示す温度である。
The Tan δ peak temperature of the styrene elastomer (C) is preferably -60°C or higher, more preferably -55°C or higher, from the viewpoint of improving the low-temperature elongation properties and room-temperature elongation properties of the obtained base material for the dicing film. , -50°C or higher is more preferred. The Tan δ peak temperature is a temperature at which a peak value is obtained in a dynamic viscoelasticity test (temperature dependent measurement 10 Hz) in accordance with JIS K 6394 (corresponding to ISO 4664-1:2005).
＜他の重合体および添加剤＞
樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて各種添加剤、帯電防止剤、紫外線吸収剤、充填材、その他の重合体等を含んでいてもよい。 <Other polymers and additives>
The resin composition may contain various additives, antistatic agents, ultraviolet absorbers, fillers, other polymers, etc., as necessary, within a range that does not impair the effects of the present invention.
樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて各種添加剤、帯電防止剤、紫外線吸収剤、充填材、その他の重合体等を含んでいてもよい。 <Other polymers and additives>
The resin composition may contain various additives, antistatic agents, ultraviolet absorbers, fillers, other polymers, etc., as necessary, within a range that does not impair the effects of the present invention.
各種添加剤の例には、酸化防止剤、熱安定剤、光安定剤、顔料、染料、滑剤、ブロッキング防止剤、防黴剤、抗菌剤、難燃剤、難燃助剤、架橋剤、架橋助剤、発泡剤、発泡助剤、繊維強化材等が含まれる。添加剤の含有量は、樹脂組成物に含まれる樹脂成分の全質量を１００質量部とした場合に、２０質量部以下が好ましく、１８質量部以下がより好ましい。
Examples of various additives include antioxidants, heat stabilizers, light stabilizers, pigments, dyes, lubricants, antiblocking agents, fungicides, antibacterial agents, flame retardants, flame retardant aids, crosslinking agents, and crosslinking aids. This includes foaming agents, foaming agents, foaming aids, fiber reinforcing materials, etc. The content of the additive is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, when the total mass of the resin components contained in the resin composition is 100 parts by mass.
また、帯電防止剤の例には、低分子型帯電防止剤や高分子型帯電防止剤が含まれるが、高分子型帯電防止剤が好ましい。本明細書において、高分子型帯電防止剤とは、導電性部位（例えば、ポリエーテル由来の構造部位、四級アンモニウム塩基部位など）と非導電性部位（例えば、ポリアミド由来の構造部位、ポリエチレンなどのポリオレフィン由来の構造部位、アクリレート由来の構造部位、メタクリレート由来の構造部位、スチレン由来の構造部位など）とを含み、分子量が３００以上（好ましくは１０００～１００００）の共重合体である。分子量はＧＰＣで測定したポリスチレン換算の重量平均分子量である。尚、導電性とは、ＡＳＴＭ Ｄ２５７に基づき測定される表面抵抗率が１０１０Ω／□以下であることを言う。当該高分子型帯電防止剤の例には、分子内にスルホン酸塩を有するビニル共重合体、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、ベタイン等が含まれる。また、高分子型帯電防止剤の他の例には、ポリエーテルアミド、ポリエーテルエステルアミド、ポリエーテルアミドの無機プロトン酸の塩、またはポリエーテルエステルアミドの無機プロトン酸の塩等も含まれる。無機プロトン酸の塩としては、アルカリ金属塩、アルカリ土類金属塩、亜鉛塩、またはアンモニウム塩が挙げられる。
Further, examples of the antistatic agent include a low molecular weight antistatic agent and a polymer type antistatic agent, and a polymer type antistatic agent is preferable. In this specification, a polymer type antistatic agent refers to conductive sites (e.g., polyether-derived structural sites, quaternary ammonium base sites, etc.) and non-conductive sites (e.g., polyamide-derived structural sites, polyethylene, etc.). It is a copolymer having a molecular weight of 300 or more (preferably 1000 to 10000). The molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC. Note that conductivity means that the surface resistivity measured based on ASTM D257 is 10 10 Ω/□ or less. Examples of the polymer type antistatic agent include vinyl copolymers having sulfonate salts in the molecule, alkyl sulfonate salts, alkylbenzene sulfonate salts, betaine, and the like. Further, other examples of the polymer type antistatic agent include polyether amide, polyether ester amide, an inorganic protonic acid salt of polyether amide, or an inorganic protonic acid salt of polyether ester amide. Salts of inorganic protic acids include alkali metal salts, alkaline earth metal salts, zinc salts, or ammonium salts.
紫外線吸収剤の例には、ベンゾフェノン系、ベンゾエート系、ベンゾトリアゾール系、シアノアクリレート系、ヒンダードアミン系等が含まれる。
Examples of ultraviolet absorbers include benzophenone-based, benzoate-based, benzotriazole-based, cyanoacrylate-based, hindered amine-based, and the like.
充填材の例には、シリカ、クレー、炭酸カルシウム、硫酸バリウム、ガラスビーズ、タルク等が含まれる。
Examples of fillers include silica, clay, calcium carbonate, barium sulfate, glass beads, talc, etc.
添加剤や帯電防止剤、紫外線吸収剤、充填材の量は、その種類に応じて適宜選択される。
The amounts of additives, antistatic agents, ultraviolet absorbers, and fillers are appropriately selected depending on their types.
その他の重合体の例には、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリアミドが含まれる。ただし、ポリアミドの量は、樹脂組成物に含まれる樹脂成分の全質量を１００質量部とした場合に、５質量部未満が好ましい。樹脂組成物は、その他の重合体として、ポリアミドを含まないことが好ましい。
Examples of other polymers include polyolefins such as polyethylene and polypropylene, and polyamides. However, the amount of polyamide is preferably less than 5 parts by mass when the total mass of the resin components contained in the resin composition is 100 parts by mass. It is preferable that the resin composition does not contain polyamide as other polymers.
＜好ましい組成＞
本発明の樹脂組成物において、上記２元系アイオノマー（Ａ）の量は、樹脂組成物全量に対して、１０質量％以上８０質量％以下が好ましく、１５質量％以上７５質量％以下がより好ましい。さらに、上記３元系アイオノマー（Ｂ）の量は、樹脂組成物全量に対して、１０質量％以上８０質量％以下が好ましく、１２質量％以上７５質量％以下がより好ましい。また、スチレン系エラストマー（Ｃ）の量は、樹脂組成物全量に対して、５質量％以上３５質量％以下が好ましく、７質量％以上３２質量％以下がより好ましい。 <Preferred composition>
In the resin composition of the present invention, the amount of the binary ionomer (A) is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, based on the total amount of the resin composition. . Further, the amount of the ternary ionomer (B) is preferably 10% by mass or more and 80% by mass or less, more preferably 12% by mass or more and 75% by mass or less, based on the total amount of the resin composition. Further, the amount of the styrene elastomer (C) is preferably 5% by mass or more and 35% by mass or less, more preferably 7% by mass or more and 32% by mass or less, based on the total amount of the resin composition.
本発明の樹脂組成物において、上記２元系アイオノマー（Ａ）の量は、樹脂組成物全量に対して、１０質量％以上８０質量％以下が好ましく、１５質量％以上７５質量％以下がより好ましい。さらに、上記３元系アイオノマー（Ｂ）の量は、樹脂組成物全量に対して、１０質量％以上８０質量％以下が好ましく、１２質量％以上７５質量％以下がより好ましい。また、スチレン系エラストマー（Ｃ）の量は、樹脂組成物全量に対して、５質量％以上３５質量％以下が好ましく、７質量％以上３２質量％以下がより好ましい。 <Preferred composition>
In the resin composition of the present invention, the amount of the binary ionomer (A) is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, based on the total amount of the resin composition. . Further, the amount of the ternary ionomer (B) is preferably 10% by mass or more and 80% by mass or less, more preferably 12% by mass or more and 75% by mass or less, based on the total amount of the resin composition. Further, the amount of the styrene elastomer (C) is preferably 5% by mass or more and 35% by mass or less, more preferably 7% by mass or more and 32% by mass or less, based on the total amount of the resin composition.
また当該樹脂組成物において、２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の合計量を１とした場合の、２元系アイオノマー（Ａ）の質量は、０．１０以上０．９５以下が好ましく、０．１５以上０．９０以下がより好ましく、０．２０以上０．８５以下がさらに好ましい。さらに、２元系アイオノマー（Ａ）、３元系アイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）の合計質量を１とした場合の、２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の合計質量は、０．６０以上１．００未満が好ましく、０．６５以上０．９５以下がより好ましい。また、樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、２元系アイオノマー（Ａ）、３元系アイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）の合計含有率が、５０質量％以上１００質量％以下であることが好ましく、６０質量％以上１００質量％以下であることがより好ましく、７０質量％以上１００質量％以下であることがさらに好ましく、８０質量％以上１００質量％以下であることがさらに好ましく、９０質量％を超えて１００質量％以下がさらに好ましく、９５質量％以上１００質量％以下であることがさらに好ましく、９５質量％を超えて１００質量％以下であることがより好ましく、９８質量％以上１００質量％以下であることがさらに好ましく、９９質量％以上１００質量％以下であることがさらに好ましい。
In addition, in the resin composition, when the total amount of the binary ionomer (A) and the ternary ionomer (B) is 1, the mass of the binary ionomer (A) is 0.10 or more and 0.95 The following are preferable, 0.15 or more and 0.90 or less are more preferable, and 0.20 or more and 0.85 or less are still more preferable. Furthermore, when the total mass of the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) is 1, the binary ionomer (A) and the ternary ionomer (B) The total mass is preferably 0.60 or more and less than 1.00, more preferably 0.65 or more and 0.95 or less. Furthermore, when the total mass of the resin components contained in the resin composition is 100% by mass, the total content of the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C) is , preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, even more preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. It is more preferably not more than 90% by mass and not more than 100% by mass, even more preferably not less than 95% by mass and not more than 100% by mass, and more than 95% by mass and not more than 100% by mass. It is more preferably at least 98% by mass and at most 100% by mass, even more preferably at least 99% by mass and at most 100% by mass.
