WO2022201656A1 - 基材フィルムおよびワーク加工用シート - Google Patents
基材フィルムおよびワーク加工用シート Download PDFInfo
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- WO2022201656A1 WO2022201656A1 PCT/JP2021/045090 JP2021045090W WO2022201656A1 WO 2022201656 A1 WO2022201656 A1 WO 2022201656A1 JP 2021045090 W JP2021045090 W JP 2021045090W WO 2022201656 A1 WO2022201656 A1 WO 2022201656A1
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- antistatic agent
- base film
- polyester resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
- H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
- H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
- H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Definitions
- the present invention relates to a base film that can be suitably used as a base film for a work processing sheet used for processing a work such as a semiconductor wafer, and the work processing sheet.
- Semiconductor wafers made of silicon, gallium arsenide, etc. and various packages are manufactured in a large diameter state, cut into chips (diced), peeled off (picked up), and then transferred to the next process, the mounting process.
- the workpiece such as a semiconductor wafer is attached to an adhesive sheet having a base film and an adhesive layer (hereinafter sometimes referred to as a "workpiece processing sheet"), and then subjected to back grinding, dicing, cleaning, and polishing. Processing such as drying, expanding, picking up, and mounting is performed.
- dicing blade As one of the dicing methods described above, there is a method of cutting the workpiece with a rotating circular blade (dicing blade). In this method, it is common to partially cut the work processing sheet to which the work is attached together with the work so that the work is surely cut.
- shavings made of the material constituting the pressure-sensitive adhesive layer and the base film may be generated from the work processing sheet.
- shavings are usually generated in the vicinity of the line (kerf line) passed by the round blade in the chips obtained by cutting or in the work processing sheet.
- the cutting debris adhering to the chip will be decomposed by the heat of the sealing, and this thermal decomposition product will destroy the package or cause the resulting device to operate. It may cause defects. Since it is difficult to remove this cutting waste by cleaning, the production of cutting waste significantly reduces the yield of the dicing process. Therefore, when dicing is performed with a rotating round blade, it is required to prevent generation of chips.
- Patent Document 1 a base film using polyester resin as one of the materials is also known.
- the inventors of the present invention have found that by using a work processing sheet as a base film and using a base film made of a predetermined polyester resin as one of the materials, it is possible to effectively suppress the generation of the above-described shavings. .
- the inventors have found that such a base film made of a polyester resin tends to attract dust due to electrification. In particular, even when an antistatic agent is incorporated into the film for the purpose of preventing adhesion of such dust, it has been found that it tends to be difficult to obtain sufficient dust adhesion prevention properties.
- the present invention has been made in view of such a situation, and provides a substrate film that has excellent dust adhesion prevention properties while sufficiently suppressing the generation of cutting debris, and a film that satisfactorily exhibits such functions. It is an object of the present invention to provide a work processing sheet capable of
- the present invention provides a substrate film comprising a first resin layer containing a polyester resin, wherein the polyester resin has an alicyclic structure and a differential scanning calorimetry
- the heat of fusion measured at a temperature increase rate of 20 ° C./min is 2 J / g or more, and the surface resistivity on at least one side of the previous base film is 1 ⁇ 10 6 ⁇ / ⁇ or more, 1 ⁇ 10 15 ⁇ / ⁇
- a base film is provided (Invention 1).
- the base film according to the invention (invention 1) is made of a material containing a polyester resin, and the polyester resin has an alicyclic structure and exhibits the heat of fusion described above. Even when the work processing sheet including the base film is used for dicing using a rotating round blade, it is possible to satisfactorily suppress the generation of shavings. Moreover, since the surface resistivity of at least one side of the base film is within the above range, electrification is suppressed when the work processing sheet including the base film is used, and the adhesion of dust is suppressed satisfactorily. be able to.
- the first resin layer preferably contains an antistatic agent (invention 2).
- the content of the antistatic agent in the first resin layer is preferably 1% by mass or more and 50% by mass or less (invention 3).
- the antistatic agent is preferably an ion-conducting antistatic agent (invention 4).
- the antistatic agent is preferably a polymeric antistatic agent (invention 5).
- the antistatic agent is preferably at least one of an ether antistatic agent, an ester antistatic agent, a polyamide antistatic agent and an acrylic antistatic agent (invention 6). .