これらを満たすと、上述のように、フィルム成形性、常温および低温におけるモジュラス強度と、常温および低温における伸び性がいずれも良好になる。
If these conditions are satisfied, as described above, film formability, modulus strength at room temperature and low temperature, and elongation at room temperature and low temperature will all be good.
また、樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に樹脂成分の全質量に対する、「２元系アイオノマー（Ａ）中の不飽和カルボン酸由来の構成単位の量（質量）および３元系アイオノマー（Ｂ）中の不飽和カルボン酸由来の構成単位の量（質量）の合計」の割合が、５質量％以上２０質量％以下となるように、各成分量を調整することが好ましく、７質量％以上１５質量％以下となるように各成分量を調整することが、より好ましく、９質量％以上１３質量％以下となるように各成分量を調整することが、さらに好ましい。樹脂組成物中の不飽和カルボン酸由来の構成単位の量が上記範囲であると、低温モジュラス性が良好になりやすい。
In addition, when the total mass of the resin components contained in the resin composition is 100% by mass, the "amount (mass) of the structural unit derived from the unsaturated carboxylic acid in the binary ionomer (A)" relative to the total mass of the resin components ) and the amount (mass) of the unsaturated carboxylic acid-derived structural units in the ternary ionomer (B)" adjust the amount of each component so that the ratio is 5% by mass or more and 20% by mass or less. It is preferable to adjust the amount of each component so that it is 7% by mass or more and 15% by mass or less, and it is more preferable to adjust the amount of each component so that it is 9% by mass or more and 13% by mass or less. preferable. When the amount of the structural unit derived from unsaturated carboxylic acid in the resin composition is within the above range, low-temperature modulus properties tend to be good.
さらに、樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に樹脂成分の全質量に対する、「３元系アイオノマー（Ｂ）中の不飽和カルボン酸エステル由来の構成単位の量（質量）」の割合が、０．５質量％以上１０質量％以下となるように、各成分量を調整することが好ましく、１質量％以上８質量％以下となるように各成分量を調整することがより好ましい。樹脂組成物中の不飽和カルボン酸エステル由来の構成単位の量が上記範囲であると、常温および低温における伸び性が良好になりやすい。
Furthermore, when the total mass of the resin components contained in the resin composition is 100% by mass, the "amount of structural units derived from the unsaturated carboxylic acid ester in the ternary ionomer (B)" relative to the total mass of the resin components ( It is preferable to adjust the amount of each component so that the ratio of "mass)" is 0.5% by mass or more and 10% by mass or less, and the amount of each component is adjusted so that the ratio of "mass)" is 1% by mass or more and 8% by mass or less. It is more preferable. When the amount of the structural unit derived from the unsaturated carboxylic acid ester in the resin composition is within the above range, the elongation properties at room temperature and low temperature tend to be good.
また、当該樹脂組成物中のカルボン酸の中和度、すなわち「２元系アイオノマー（Ａ）中の不飽和カルボン酸および３元系アイオノマー（Ｂ）中の不飽和カルボン酸」の中和度は、４０％以上９０％以下が好ましく、４５％以上８５％以下がより好ましく、５０％以上８０％以下がさらに好ましく、５５％以上７５％以下がさらに好ましく、６０％以上７０％以下がさらに好ましい。上記中和度は、例えば２元系アイオノマー（Ａ）中の不飽和カルボン酸の中和度、および３元系アイオノマー（Ｂ）中の不飽和カルボン酸の中和度がそれぞれ判明している場合には、「２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の総質量に対する、２元系アイオノマー（Ａ）の質量の割合ａ」、および「２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の総質量に対する、３元系アイオノマー（Ｂ）の質量の割合ｂ」をそれぞれ算出し、「２元系アイオノマー（Ａ）の中和度×ａ＋３元系アイオノマー（Ｂ）の中和度×ｂ」によって、特定できる。樹脂組成物全体における、不飽和カルボン酸の中和度が４０％以上であると、樹脂組成物をダイシングフィルムの基材としたとき、基材フィルムの常温および低温におけるモジュラス強度が高くなる。一方、中和度が９０％以下であると、樹脂組成物の加工性や成形性が良好になる。
In addition, the degree of neutralization of the carboxylic acid in the resin composition, that is, the degree of neutralization of "the unsaturated carboxylic acid in the binary ionomer (A) and the unsaturated carboxylic acid in the ternary ionomer (B)" is , is preferably 40% or more and 90% or less, more preferably 45% or more and 85% or less, further preferably 50% or more and 80% or less, further preferably 55% or more and 75% or less, and even more preferably 60% or more and 70% or less. The above degree of neutralization is, for example, when the degree of neutralization of the unsaturated carboxylic acid in the binary ionomer (A) and the degree of neutralization of the unsaturated carboxylic acid in the ternary ionomer (B) are known. "Ratio a of the mass of the binary ionomer (A) to the total mass of the binary ionomer (A) and the ternary ionomer (B)," and "Ratio a of the mass of the binary ionomer (A) and the ternary ionomer (B)." Calculate the ratio b of the mass of the ternary ionomer (B) to the total mass of the ionomer (B), and calculate the ratio b of the mass of the ternary ionomer (B) to the total mass of the ionomer (B). It can be specified by ``Japanese degree x b''. When the degree of neutralization of the unsaturated carboxylic acid in the entire resin composition is 40% or more, when the resin composition is used as a base material for a dicing film, the modulus strength of the base film at room temperature and low temperature becomes high. On the other hand, when the degree of neutralization is 90% or less, the processability and moldability of the resin composition will be good.
＜樹脂組成物の製造法方法および樹脂組成物の物性＞
本発明の樹脂組成物の製造方法は特に制限されず、２元系アイオノマー（Ａ）、３元系アイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）、さらに必要に応じてその他の重合体や添加剤等を混合可能な方法であれば特に制限されない。例えば、全ての成分をドライブレンドした後に溶融混練してもよく、一部の成分を先に混練してから、後の成分を加えてもよい。 <Production method of resin composition and physical properties of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and includes a binary ionomer (A), a ternary ionomer (B), and a styrene elastomer (C), and if necessary, other polymers and additives. There are no particular restrictions on the method as long as it allows mixing of agents and the like. For example, all components may be dry-blended and then melt-kneaded, or some components may be kneaded first and then subsequent components may be added.
本発明の樹脂組成物の製造方法は特に制限されず、２元系アイオノマー（Ａ）、３元系アイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）、さらに必要に応じてその他の重合体や添加剤等を混合可能な方法であれば特に制限されない。例えば、全ての成分をドライブレンドした後に溶融混練してもよく、一部の成分を先に混練してから、後の成分を加えてもよい。 <Production method of resin composition and physical properties of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and includes a binary ionomer (A), a ternary ionomer (B), and a styrene elastomer (C), and if necessary, other polymers and additives. There are no particular restrictions on the method as long as it allows mixing of agents and the like. For example, all components may be dry-blended and then melt-kneaded, or some components may be kneaded first and then subsequent components may be added.
上記混練後の樹脂組成物の形状は特に制限されず、例えばペレット状等であってもよく、長尺状または枚葉状のシート状に加工してもよい。
The shape of the resin composition after the kneading is not particularly limited, and may be, for example, in the form of pellets, or may be processed into a long or single sheet.
上記樹脂組成物のＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠して、１９０℃、荷重２１６０ｇにて測定されるメルトフローレートは、０．１ｇ／１０分以上３０ｇ／１０分以下が好ましく、０．２ｇ／１０分以上２０ｇ／１０分以下がより好ましく、０．３ｇ／１０分以上１０ｇ／１０分以下がさらに好ましく、０．４ｇ／１０分以上５ｇ／１０分以下がさらに好ましく、０．５ｇ／１０分以上３ｇ／１０分以下がさらに好ましい。樹脂組成物のメルトフローレートが当該範囲であると、当該樹脂組成物から得られる基材の常温および低温におけるモジュラス強度、ならびに常温および低温における伸び性が良好になりやすい。
According to JIS K 7210:1999 (equivalent to ISO 1133:1997), the melt flow rate of the resin composition measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less. is preferable, 0.2 g/10 minutes or more and 20 g/10 minutes or less, more preferably 0.3 g/10 minutes or more and 10 g/10 minutes or less, even more preferably 0.4 g/10 minutes or more and 5 g/10 minutes or less. , more preferably 0.5 g/10 minutes or more and 3 g/10 minutes or less. When the melt flow rate of the resin composition is within this range, the modulus strength at room temperature and low temperature and the elongation property at room temperature and low temperature of the base material obtained from the resin composition tend to be good.
２．ダイシングフィルム基材
ダイシング基材は、上述の樹脂組成物を含む層を少なくとも一層有する基材であればよい。当該ダイシングフィルム基材は、上述の樹脂組成物を含む層を有するため、常温および低温において、優れたモジュラス強度や伸び性を発揮する。当該ダイシングフィルム基材は、ダイシングフィルムの基材として好適に用いられるが、当該用途に限定されない。 2. Dicing Film Base Material The dicing base material may be any base material as long as it has at least one layer containing the above-mentioned resin composition. Since the dicing film base material has a layer containing the above-mentioned resin composition, it exhibits excellent modulus strength and elongation at room temperature and low temperature. The dicing film base material is suitably used as a base material for a dicing film, but is not limited to this use.
ダイシング基材は、上述の樹脂組成物を含む層を少なくとも一層有する基材であればよい。当該ダイシングフィルム基材は、上述の樹脂組成物を含む層を有するため、常温および低温において、優れたモジュラス強度や伸び性を発揮する。当該ダイシングフィルム基材は、ダイシングフィルムの基材として好適に用いられるが、当該用途に限定されない。 2. Dicing Film Base Material The dicing base material may be any base material as long as it has at least one layer containing the above-mentioned resin composition. Since the dicing film base material has a layer containing the above-mentioned resin composition, it exhibits excellent modulus strength and elongation at room temperature and low temperature. The dicing film base material is suitably used as a base material for a dicing film, but is not limited to this use.
当該ダイシングフィルム基材の構成は特に限定されず、上述の樹脂組成物を含む層を一層のみ有していてもよく、上述の樹脂組成物を含む層を２層以上有していてもよい。さらに、必要に応じて他の樹脂層が積層されていてもよい。
The structure of the dicing film base material is not particularly limited, and may have only one layer containing the above-mentioned resin composition, or may have two or more layers containing the above-mentioned resin composition. Furthermore, other resin layers may be laminated as necessary.
ダイシングフィルム基材の例には、上述の樹脂組成物を含む層のみからなる１層構造の積層体；上述の樹脂組成物を含む層および他の樹脂層の２層からなる２層構造の積層体；上述の樹脂組成物を含む層／他の樹脂層／上述の樹脂組成物を含む層の３層からなる３層構造の積層体；等が含まれる。また、ダイシングフィルム基材は、上記以外にも、粘着剤を含む層や、粘着シート等をさらに含んでいてもよい。
Examples of the dicing film base material include a laminate with a one-layer structure consisting only of a layer containing the above-mentioned resin composition; a laminate with a two-layer structure consisting of a layer containing the above-mentioned resin composition and another resin layer. body; a laminate having a three-layer structure consisting of three layers: a layer containing the above-mentioned resin composition/another resin layer/a layer containing the above-mentioned resin composition; and the like. Moreover, the dicing film base material may further contain a layer containing an adhesive, an adhesive sheet, etc. in addition to the above.
ここで、上述の樹脂組成物を含む層は、上述の樹脂組成物のみからなる層であってもよく、上述の樹脂組成物と、本発明の目的および効果を損なわない範囲で、他の成分とを含む層であってもよいが、実質的に上述の樹脂組成物からなる層であることが、ダイシングフィルム基材の伸び性やモジュラス強度の観点で好ましい。
Here, the layer containing the above-mentioned resin composition may be a layer consisting only of the above-mentioned resin composition, or may include the above-mentioned resin composition and other components within the range that does not impair the purpose and effects of the present invention. However, a layer consisting essentially of the above-mentioned resin composition is preferable from the viewpoint of the extensibility and modulus strength of the dicing film base material.
上述の樹脂組成物を含む層の厚みは特に制限されないが、ダイシングフィルム基材の強度や、モジュラス強度、伸び性等を良好にするとの観点で、５０μｍ以上２００μｍ以下が好ましく、６０μｍ以上１８０μｍ以下がより好ましい。
The thickness of the layer containing the above resin composition is not particularly limited, but from the viewpoint of improving the strength, modulus strength, elongation, etc. of the dicing film base material, it is preferably 50 μm or more and 200 μm or less, and 60 μm or more and 180 μm or less. More preferred.
また、樹脂組成物を含む層の２３℃で測定したＭＤ方向（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ）の３０％モジュラスおよびＴＤ方向（Ｔｒａｎｓｖｅｒｓｅ Ｄｉｒｅｃｔｉｏｎ）の３０％モジュラスの平均値は、８ＭＰａ以上１７ＭＰａ以下が好ましく、１０ＭＰａ以上１５ＭＰａ以下がより好ましい。２３℃における３０％モジュラスの平均値が当該範囲であると、常温でのダイシングフィルム基材の伸び性が良好になりやすい。上記３０％モジュラスは、上記樹脂組成物を含む層と同様の組成の、厚み１００μｍ、ＴＤ方向長さ１０ｍｍ、ＭＤ方向長さ１８０ｍｍのフィルムを準備し、当該フィルムについてＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置である島津卓上型精密万能試験機ＡＧ－Ｘによって測定される値である。チャック間距離は１００ｍｍ、試験速度は３００ｍｍ／分とする。
Further, the average value of the 30% modulus in the MD direction (Machine Direction) and the 30% modulus in the TD direction (Transverse Direction) measured at 23° C. of the layer containing the resin composition is preferably 8 MPa or more and 17 MPa or less, and 10 MPa or more and 15 MPa or less. The following are more preferred. When the average value of the 30% modulus at 23° C. is within this range, the extensibility of the dicing film base material at room temperature tends to be good. The above 30% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 μm, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The distance between chucks is 100 mm, and the test speed is 300 mm/min.
一方、樹脂組成物を含む層の－１５℃で測定したＭＤ方向の１０％モジュラスおよびＴＤ方向の１０％モジュラスの平均値は、２０ＭＰａ以上が好ましく、２４ＭＰａ以上がより好ましい。－１５℃における１０％モジュラスの平均値が２０ＭＰａ以上であると、低温でのダイシングフィルム基材の分断性と伸び性が良好になりやすい。上記１０％モジュラスは、上記樹脂組成物を含む層と同様の組成の、厚み１００μｍ、ＴＤ方向長さ１０ｍｍ、ＭＤ方向長さ１８０ｍｍのフィルムを準備し、当該フィルムについてＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置である島津卓上型精密万能試験機ＡＧ－Ｘによって測定される値である。チャック間距離は１００ｍｍ、試験速度は１０００ｍｍ／分とする。
On the other hand, the average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15° C. of the layer containing the resin composition is preferably 20 MPa or more, more preferably 24 MPa or more. When the average value of 10% modulus at -15°C is 20 MPa or more, the dicing film base material tends to have good separability and elongation at low temperatures. The above 10% modulus is determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 μm, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The distance between the chucks is 100 mm, and the test speed is 1000 mm/min.
樹脂組成物を含む層は、２３℃においてＭＤ方向の２００％モジュラスおよびＴＤ方向の２００％モジュラスを、いずれも測定可能であることが好ましい。２３℃におけるＭＤ方向の２００％モジュラスと２３℃におけるＴＤ方向の２００％モジュラスとがいずれも測定可能であると、ピックアップ工程において、チップに応力が掛かりにくく、チップ内の破損が起こりにくい。上記２００％モジュラスは、上記樹脂組成物を含む層と同様の組成の、厚み１００μｍ、ＴＤ方向長さ１０ｍｍ、ＭＤ方向長さ１８０ｍｍのフィルムを準備し、当該フィルムについてＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置である島津卓上型精密万能試験機ＡＧ－Ｘによって測定される値である。試験速度は３００ｍｍ／分とする。
It is preferable that the layer containing the resin composition can measure both the 200% modulus in the MD direction and the 200% modulus in the TD direction at 23°C. If both the 200% modulus in the MD direction at 23° C. and the 200% modulus in the TD direction at 23° C. can be measured, stress is less likely to be applied to the chip in the pick-up process, and damage within the chip is less likely to occur. The above 200% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 μm, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm, and the film was determined according to JIS K 7127:1999 (ISO 527). -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The test speed is 300 mm/min.
樹脂組成物を含む層は、－１５℃においてＭＤ方向の２００％モジュラスおよびＴＤ方向の２００％モジュラスを、いずれも測定可能であることが好ましい。－１５℃におけるＭＤ方向の２００％モジュラスと－１５℃におけるＴＤ方向の２００％モジュラスとがいずれも測定可能であると、低温でチップとダイボンドフィルムの分断と拡張（エキスパンド）を行う工程において分断と拡張（エキスパンド）を良好に実施しやすい。上記２００％モジュラスは、上記樹脂組成物を含む層と同様の組成の、厚み１００μｍ、ＴＤ方向長さ１０ｍｍ、ＭＤ方向長さ１８０ｍｍのフィルムを準備し、当該フィルムについてＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置である島津卓上型精密万能試験機ＡＧ－Ｘによって測定される値である。試験速度は１０００ｍｍ／分とする。
It is preferable that the layer containing the resin composition can measure both the 200% modulus in the MD direction and the 200% modulus in the TD direction at -15°C. If both the 200% modulus in the MD direction at -15°C and the 200% modulus in the TD direction at -15°C can be measured, it is possible to measure both the 200% modulus in the MD direction at -15°C and the 200% modulus in the TD direction at -15°C. Easy to perform expansion. The above 200% modulus was determined by preparing a film having the same composition as the layer containing the resin composition, having a thickness of 100 μm, a length in the TD direction of 10 mm, and a length in the MD direction of 180 mm. -3:1995), and is a value measured by a Shimadzu desktop precision universal testing machine AG-X. The test speed is 1000 mm/min.