- the antistatic agent preferably has a melt flow rate of 1 g/10 min or more and 100 g/10 min or less at a temperature of 210°C and a load of 5.0 kg (invention 7).
- the antistatic agent preferably has a 5% weight loss temperature of 250°C or higher in an air atmosphere (invention 8).
- the antistatic agent preferably has a 5% weight loss temperature of 250°C or higher in a nitrogen atmosphere (Invention 9).
- the polyester resin preferably contains the dicarboxylic acid having the alicyclic structure as a monomer unit constituting the polyester resin (Invention 10).
- the polyester resin preferably contains the diol having the alicyclic structure as a monomer unit constituting the polyester resin (invention 11).
- the alicyclic structure preferably has 6 or more and 14 or less carbon atoms forming the ring (Invention 12).
- the polyester resin contains a dimer acid obtained by dimerizing an unsaturated fatty acid as a monomer unit constituting the polyester resin, and the unsaturated fatty acid has 10 or more carbon atoms. , 30 or less (Invention 13).
- the ratio of the dimer acid as a monomer unit constituting the polyester resin to the total dicarboxylic acid as a monomer unit constituting the polyester resin is 2 mol% or more and 25 mol% or less. It is preferable that there is (Invention 14).
- the thickness of the base film is preferably 20 ⁇ m or more and 600 ⁇ m or less (Invention 15).
- the present invention provides a work processing sheet comprising the base film (Inventions 1 to 15) and an adhesive layer laminated on one side of the base film (Invention 16).
- the work processing sheet is preferably a dicing sheet (invention 17).
- the base film of the present invention it is possible to manufacture a work processing sheet that has excellent dust adhesion prevention properties while sufficiently suppressing the generation of cutting waste.
- the work processing sheet according to the present invention has excellent dust adhesion prevention properties while sufficiently suppressing the generation of cutting chips.
- the base film according to this embodiment includes a first resin layer containing a polyester resin.
- the polyester resin has an alicyclic structure and has a heat of fusion of 2 J/g or more as measured by differential scanning calorimetry at a heating rate of 20° C./min.
- the base film according to the present embodiment is provided with the first resin layer containing the polyester resin described above, so that the work processing sheet configured using the base film uses a rotating round blade. When used for dicing a work, it is possible to satisfactorily suppress the generation of chips.
- the base film according to the present embodiment has a surface resistivity of 1 ⁇ 10 6 ⁇ / ⁇ or more and 1 ⁇ 10 15 ⁇ / ⁇ or less on at least one surface thereof. Since the base film according to the present embodiment has such a surface resistivity, the work processing sheet formed using the base film is difficult to be charged during storage and use, and is charged. It is possible to satisfactorily suppress the adhesion of dust to the work processing sheet caused by this.
- the surface resistivity is preferably 5.0 ⁇ 10 14 ⁇ / ⁇ or less, particularly 2.0 ⁇ 10 14 ⁇ / ⁇ or less. is preferred.
- the lower limit of the surface resistivity is not particularly limited, and may be, for example, 1 ⁇ 10 8 ⁇ / ⁇ or more, particularly 1 ⁇ 10 7 ⁇ / ⁇ or more.
- the details of the method for measuring the surface resistivity are as described in the column of test examples described later.
- the polyester resin is expected to be easily cut at the position of the ester bond when a dicing force is applied to the base material produced using the polyester resin. Furthermore, the polyester resin in the present embodiment has an alicyclic structure as described above and exhibits the heat of fusion, so that a part of the polymer chain is regularly folded (lamellar structure). become a thing. Therefore, when a dicing force is applied, the polyester resin is expected to be easily cut even at the position of the lamellar structure. As described above, the polyester resin in the present embodiment is more likely to be cut at a specific position when a dicing force is applied than the resin used in the conventional base film. .
- the mechanism by which shavings are generated from the base material of a general dicing sheet is that the base material is softened by frictional heat generated during dicing, and then the base material is cut by contact with a rotating round blade. This is probably because the cut portion of the base material is scraped off while being stretched by applying a pulling force. In particular, most of the cutting waste generated in this way has a filamentous form.
- the generation of shavings is suppressed as a result of effective cutting in the vicinity of the ester bond and the lamellar structure before being stretched as described above.