一方、他の樹脂層の例には、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、エチレン・αオレフィン共重合体、ポリプロピレン、エチレン・不飽和カルボン酸共重合体またはそのアイオノマー、エチレン・不飽和カルボン酸・不飽和カルボン酸アルキルエステル三元共重合体またはそのアイオノマー、エチレン・不飽和カルボン酸アルキルエステル共重合体、エチレン・ビニルエステル共重合体、エチレン・不飽和カルボン酸アルキルエステル・一酸化炭素共重合体、これらの不飽和カルボン酸グラフト物、ポリ塩化ビニル等を含む層が含まれる。他の樹脂層は、上記樹脂を一種のみ含んでいてもよく、二種以上含んでいてもよい。
On the other hand, examples of other resin layers include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene/α-olefin copolymer, polypropylene, ethylene/unsaturated carboxylic acid copolymer or its ionomer. , ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid alkyl ester terpolymer or its ionomer, ethylene/unsaturated carboxylic acid alkyl ester copolymer, ethylene/vinyl ester copolymer, ethylene/unsaturated alkyl carboxylate A layer containing an ester/carbon monoxide copolymer, an unsaturated carboxylic acid graft product thereof, polyvinyl chloride, etc. is included. The other resin layer may contain only one type of the above resin, or may contain two or more types of the above resin.
他の樹脂層の厚みは特に制限されないが、上記樹脂組成物を含む層のモジュラス強度や伸び性を損なわないとの観点で、１０μｍ以上１００μｍ以下が好ましく、１５μｍ以上８０μｍ以下がより好ましい。
The thickness of the other resin layer is not particularly limited, but from the viewpoint of not impairing the modulus strength and elongation of the layer containing the resin composition, it is preferably 10 μm or more and 100 μm or less, and more preferably 15 μm or more and 80 μm or less.
ここで、ダイシングフィルム基材全体の厚みは、ダイシングフィルムの構成部材として用いることを考慮すると、ダイシング時のフレーム保持の観点から５０μｍ以上、拡張性（エキスパンド性）の観点から２００μｍ以下が好ましい。
Here, the thickness of the entire dicing film base material is preferably 50 μm or more from the viewpoint of frame retention during dicing and 200 μm or less from the viewpoint of expandability, considering that it is used as a component of the dicing film.
上記ダイシングフィルム基材表面は、各種処理がされていてもよく、例えばコロナ処理等が施されていてもよい。さらに、電子線照射当が行われていてもよい。
The surface of the dicing film base material may be subjected to various treatments, such as corona treatment. Furthermore, electron beam irradiation may be performed.
上記ダイシングフィルム基材の製造方法は特に制限されず、公知の成形法によって製造できる。例えば、上述の樹脂組成物を含む層のみからなるダイシングフィルム基材を製造する場合、従来公知のＴダイキャスト成形法、Ｔダイニップ成形法、インフレーション成形法、押出ラミネート法、カレンダー成形法等によって、上記樹脂組成物等を成形すればよい。
The manufacturing method of the above-mentioned dicing film base material is not particularly limited, and it can be manufactured by a known molding method. For example, when manufacturing a dicing film base material consisting only of a layer containing the above-mentioned resin composition, conventionally known T die casting method, T die nip molding method, inflation molding method, extrusion lamination method, calendar molding method, etc. The above resin composition etc. may be molded.
一方、ダイシングフィルム基材が、上述の樹脂組成物を含む層と、他の樹脂層との積層体である場合には、上述の樹脂組成物と、他の樹脂とを、共押出ラミネート法等によって成形すればよい。また、上述の樹脂組成物を含む層と、他の樹脂層とをそれぞれ別に作製し、これらを接着剤や接着シート等によって貼り合わせてもよい。接着剤や接着シートの材料の例には、各種エチレン共重合体、あるいはこれらの不飽和カルボン酸グラフト物等が含まれる。また、ダイシングフィルム基材が、上述の樹脂組成物を含む層と、他の樹脂層との積層体である場合、上述の樹脂組成物を含む層および他の樹脂層のうち、いずれか一方を先に形成し、当該一方の層上に、Ｔダイフィルム成形機、押出コーティング成形機等によって他方の層を形成し、積層してもよい。
On the other hand, when the dicing film base material is a laminate of a layer containing the above-mentioned resin composition and another resin layer, the above-mentioned resin composition and other resin are combined by a coextrusion lamination method, etc. It can be formed by Alternatively, a layer containing the above-mentioned resin composition and another resin layer may be produced separately, and then bonded together using an adhesive, an adhesive sheet, or the like. Examples of materials for adhesives and adhesive sheets include various ethylene copolymers and unsaturated carboxylic acid grafts thereof. In addition, when the dicing film base material is a laminate of a layer containing the above-mentioned resin composition and another resin layer, one of the layer containing the above-mentioned resin composition and the other resin layer is The first layer may be formed first, and then the other layer may be formed on the one layer using a T-die film molding machine, an extrusion coating molding machine, etc., and then laminated.
３．ダイシングフィルム
本発明のダイシングフィルムは、上述のダイシングフィルム基材と、その少なくとも一方の面に積層された粘着層と、を備えていればよく、必要に応じて他の構成を含んでいてもよい。なお、上述のダイシングフィルム基材が多層からなる場合、ダイシングフィルム基材中の樹脂組成物を含む層と、粘着層とが積層されていることが好ましい。 3. Dicing Film The dicing film of the present invention only needs to include the above-described dicing film base material and an adhesive layer laminated on at least one surface thereof, and may include other configurations as necessary. . In addition, when the above-mentioned dicing film base material consists of multiple layers, it is preferable that the layer containing the resin composition in the dicing film base material and the adhesive layer are laminated.
本発明のダイシングフィルムは、上述のダイシングフィルム基材と、その少なくとも一方の面に積層された粘着層と、を備えていればよく、必要に応じて他の構成を含んでいてもよい。なお、上述のダイシングフィルム基材が多層からなる場合、ダイシングフィルム基材中の樹脂組成物を含む層と、粘着層とが積層されていることが好ましい。 3. Dicing Film The dicing film of the present invention only needs to include the above-described dicing film base material and an adhesive layer laminated on at least one surface thereof, and may include other configurations as necessary. . In addition, when the above-mentioned dicing film base material consists of multiple layers, it is preferable that the layer containing the resin composition in the dicing film base material and the adhesive layer are laminated.
粘着層を構成する粘着剤は一般的なダイシングフィルムの粘着層用の粘着剤とすることができる。粘着剤の例には、ゴム系、アクリル系、シリコーン系、ポリビニルエーテル系の粘着剤；放射線硬化型粘着剤；加熱発泡型粘着剤等が含まれる。なかでも、半導体ウエハからのダイシングフィルムの剥離性を考慮すると、粘着層は放射線硬化型粘着剤を含むことが好ましく、紫外線硬化型粘着剤を含むことがより好ましい。
The adhesive constituting the adhesive layer can be an adhesive for the adhesive layer of a general dicing film. Examples of the adhesive include rubber-based, acrylic-based, silicone-based, and polyvinyl ether-based adhesives; radiation-curable adhesives; heat-foaming adhesives, and the like. Among these, in consideration of the releasability of the dicing film from the semiconductor wafer, the adhesive layer preferably contains a radiation-curable adhesive, and more preferably contains an ultraviolet-curable adhesive.
紫外線硬化型粘着剤は通常、ラジカル重合可能なラジカル重合性化合物（モノマー、オリゴマー、またはポリマーのいずれでもよい）と、光重合開始剤とを含み、必要に応じて架橋剤、粘着付与剤、充填剤、老化防止剤、着色剤等の添加剤等を含む。
UV-curable adhesives usually contain a radically polymerizable compound (which can be a monomer, oligomer, or polymer) and a photopolymerization initiator, and optionally a crosslinker, tackifier, and filler. Contains additives such as anti-aging agents, anti-aging agents, and coloring agents.
ラジカル重合性化合物の例には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソノニル等の（メタ）アクリル酸アルキルエステルのモノマーまたはオリゴマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシヘキシル等の（メタ）アクリル酸ヒドロキシアルキルエステルのモノマーまたはオリゴマー；上記（メタ）アクリル酸アルキルエステルおよび／または（メタ）アクリル酸ヒドロキシアルキルエステルと、他の単量体（例えば（メタ）アクリル酸、イタコン酸、無水マレイン酸、（メタ）アクリル酸アミド、（メタ）アクリル酸Ｎ－ヒドロキシメチルアミド、（メタ）アクリル酸アルキルアミノアルキルエステル、酢酸ビニル、スチレン、アクリロニトリル等）との共重合モノマーまたはオリゴマー；（メタ）アクリル酸グリシジルエステトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，６－へキサンジオール（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステルモノマー、またそのオリゴマー；２－プロペニルジ－３－ブテニルシアヌレート、２－ヒドロキシエチルビス（２－アクリロキシエチル）イソシアヌレート、トリス（２－メクリロキシエチル）イソシアヌレート、トリス（２－メタクリロキシエチル）イソシアヌレート等のイソシアヌレート等が含まれる。
Examples of radically polymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and (meth)acrylate. Monomers or oligomers of alkyl (meth)acrylates such as isononyl acid; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, etc. Monomer or oligomer; the above (meth)acrylic acid alkyl ester and/or (meth)acrylic acid hydroxyalkyl ester and other monomers (such as (meth)acrylic acid, itaconic acid, maleic anhydride, (meth)acrylic acid amide, (meth)acrylic acid N-hydroxymethylamide, (meth)acrylic acid alkylaminoalkyl ester, vinyl acetate, styrene, acrylonitrile, etc.); (meth)acrylic acid glycidyl ester trimethylolpropanetri (meth)acrylate, pentaerythritol tri(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol(meth)acrylate, neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester monomers of (meth)acrylic acid and polyhydric alcohol such as acrylate, and oligomers thereof; 2-propenyl di-3-butenyl cyanurate, 2-hydroxyethyl bis(2-acryloxyethyl) isocyanurate, tris(2 -Mecryloxyethyl) isocyanurate, tris(2-methacryloxyethyl) isocyanurate, and other isocyanurates.
光重合開始剤の具体例には、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインアルキルエーテル類；α－ヒドロキシシクロヘキシルフェニルケトンなどの芳香族ケトン類；ベンジルジメチルケタール等の芳香族ケタール類；ポリビニルベンゾフェノン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン等のチオキサントン類が含まれる。
Specific examples of photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; aromatic ketones such as α-hydroxycyclohexylphenyl ketone; aromatic ketals such as benzyl dimethyl ketal. ; Includes thioxanthone such as polyvinylbenzophenone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone.
架橋剤の例には、ポリイソシアネート化合物、メラミン樹脂、尿素樹脂、ポリアミン、カルボキシル基含有ポリマー等が含まれる。
Examples of crosslinking agents include polyisocyanate compounds, melamine resins, urea resins, polyamines, carboxyl group-containing polymers, and the like.
上記粘着層の厚さは、粘着剤の種類に応じて適宜選択され、３～１００μｍが好ましく、３～５０μｍがさらに好ましい。
The thickness of the adhesive layer is appropriately selected depending on the type of adhesive, and is preferably 3 to 100 μm, more preferably 3 to 50 μm.
また、ダイシングフィルムの粘着層は、セパレータによって保護されていてもよい。粘着層がセパレータで保護されていると、粘着層の表面を平滑に保つことができる。また、ダイシングフィルムの取り扱いや運搬が容易になるとともに、セパレータ上にラベル加工することも可能となる。当該セパレータは、ダイシングフィルムを使用する際に剥離される。
Additionally, the adhesive layer of the dicing film may be protected by a separator. When the adhesive layer is protected with a separator, the surface of the adhesive layer can be kept smooth. Furthermore, the dicing film can be easily handled and transported, and it is also possible to process a label on the separator. The separator is peeled off when using the dicing film.
セパレータは、紙、またはポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の合成樹脂フィルム等であってもよい。また、セパレータの粘着層と接する面には、粘着層からの剥離性を高めるために、必要に応じてシリコーン処理やフッ素処理等の離型処理が施されていてもよい。セパレータの厚みは、通常１０～２００μｍ、好ましくは２５～１００μｍ程度が好ましい。
The separator may be paper or a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, etc. Furthermore, the surface of the separator that comes into contact with the adhesive layer may be subjected to a release treatment such as silicone treatment or fluorine treatment, as necessary, in order to improve the releasability from the adhesive layer. The thickness of the separator is usually about 10 to 200 μm, preferably about 25 to 100 μm.
上記ダイシングフィルムの製造方法は特に制限されず、例えば、上述のダイシング基材上に、粘着剤を公知の方法で塗布して製造してもよい。このとき粘着剤の塗布は、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター等によって行うことができる。また、剥離シート上に粘着剤を塗布して粘着層を形成し、ダイシングフィルム基材に当該粘着層を転写して、ダイシングフィルム基材と粘着層とを積層してもよい。また、ダイシングフィルム基材と、粘着層とを共押し出し等によって、同時に形成してもよい。
The method for producing the dicing film is not particularly limited, and for example, the dicing film may be produced by applying an adhesive onto the dicing base material using a known method. At this time, the adhesive can be applied using a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, or the like. Alternatively, an adhesive layer may be formed by applying an adhesive on a release sheet, and the adhesive layer may be transferred to a dicing film base material to laminate the dicing film base material and the adhesive layer. Alternatively, the dicing film base material and the adhesive layer may be formed simultaneously by coextrusion or the like.
以下において、実施例を参照して本発明を説明する。実施例によって、本発明の範囲は限定して解釈されない。
In the following, the present invention will be explained with reference to examples. The scope of the present invention is not interpreted to be limited by the Examples.
［材料の準備］
各成分は、以下のものを用いた。
＜エチレン・不飽和カルボン酸系共重合体のアイオノマー（Ａ）＞
ＩＯ１：エチレン・メタクリル酸共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８５質量％、メタクリル酸に由来する構成単位の含有量：１５質量％、中和度：５９％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：８．９ｇ／１０分）
ＩＯ２：エチレン・メタクリル酸共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８０質量％、メタクリル酸に由来する構成単位の含有量：２０質量％、中和度：４０％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：８．０ｇ／１０分） [Preparation of materials]
The following components were used.
<Ionomer of ethylene/unsaturated carboxylic acid copolymer (A)>
IO1: Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 85% by mass, content of structural units derived from methacrylic acid: 15% by mass, degree of neutralization: 59% zinc, JIS MFR: 8.9 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
IO2: Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 20% by mass, degree of neutralization: 40% zinc, JIS MFR: 8.0 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
各成分は、以下のものを用いた。
＜エチレン・不飽和カルボン酸系共重合体のアイオノマー（Ａ）＞
ＩＯ１：エチレン・メタクリル酸共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８５質量％、メタクリル酸に由来する構成単位の含有量：１５質量％、中和度：５９％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：８．９ｇ／１０分）
ＩＯ２：エチレン・メタクリル酸共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８０質量％、メタクリル酸に由来する構成単位の含有量：２０質量％、中和度：４０％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：８．０ｇ／１０分） [Preparation of materials]
The following components were used.
<Ionomer of ethylene/unsaturated carboxylic acid copolymer (A)>
IO1: Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 85% by mass, content of structural units derived from methacrylic acid: 15% by mass, degree of neutralization: 59% zinc, JIS MFR: 8.9 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
IO2: Ionomer of ethylene/methacrylic acid copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 20% by mass, degree of neutralization: 40% zinc, JIS MFR: 8.0 g/10 min, measured at 190°C and 2160 g load according to K 7210:1999 (equivalent to ISO 1133:1997)
＜エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）＞
ＩＯ３：エチレン・メタクリル酸・アクリル酸ブチルエステル共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８０質量％、メタクリル酸に由来する構成単位の含有量：１０質量％、アクリル酸ブチルエステルに由来する構成単位の含有量：１０質量％、中和度：７０％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：１ｇ／１０分） <Ionomer of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (B)>
IO3: Ionomer of ethylene/methacrylic acid/butyl acrylate copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 10% by mass, butyl acrylate) Content of structural units derived from: 10% by mass, degree of neutralization: 70% zinc, MFR measured at 190°C and 2160g load according to JIS K 7210:1999 (equivalent to ISO 1133:1997): 1g /10 minutes)
ＩＯ３：エチレン・メタクリル酸・アクリル酸ブチルエステル共重合体のアイオノマー（エチレンに由来する構成単位の含有量：８０質量％、メタクリル酸に由来する構成単位の含有量：１０質量％、アクリル酸ブチルエステルに由来する構成単位の含有量：１０質量％、中和度：７０％亜鉛、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、１９０℃、２１６０ｇ荷重で測定されるＭＦＲ：１ｇ／１０分） <Ionomer of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer (B)>
IO3: Ionomer of ethylene/methacrylic acid/butyl acrylate copolymer (content of structural units derived from ethylene: 80% by mass, content of structural units derived from methacrylic acid: 10% by mass, butyl acrylate) Content of structural units derived from: 10% by mass, degree of neutralization: 70% zinc, MFR measured at 190°C and 2160g load according to JIS K 7210:1999 (equivalent to ISO 1133:1997): 1g /10 minutes)
＜スチレン系エラストマー（Ｃ）＞
・スチレン系エラストマー１：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、Ｓ．Ｏ．Ｅ．Ｓ１６１１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：１２．０ｇ／１０分、Ｔａｎδピーク温度：９℃）
・スチレン系エラストマー２：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１２２１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：４．５ｇ／１０分、Ｔａｎδピーク温度：－１９℃）
・スチレン系エラストマー３：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１０６２（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：４．５ｇ／１０分、Ｔａｎδピーク温度：－４７℃）
・スチレン系エラストマー４：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１０４１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：５．０ｇ／１０分、Ｔａｎδピーク温度：－４５℃）
・スチレン系エラストマー５：ＨＳＢＲ（スチレン・ブタジエンランダム共重合体の水素添加物（ＪＳＲ社製、ダイナロン１３２０Ｐ（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：３．５ｇ／１０分、Ｔａｎδピーク温度：－１５℃）
・スチレン系エラストマー６：ＳＥＰＳ（スチレン－エチレン・プロピレン－スチレンブロック共重合体（クラレ社製、セプトン２００２、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：７０．０ｇ／１０分） <Styrenic elastomer (C)>
・Styrenic elastomer 1: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, S.O.E.S1611 (product name), JIS K 7210:1999 (equivalent to ISO 1133:1997) MFR measured at 230°C and 2160g load: 12.0g/10 minutes, Tanδ peak temperature: 9°C)