- the heat of fusion of the polyester resin measured at a temperature increase rate of 20 ° C./min by differential scanning calorimetry is preferably 5 J / g or more. In particular, it is preferably 10 J/g or more, more preferably 15 J/g or more.
- the upper limit of the heat of fusion is not particularly limited. or less, especially 30 J/g or less. The details of the method for measuring the heat of fusion described above are as described in the section of Examples described later.
- polyester resin is not particularly limited as long as it has an alicyclic structure and exhibits the heat of fusion described above.
- the alicyclic structure of the polyester resin preferably has 6 or more carbon atoms forming the ring.
- the number of carbon atoms is preferably 14 or less, particularly preferably 10 or less.
- the number of carbon atoms is preferably 6.
- the alicyclic structure may be a monocyclic structure consisting of one ring, a bicyclic structure consisting of two rings, or a structure consisting of three or more rings.
- the polyester resin preferably contains a dicarboxylic acid having an alicyclic structure as a monomer unit constituting the polyester resin.
- the polyester resin preferably contains a diol having an alicyclic structure as a monomer unit constituting the polyester resin.
- the polyester resin should contain both such dicarboxylic acid and diol. is preferred.
- the structure of the dicarboxylic acid described above is not particularly limited as long as it has an alicyclic structure and two carboxy groups.
- the dicarboxylic acid may have a structure in which two carboxy groups are bonded to an alicyclic structure, and a structure in which an alkyl group or the like is further inserted between such an alicyclic structure and the carboxy group.
- dicarboxylic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-deca Hydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, 2,7-decahydronaphthalenedicarboxylic acid and the like can be mentioned, and among these, 1,4-cyclohexanedicarboxylic acid is preferably used.
- These dicarboxylic acids may be derivatives such as alkyl esters.
- Such an alkyl ester derivative may be, for example, an alkyl ester having 1 or more and 10 or less carbon atoms. More specific examples include dimethyl ester and diethyl ester, with dimethyl ester being particularly preferred.
- the ratio of the dicarboxylic acid monomer to the total monomer units constituting the polyester resin is 20 mol% or more. , more preferably 25 mol % or more, particularly preferably 30 mol % or more, further preferably 35 mol % or more. Also, the ratio is preferably 60 mol % or less, more preferably 55 mol % or less, particularly preferably 50 mol % or less, further preferably 45 mol % or less. Within these ranges, the polyester resin tends to exhibit the heat of fusion described above, and as a result, the work processing sheet obtained using the base film according to the present embodiment exhibits a more excellent effect of suppressing cutting waste. be easily achievable.
- the polyester resin in the present embodiment contains a dicarboxylic acid having an alicyclic structure as a monomer unit constituting it
- the dicarboxylic acid having an alicyclic structure for the entire dicarboxylic acid having a ring structure constituting the polyester resin The proportion of acid is preferably 60% or more, more preferably 70% or more, particularly preferably 80% or more, further preferably 90% or more.
- the ratio is 60% or more, the work processing sheet obtained by using the base film according to the present embodiment can easily achieve an excellent effect of suppressing cutting waste.
- the upper limit of the ratio is not particularly limited, and may be 100% or less, for example.
- dicarboxylic acids having an alicyclic structure as well as dicarboxylic acids having an aromatic ring structure are included in the dicarboxylic acids having the ring structure.
- the structure of the diol described above is not particularly limited as long as it has an alicyclic structure and two hydroxy groups.
- the diol may have a structure in which two hydroxy groups are bonded to an alicyclic structure, and a structure in which an alkyl group is further inserted between the alicyclic structure and the hydroxy group.
- Preferred examples of such diols include 1,2-cyclohexanediol (especially 1,2-cyclohexanedimethanol), 1,3-cyclohexanediol (especially 1,3-cyclohexanedimethanol), 1,4-cyclohexanediol. (especially 1,4-cyclohexanedimethanol), 2,2-bis-(4-hydroxycyclohexyl)-propane, etc.
- 1,4-cyclohexanedimethanol is preferably used.