- Styrenic elastomer 2: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1221 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 4.5g/10min, Tan δ peak temperature: -19℃)
- Styrenic elastomer 3: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1062 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 4.5g/10min, Tan δ peak temperature: -47℃)
- Styrenic elastomer 4: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1041 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 5.0g/10 minutes, Tan δ peak temperature: -45℃)
・Styrenic elastomer 5: HSBR (hydrogenated styrene-butadiene random copolymer (manufactured by JSR Corporation, Dynalon 1320P (trade name), according to JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ° C. , MFR measured at 2160g load: 3.5g/10min, Tanδ peak temperature: -15°C)
・Styrenic elastomer 6: SEPS (styrene-ethylene propylene-styrene block copolymer (manufactured by Kuraray Co., Ltd., Septon 2002, based on JIS K 7210:1999 (equivalent to ISO 1133:1997), at 230°C and a load of 2160g. Measured MFR: 70.0g/10min)
・スチレン系エラストマー１：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、Ｓ．Ｏ．Ｅ．Ｓ１６１１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：１２．０ｇ／１０分、Ｔａｎδピーク温度：９℃）
・スチレン系エラストマー２：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１２２１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：４．５ｇ／１０分、Ｔａｎδピーク温度：－１９℃）
・スチレン系エラストマー３：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１０６２（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：４．５ｇ／１０分、Ｔａｎδピーク温度：－４７℃）
・スチレン系エラストマー４：ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体（旭化成ケミカルズ社製、タフテックＨ１０４１（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：５．０ｇ／１０分、Ｔａｎδピーク温度：－４５℃）
・スチレン系エラストマー５：ＨＳＢＲ（スチレン・ブタジエンランダム共重合体の水素添加物（ＪＳＲ社製、ダイナロン１３２０Ｐ（商品名）、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：３．５ｇ／１０分、Ｔａｎδピーク温度：－１５℃）
・スチレン系エラストマー６：ＳＥＰＳ（スチレン－エチレン・プロピレン－スチレンブロック共重合体（クラレ社製、セプトン２００２、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠し、２３０℃、２１６０ｇ荷重で測定されるＭＦＲ：７０．０ｇ／１０分） <Styrenic elastomer (C)>
・Styrenic elastomer 1: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, S.O.E.S1611 (product name), JIS K 7210:1999 (equivalent to ISO 1133:1997) MFR measured at 230°C and 2160g load: 12.0g/10 minutes, Tanδ peak temperature: 9°C)
- Styrenic elastomer 2: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1221 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 4.5g/10min, Tan δ peak temperature: -19℃)
- Styrenic elastomer 3: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1062 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 4.5g/10min, Tan δ peak temperature: -47℃)
- Styrenic elastomer 4: SEBS (styrene-ethylene/butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, Tuftec H1041 (product name), based on JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ℃, MFR measured at 2160g load: 5.0g/10 minutes, Tan δ peak temperature: -45℃)
・Styrenic elastomer 5: HSBR (hydrogenated styrene-butadiene random copolymer (manufactured by JSR Corporation, Dynalon 1320P (trade name), according to JIS K 7210:1999 (equivalent to ISO 1133:1997), 230 ° C. , MFR measured at 2160g load: 3.5g/10min, Tanδ peak temperature: -15°C)
・Styrenic elastomer 6: SEPS (styrene-ethylene propylene-styrene block copolymer (manufactured by Kuraray Co., Ltd., Septon 2002, based on JIS K 7210:1999 (equivalent to ISO 1133:1997), at 230°C and a load of 2160g. Measured MFR: 70.0g/10min)
［実施例１～１１および比較例１～５］
表１に示す割合（質量比）で、エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）をドライブレンドした。次に、３０ｍｍφ二軸押出機の樹脂投入口にドライブレンドした混合物を投入して、ダイス温度２３０℃で溶融混練し、ダイシングフィルム基材用樹脂組成物を得た。得られたダイシングフィルム基材用樹脂組成物について、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠して、１９０℃、２１６０ｇ荷重でＭＦＲを測定した。結果を表１に示す。 [Examples 1 to 11 and Comparative Examples 1 to 5]
In the proportions (mass ratio) shown in Table 1, the ionomer (A) of ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene-based The elastomer (C) was dry blended. Next, the dry blended mixture was charged into a resin inlet of a 30 mmφ twin screw extruder and melt-kneaded at a die temperature of 230° C. to obtain a resin composition for a dicing film base material. Regarding the obtained resin composition for a dicing film base material, MFR was measured at 190° C. and a load of 2160 g in accordance with JIS K 7210:1999 (corresponding to ISO 1133:1997). The results are shown in Table 1.
表１に示す割合（質量比）で、エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、およびスチレン系エラストマー（Ｃ）をドライブレンドした。次に、３０ｍｍφ二軸押出機の樹脂投入口にドライブレンドした混合物を投入して、ダイス温度２３０℃で溶融混練し、ダイシングフィルム基材用樹脂組成物を得た。得られたダイシングフィルム基材用樹脂組成物について、ＪＩＳ Ｋ ７２１０：１９９９（ＩＳＯ １１３３：１９９７に相当）に準拠して、１９０℃、２１６０ｇ荷重でＭＦＲを測定した。結果を表１に示す。 [Examples 1 to 11 and Comparative Examples 1 to 5]
In the proportions (mass ratio) shown in Table 1, the ionomer (A) of ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene-based The elastomer (C) was dry blended. Next, the dry blended mixture was charged into a resin inlet of a 30 mmφ twin screw extruder and melt-kneaded at a die temperature of 230° C. to obtain a resin composition for a dicing film base material. Regarding the obtained resin composition for a dicing film base material, MFR was measured at 190° C. and a load of 2160 g in accordance with JIS K 7210:1999 (corresponding to ISO 1133:1997). The results are shown in Table 1.
［評価］
得られたダイシングフィルム基材用樹脂組成物を、４０ｍｍφＴダイフィルム成形機を用いて、加工温度２３０℃で成形し、１００μｍ厚のＴダイフィルムを作製した。得られたＴダイフィルムをダイシングフィルム基材とし、下記の方法で評価した。 [evaluation]
The obtained resin composition for a dicing film base material was molded using a 40 mmφ T-die film molding machine at a processing temperature of 230° C. to produce a 100 μm thick T-die film. The obtained T-die film was used as a dicing film base material and evaluated by the following method.
得られたダイシングフィルム基材用樹脂組成物を、４０ｍｍφＴダイフィルム成形機を用いて、加工温度２３０℃で成形し、１００μｍ厚のＴダイフィルムを作製した。得られたＴダイフィルムをダイシングフィルム基材とし、下記の方法で評価した。 [evaluation]
The obtained resin composition for a dicing film base material was molded using a 40 mmφ T-die film molding machine at a processing temperature of 230° C. to produce a 100 μm thick T-die film. The obtained T-die film was used as a dicing film base material and evaluated by the following method.
さらに、不飽和カルボン酸由来の構成単位の総量は、「２元系アイオノマー（Ａ）の含有割合×２元系アイオノマー（Ａ）中のカルボン酸由来の構成単位の量」と「３元系アイオノマー（Ｂ）の含有割合×３元系アイオノマー（Ｂ）中のカルボン酸由来の構成単位の量」との和から算出した。
Furthermore, the total amount of structural units derived from unsaturated carboxylic acids is determined by "content ratio of binary ionomer (A) x amount of structural units derived from carboxylic acid in binary ionomer (A)" and "amount of structural units derived from carboxylic acid in ternary ionomer (A)" It was calculated from the sum of the content ratio of (B) x the amount of structural units derived from carboxylic acid in the ternary ionomer (B).
不飽和カルボン酸エステル由来の構成単位の総量は、「３元系アイオノマー（Ｂ）の含有割合×３元系アイオノマー（Ｂ）中のカルボン酸エステル由来の構成単位の量」から算出した。
The total amount of structural units derived from unsaturated carboxylic acid esters was calculated from "content ratio of ternary ionomer (B) x amount of structural units derived from carboxylic acid esters in ternary ionomer (B)".
中和度（モル％）は、「２元系アイオノマー（Ａ）の中和度×（２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の総量に対する、２元系アイオノマー（Ａ）の量の割合）」＋「３元系アイオノマー（Ｂ）の中和度×（２元系アイオノマー（Ａ）および３元系アイオノマー（Ｂ）の総量に対する、３元系アイオノマー（Ｂ）の量の割合）」によって、特定した。さらに、「不飽和カルボン酸由来の構成単位の総量×中和度／１００」も算出した。各結果を表１に示す。
The degree of neutralization (mol%) is calculated as follows: "Degree of neutralization of the binary ionomer (A) x (of the binary ionomer (A) relative to the total amount of the binary ionomer (A) and the ternary ionomer (B)") "Amount ratio)" + "Neutralization degree of ternary ionomer (B) x (Ratio of amount of ternary ionomer (B) to the total amount of binary ionomer (A) and ternary ionomer (B) )”. Furthermore, "total amount of structural units derived from unsaturated carboxylic acid x degree of neutralization/100" was also calculated. The results are shown in Table 1.
（１）常温モジュラス強度
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、試料（ダイシングフィルム基材）のＭＤ方向（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ）およびＴＤ方向（Ｔｒａｎｓｖｅｒｓｅ Ｄｉｒｅｃｔｉｏｎ）のそれぞれについて、２３℃にて、３０％モジュラスを測定した。チャック間距離は１００ｍｍ、試験速度は３００ｍｍ／分とした。 (1) Room temperature modulus strength The above dicing film base material was cut into strips of 10 mm width x 180 mm length. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), the MD direction (Machine Direction) of the sample (dicing film base material) was ) and TD direction (Transverse Direction), the 30% modulus was measured at 23°C. The distance between chucks was 100 mm, and the test speed was 300 mm/min.
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、試料（ダイシングフィルム基材）のＭＤ方向（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ）およびＴＤ方向（Ｔｒａｎｓｖｅｒｓｅ Ｄｉｒｅｃｔｉｏｎ）のそれぞれについて、２３℃にて、３０％モジュラスを測定した。チャック間距離は１００ｍｍ、試験速度は３００ｍｍ／分とした。 (1) Room temperature modulus strength The above dicing film base material was cut into strips of 10 mm width x 180 mm length. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), the MD direction (Machine Direction) of the sample (dicing film base material) was ) and TD direction (Transverse Direction), the 30% modulus was measured at 23°C. The distance between chucks was 100 mm, and the test speed was 300 mm/min.
上記試験により得られたＭＤ方向の３０％モジュラスおよびＴＤ方向の３０％モジュラスを平均し、以下の基準によりダイシングフィルム基材の常温モジュラス強度を評価した。
Ａ（良好） ：１０ＭＰａ以上１５ＭＰａ以下
Ｂ（やや良好）：８ＭＰａ以上１０ＭＰａ未満、または、１５ＭＰａ超１７ＭＰａ以下
Ｃ（不良） ：８ＭＰａ未満、または、１７ＭＰａ超 The 30% modulus in the MD direction and the 30% modulus in the TD direction obtained in the above test were averaged, and the room temperature modulus strength of the dicing film base material was evaluated according to the following criteria.
A (good): 10 MPa or more and 15 MPa or less B (slightly good): 8 MPa or more and less than 10 MPa, or more than 15 MPa and 17 MPa or less C (bad): Less than 8 MPa, or more than 17 MPa
Ａ（良好） ：１０ＭＰａ以上１５ＭＰａ以下
Ｂ（やや良好）：８ＭＰａ以上１０ＭＰａ未満、または、１５ＭＰａ超１７ＭＰａ以下
Ｃ（不良） ：８ＭＰａ未満、または、１７ＭＰａ超 The 30% modulus in the MD direction and the 30% modulus in the TD direction obtained in the above test were averaged, and the room temperature modulus strength of the dicing film base material was evaluated according to the following criteria.
A (good): 10 MPa or more and 15 MPa or less B (slightly good): 8 MPa or more and less than 10 MPa, or more than 15 MPa and 17 MPa or less C (bad): Less than 8 MPa, or more than 17 MPa
（２）低温モジュラス強度
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、試料（ダイシングフィルム基材）のＭＤ方向およびＴＤ方向のそれぞれについて、－１５℃にて、１０％モジュラスを測定した。チャック間距離は１００ｍｍ、試験速度は１０００ｍｍ／分とした。 (2) Low-temperature modulus strength The above-mentioned dicing film base material was cut into strips with a width of 10 mm and a length of 180 mm. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), the MD and TD directions of the sample (dicing film base material) were measured using Shimadzu desktop precision universal testing machine AG-X as the measuring device. For each, the 10% modulus was measured at -15°C. The distance between the chucks was 100 mm, and the test speed was 1000 mm/min.
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、試料（ダイシングフィルム基材）のＭＤ方向およびＴＤ方向のそれぞれについて、－１５℃にて、１０％モジュラスを測定した。チャック間距離は１００ｍｍ、試験速度は１０００ｍｍ／分とした。 (2) Low-temperature modulus strength The above-mentioned dicing film base material was cut into strips with a width of 10 mm and a length of 180 mm. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), the MD and TD directions of the sample (dicing film base material) were measured using Shimadzu desktop precision universal testing machine AG-X as the measuring device. For each, the 10% modulus was measured at -15°C. The distance between the chucks was 100 mm, and the test speed was 1000 mm/min.
上記試験により得られたＭＤ方向の１０％モジュラスおよびＴＤ方向の１０％モジュラスを平均し、以下の基準によりダイシングフィルム基材の低温モジュラス強度を評価した。
Ａ（良好） ：２４ＭＰａ以上
Ｂ（やや良好）：２０ＭＰａ以上２４ＭＰａ未満
Ｃ（不良） ：２０ＭＰａ未満 The 10% modulus in the MD direction and the 10% modulus in the TD direction obtained in the above test were averaged, and the low-temperature modulus strength of the dicing film base material was evaluated based on the following criteria.
A (good): 24 MPa or more B (slightly good): 20 MPa or more and less than 24 MPa C (bad): less than 20 MPa
Ａ（良好） ：２４ＭＰａ以上
Ｂ（やや良好）：２０ＭＰａ以上２４ＭＰａ未満
Ｃ（不良） ：２０ＭＰａ未満 The 10% modulus in the MD direction and the 10% modulus in the TD direction obtained in the above test were averaged, and the low-temperature modulus strength of the dicing film base material was evaluated based on the following criteria.
A (good): 24 MPa or more B (slightly good): 20 MPa or more and less than 24 MPa C (bad): less than 20 MPa
（３）常温伸び性
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、測定対象のＭＤ方向およびＴＤ方向のそれぞれについて、２３℃で２００％モジュラスを測定した。 (3) Room-temperature extensibility The dicing film base material was cut into strips of 10 mm width x 180 mm length. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), Shimadzu tabletop precision universal testing machine AG-X was used as the measuring device, and the measurement target was measured in both the MD and TD directions. The 200% modulus was measured at °C.
上記ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、測定対象のＭＤ方向およびＴＤ方向のそれぞれについて、２３℃で２００％モジュラスを測定した。 (3) Room-temperature extensibility The dicing film base material was cut into strips of 10 mm width x 180 mm length. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), Shimadzu tabletop precision universal testing machine AG-X was used as the measuring device, and the measurement target was measured in both the MD and TD directions. The 200% modulus was measured at °C.
得られた測定結果について、以下の基準でダイシングフィルム基材の常温伸び性を評価した。
Ａ（良好）：２３℃で２００％モジュラスを測定可能
Ｃ（不良）：測定中にダイシングフィルム基材が破断してしまい、２３℃で２００％モジュラスを測定不可 Regarding the obtained measurement results, the room temperature elongation of the dicing film base material was evaluated based on the following criteria.
A (good): 200% modulus can be measured at 23°C C (bad): The dicing film base material breaks during measurement, and 200% modulus cannot be measured at 23°C
Ａ（良好）：２３℃で２００％モジュラスを測定可能
Ｃ（不良）：測定中にダイシングフィルム基材が破断してしまい、２３℃で２００％モジュラスを測定不可 Regarding the obtained measurement results, the room temperature elongation of the dicing film base material was evaluated based on the following criteria.
A (good): 200% modulus can be measured at 23°C C (bad): The dicing film base material breaks during measurement, and 200% modulus cannot be measured at 23°C
（４）低温伸び性
ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、測定対象のＭＤ方向、ＴＤ方向のそれぞれについて、－１５℃で２００％モジュラスを測定した。 (4) Low-temperature elongation The dicing film base material was cut into strips with a width of 10 mm and a length of 180 mm. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), using the Shimadzu tabletop precision universal testing machine AG-X as the measuring device, each of the MD direction and TD direction of the measurement target was - 200% modulus was measured at 15°C.
ダイシングフィルム基材を１０ｍｍ幅×１８０ｍｍ長の短冊状に裁断した。ＪＩＳ Ｋ ７１２７：１９９９（ＩＳＯ ５２７－３：１９９５に相当）に準拠し、測定装置として島津卓上型精密万能試験機ＡＧ－Ｘを使用して、測定対象のＭＤ方向、ＴＤ方向のそれぞれについて、－１５℃で２００％モジュラスを測定した。 (4) Low-temperature elongation The dicing film base material was cut into strips with a width of 10 mm and a length of 180 mm. In accordance with JIS K 7127:1999 (equivalent to ISO 527-3:1995), using the Shimadzu tabletop precision universal testing machine AG-X as the measuring device, each of the MD direction and TD direction of the measurement target was - 200% modulus was measured at 15°C.
得られた測定結果について、以下の基準でダイシングフィルム基材の低温伸び性を評価した。
Ａ（良好）：－１５℃で２００％モジュラスを測定可能
Ｃ（不良）：測定中にダイシングフィルム基材が破断してしまい、－１５℃で２００％モジュラスを測定不可 Regarding the obtained measurement results, the low temperature elongation of the dicing film base material was evaluated based on the following criteria.
A (good): 200% modulus can be measured at -15°C C (bad): The dicing film base material broke during measurement, and 200% modulus could not be measured at -15°C
Ａ（良好）：－１５℃で２００％モジュラスを測定可能
Ｃ（不良）：測定中にダイシングフィルム基材が破断してしまい、－１５℃で２００％モジュラスを測定不可 Regarding the obtained measurement results, the low temperature elongation of the dicing film base material was evaluated based on the following criteria.