- the ratio of the diol monomer to the total monomer units constituting the polyester resin is 35 mol% or more. is preferably 40 mol % or more, and more preferably 45 mol % or more. Also, the ratio is preferably 65 mol % or less, particularly preferably 60 mol % or less, further preferably 55 mol % or less. Within these ranges, the polyester resin tends to exhibit the heat of fusion described above, and as a result, the work processing sheet obtained using the base film according to the present embodiment exhibits a more excellent effect of suppressing cutting waste. be easily achievable.
- the polyester resin in the present embodiment preferably contains a dimer acid obtained by dimerizing an unsaturated fatty acid as a monomer unit constituting the polyester resin from the viewpoint that the base material is likely to have desired flexibility.
- the number of carbon atoms in the unsaturated fatty acid is preferably 10 or more, particularly preferably 15 or more.
- the number of carbon atoms is preferably 30 or less, particularly preferably 25 or less.
- dimer acids include dicarboxylic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, and unsaturated fatty acids with 22 carbon atoms such as erucic acid.
- C44 dicarboxylic acid obtained by dimerization, etc. are mentioned.
- a small amount of trimer acid obtained by trimerizing the unsaturated fatty acid may also occur.
- the polyester resin in the present embodiment may contain such a trimer acid together with the dimer acid.
- the ratio of the dimer acid to the total dicarboxylic acid units constituting the polyester resin is 2 mol% or more. It is preferably 5 mol % or more, and more preferably 10 mol % or more. Moreover, the ratio is preferably 25 mol % or less, particularly preferably 23 mol % or less, further preferably 20 mol % or less. Within these ranges, the polyester resin tends to have the desired flexibility, and as a result, the work processing sheet obtained using the base film according to the present embodiment has excellent expandability and pick-up property. can also be achieved.
- the polyester resin in the present embodiment may contain monomers other than the above-described dicarboxylic acid, diol and dimer acid as monomer units constituting it.
- monomers include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; phthalic acid, terephthalic acid, isophthalic acid, 2,6-naphthalene.
- Dicarboxylic acids, aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid and 4,4'-diphenyldicarboxylic acid, and the like.
- a diol component other than the diol having an alicyclic structure may be contained.
- it may contain ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, decanediol; ethylene oxide adducts such as bisphenol A and bisphenol S; trimethylolpropane and the like.
- a monomer having an alicyclic structure (a dicarboxylic acid having an alicyclic structure and a diol having an aliphatic structure as described above) , is preferably contained in a larger amount than the monomer having an aromatic ring structure.
- the molar ratio of the monomer units having an aromatic ring structure to the monomer units having an alicyclic structure is preferably less than 1 and 0.5 or less.
- ⁇ 0.2 or less is more preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.05 or less, more preferably 0.03 or less, and 0 It is more preferably 0.01 or less, particularly preferably 0.005 or less, further preferably 0.001 or less, and most preferably 0.
- the method for producing the polyester resin in the present embodiment is not particularly limited, and the polyester resin can be obtained by polymerizing the monomer components described above using a known catalyst.
- the polyester resin accounts for preferably 50% or more, particularly preferably 60% or more, and more preferably 70% or more of all the components constituting the base material in the present embodiment.
- the ratio is 50% or more, the work processing sheet obtained by using the base film according to the present embodiment can easily achieve a more excellent effect of suppressing cutting waste.
- the upper limit of the ratio is not particularly limited, and may be 100% or less, for example.
- the first resin layer in the present embodiment preferably contains an antistatic agent from the viewpoint of easily achieving the surface resistivity described above.
- the antistatic agent is not limited as long as it can achieve the surface resistivity described above, and may be, for example, an ion conductive antistatic agent or an electronic conductive antistatic agent. However, it is preferable to use an ion-conducting antistatic agent from the viewpoint that the above-described effect of suppressing shavings can be easily maintained and damage to the dicing blade can be easily prevented.
- the antistatic agent may be of a low-molecular-weight type or a high-molecular-weight type, but from the viewpoint of facilitating suppression of bleeding out from the first resin layer, It is preferable to use a polymeric type (polymeric antistatic agent). In particular, as the antistatic agent in the present embodiment, it is preferable to use an ion-conducting and polymeric antistatic agent.
- the term "polymeric antistatic agent” refers to an antistatic agent having at least two or more repeating units.
- the polymer-type antistatic agent in the present embodiment preferably has a weight-average molecular weight of 300 or more, particularly preferably 1000 or more.