A (good): 200% modulus can be measured at -15°C C (bad): The dicing film base material broke during measurement, and 200% modulus could not be measured at -15°C
表１に示されるように、３元系アイオノマー（Ｂ）およびスチレン系エラストマー（Ｃ）を含まない比較例１では、常温モジュラス強度、常温伸び性および低温伸び性が低く、比較例２では、常温モジュラス強度および常温伸び性が低かった。
As shown in Table 1, Comparative Example 1, which does not contain the ternary ionomer (B) and the styrene elastomer (C), has low room temperature modulus strength, room temperature elongation, and low temperature elongation, and Modulus strength and room temperature elongation were low.
一方、２元系アイオノマー（Ａ）およびスチレン系エラストマー（Ｃ）を含まない比較例３では、低温伸び性が低かった。さらに、スチレン系エラストマー（Ｃ）を含まない比較例４では、低温伸び性が低かった。さらに、３元系のアイオノマー（Ｂ）を含まない比較例５では、低温伸び性が低かった。
On the other hand, in Comparative Example 3, which did not contain the binary ionomer (A) and the styrene elastomer (C), the low-temperature elongation properties were low. Furthermore, in Comparative Example 4, which did not contain the styrene elastomer (C), low-temperature elongation was low. Furthermore, in Comparative Example 5, which did not contain the ternary ionomer (B), low-temperature elongation was low.
これに対し、２元系アイオノマー（Ａ）と、３元系アイオノマー（Ｂ）と、スチレン系エラストマー（Ｃ）と、を含む実施例１～１１の樹脂組成物を用いたダイシングフィルム基材では、常温モジュラス強度、低温モジュラス強度、常温伸び性、および低温伸び性に優れていた（実施例１～１１）。２元系アイオノマー（Ａ）と、３元系アイオノマー（Ｂ）と、スチレン系エラストマー（Ｃ）と、を組み合わせることで、２元系アイオノマー（Ａ）と３元系アイオノマー（Ｂ）とスチレン系エラストマー（Ｃ）とが均一に混合され、常温または低温におけるモジュラス強度や常温伸び性を互いに補うだけではなく、低温伸び性が非常に良好になった。
In contrast, in the dicing film base materials using the resin compositions of Examples 1 to 11 containing a binary ionomer (A), a ternary ionomer (B), and a styrene elastomer (C), Excellent room temperature modulus strength, low temperature modulus strength, room temperature elongation, and low temperature elongation (Examples 1 to 11). By combining the binary ionomer (A), the ternary ionomer (B), and the styrene elastomer (C), the binary ionomer (A), the ternary ionomer (B), and the styrenic elastomer can be combined. (C) were uniformly mixed, and not only did they mutually compensate for the modulus strength and room temperature elongation at room temperature or low temperature, but also the low temperature elongation became very good.
以上の結果から、本発明のダイシングフィルム基材用樹脂組成物によれば、常温モジュラス強度、低温モジュラス強度、常温伸び性、および低温伸び性に優れたダイシングフィルム基材を実現できることが確認できた。
From the above results, it was confirmed that according to the resin composition for dicing film base material of the present invention, a dicing film base material having excellent room temperature modulus strength, low temperature modulus strength, room temperature elongation property, and low temperature elongation property can be realized. .
本出願は、２０２２年９月９日出願の特願２０２２－１４４１００号に基づく優先権を主張する。当該出願明細書に記載された内容は、すべて本願明細書に援用される。
This application claims priority based on Japanese Patent Application No. 2022-144100 filed on September 9, 2022. All contents described in the specification of the application are incorporated herein by reference.
本発明のダイシングフィルム基材用樹脂組成物によれば、常温および低温での伸び性に優れ、さらには常温および低温でのモジュラス強度にも優れるダイシングフィルム基材が実現される。したがって、半導体装置の製造分野で非常に有用である。
According to the resin composition for a dicing film base material of the present invention, a dicing film base material that has excellent elongation at room temperature and low temperature, and also excellent modulus strength at room temperature and low temperature is realized. Therefore, it is very useful in the field of manufacturing semiconductor devices.
Claims (14)
- エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）と、
エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）と、
スチレン系エラストマー（Ｃ）と、
を含むダイシングフィルム基材用樹脂組成物。 an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer;
an ionomer (B) of ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer;
Styrenic elastomer (C),
A resin composition for a dicing film base material comprising: - 前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）中の不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の全構成単位の量に対して、１質量％以上３０質量％以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 The amount of structural units derived from unsaturated carboxylic acid in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is the amount of all structural units of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer. 1% by mass or more and 30% by mass or less,
The resin composition for a dicing film base material according to claim 1. - 前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）中の、不飽和カルボン酸由来の構成単位の量が、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の全構成単位の量に対して、１質量％以上３０質量％以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 The amount of structural units derived from unsaturated carboxylic acid in the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic ester copolymer is 1% by mass or more and 30% by mass or less based on the amount of all structural units of the ionomer (B) of the polymer,
The resin composition for a dicing film base material according to claim 1. - 前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の中和度が、１０％以上９０％以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 The degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 10% or more and 90% or less,
The resin composition for a dicing film base material according to claim 1. - 前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の中和度が、１０％以上９０％以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 The degree of neutralization of the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 10% or more and 90% or less,
The resin composition for a dicing film base material according to claim 1. - 前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）および前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の合計質量を１とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）の質量が、０．１０以上０．９５以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 When the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 1, the ethylene/unsaturated carboxylic acid copolymer (B) is 1. The mass of the ionomer (A) of the unsaturated carboxylic acid copolymer is 0.10 or more and 0.95 or less,
The resin composition for a dicing film base material according to claim 1. - 前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量を１とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）および前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）の合計質量が、０．６０以上１．００未満である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 The total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer, and the styrene elastomer (C). 1, the total mass of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the ionomer (B) of the ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester copolymer is 0. 60 or more and less than 1.00,
The resin composition for a dicing film base material according to claim 1. - ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計質量の割合が、５０質量％以上１００質量％以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid/unsaturated The ratio of the total mass of the ionomer (B) of the saturated carboxylic acid ester copolymer and the styrene elastomer (C) is 50% by mass or more and 100% by mass or less,
The resin composition for a dicing film base material according to claim 1. - ダイシングフィルム基材用樹脂組成物に含まれる樹脂成分の全質量を１００質量％とした場合に、前記エチレン・不飽和カルボン酸共重合体のアイオノマー（Ａ）、前記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体のアイオノマー（Ｂ）、および前記スチレン系エラストマー（Ｃ）の合計含有率が、９０質量％を超えて１００質量％以下である、
請求項８に記載のダイシングフィルム基材用樹脂組成物。 When the total mass of the resin components contained in the resin composition for dicing film base material is 100% by mass, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, the ethylene/unsaturated carboxylic acid/unsaturated The total content of the ionomer (B) of the saturated carboxylic acid ester copolymer and the styrenic elastomer (C) is more than 90% by mass and 100% by mass or less,
The resin composition for a dicing film base material according to claim 8. - ＪＩＳ Ｋ ７２１０：１９９９に準拠して、１９０℃、荷重２１６０ｇにて測定されるメルトフローレートが、０．１ｇ／１０分以上３０ｇ／１０分以下である、
請求項１に記載のダイシングフィルム基材用樹脂組成物。 In accordance with JIS K 7210:1999, the melt flow rate measured at 190°C and a load of 2160 g is 0.1 g/10 minutes or more and 30 g/10 minutes or less,
The resin composition for a dicing film base material according to claim 1. - 請求項１～１０のいずれか一項に記載のダイシングフィルム基材用樹脂組成物を含む層を、少なくとも一層有する、
ダイシングフィルム基材。 having at least one layer containing the resin composition for dicing film base material according to any one of claims 1 to 10,
Dicing film base material. - 前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して２３℃で測定したＭＤ方向の３０％モジュラスおよびＴＤ方向の３０％モジュラスの平均値が、８ＭＰａ以上１７ＭＰａ以下である、
請求項１１に記載のダイシングフィルム基材。 The average value of the 30% modulus in the MD direction and the 30% modulus in the TD direction measured at 23°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is 8 MPa or more and 17 MPa or less. is,
The dicing film base material according to claim 11. - 前記ダイシングフィルム基材用樹脂組成物を含む層の、ＪＩＳ Ｋ ７１２７：１９９９に準拠して－１５℃で測定したＭＤ方向の１０％モジュラスおよびＴＤ方向の１０％モジュラスの平均値が、２０ＭＰａ以上である、
請求項１１に記載のダイシングフィルム基材。 The average value of the 10% modulus in the MD direction and the 10% modulus in the TD direction measured at -15°C in accordance with JIS K 7127:1999 of the layer containing the resin composition for dicing film base material is 20 MPa or more. be,
The dicing film base material according to claim 11. - 請求項１１に記載のダイシングフィルム基材と、
前記ダイシングフィルム基材の少なくとも一方の面に積層された粘着層と、を有する、
ダイシングフィルム。 The dicing film base material according to claim 11;
an adhesive layer laminated on at least one surface of the dicing film base material,
dicing film.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015109436A (en) * | 2013-10-23 | 2015-06-11 | リンテック株式会社 | Dicing sheet |
| JP2017098369A (en) * | 2015-11-20 | 2017-06-01 | 三井・デュポンポリケミカル株式会社 | Resin composition for dicing film base, dicing film base and dicing film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015109436A (en) * | 2013-10-23 | 2015-06-11 | リンテック株式会社 | Dicing sheet |
| JP2017098369A (en) * | 2015-11-20 | 2017-06-01 | 三井・デュポンポリケミカル株式会社 | Resin composition for dicing film base, dicing film base and dicing film |
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