- the weight average molecular weight is preferably 100,000 or less, particularly preferably 75,000 or less, and further preferably 50,000 or less.
- the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
- polymeric antistatic agents include ether-based antistatic agents, ester-based antistatic agents, polyamide-based antistatic agents, and acrylic antistatic agents.
- a particularly preferred example of the antistatic agent in the present embodiment is a polyether ester amide antistatic agent.
- the polyetheresteramide-based antistatic agent is classified into any of an ether-based antistatic agent, an ester-based antistatic agent and a polyamide-based antistatic agent.
- Preferred examples of the polyether ester amide-based antistatic include salt of inorganic protonic acid of polyether ester amide.
- Examples of salts of the inorganic protonic acid include alkali metal salts, alkaline earth metal salts, zinc salts and ammonium salts.
- the polyether ester amide is not particularly limited as long as it is a polymer having amide units with amide bonds and ether units with ether bonds. These units may be randomly arranged in the polyether ester amide, or may be arranged in blocks. In particular, the amide units may be randomly arranged in the polyetheresteramide. Moreover, these units may be linked by an ester bond, an amide bond, or the like.
- Preferred polyetheresteramides include those in which polyamide blocks consisting of a plurality of polyamide units and polyether blocks consisting of a plurality of polyether units are alternately arranged.
- the amide units are, for example, dicarboxylic acids (eg, oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, etc.) and diamines (eg, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1 , 4-bis(aminomethyl)cyclohexane, methylenebis(4-aminocyclohexane), m-xylylenediamine, p-xylylenediamine, etc.) and condensation and polycondensation with lactams such as ⁇ -
- Ring-opening polymerization polycondensation of aminocarboxylic acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, or ring-opening products of the above lactams or aminocarboxylic acids and dicarboxylic acids They are obtained by condensation, ring-opening products of the above lactams, or polycondensation of aminocarboxylic acids, dicarboxylic acids and diamines.
- Such amide units include nylon 4, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 11, nylon 12, nylon 6/66, nylon 6/12, nylon 6/610, nylon 66/12, nylon 6/66/610 and the like, and nylon 11 and nylon 12 are particularly preferred.
- the molecular weight of the amide unit is preferably, for example, about 100-5000.
- ether unit examples include polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene/polyoxypropylene glycol, and mixtures thereof. These molecular weights are preferably, for example, about 400 to 6,000, more preferably about 600 to 5,000.
- a particularly preferred example of the antistatic agent in the present embodiment also includes an acrylic antistatic agent.
- the acrylic antistatic agent refers to an antistatic agent containing at least one of acrylic acid and its derivatives (acrylic acid ester, methacrylic acid, methacrylic acid ester, etc.) as a constituent component.
- Preferred examples of acrylic antistatic agents include ionomer resins obtained by intermolecularly cross-linking the molecules of a copolymer of ethylene and at least one of acrylic acid and its derivatives with metal ions. Examples of such metal ions include lithium, sodium, potassium, calcium and the like.
- the antistatic agent in the present embodiment preferably has a melt flow rate of 100 g/10 min or less at a temperature of 210° C. and a load of 5.0 kg, more preferably 95 g/10 min or less, particularly 90 g/10 min or less. It is preferably 80 g/10 min or less.
- the melt flow rate is preferably 1 g/10 min or more, particularly preferably 5 g/10 min or more, and most preferably 10 g/10 min or more. When the melt flow rate is within the above range, it becomes easier to adjust the difference from the melt flow rate of the polyester resin in the present embodiment.
- the antistatic agent is easily dispersed appropriately in the first resin layer, and a conductive path is formed, so that the anti-dust adhesion property is easily exhibited satisfactorily.
- the details of the method for measuring the melt flow rate are as described in Examples below.
- the antistatic agent in the present embodiment preferably has a 5% weight loss temperature of 250°C or higher, more preferably 270°C or higher, and more preferably 300°C or higher in an air atmosphere.
- the 5% weight loss temperature is 250° C. or higher, the antistatic agent is difficult to decompose even when heated during kneading or film formation of the material of the base film, and sufficient dust adhesion prevention is achieved. It becomes easy to perform.
- the upper limit of the 5% weight loss temperature is not particularly limited.
- the antistatic agent in the present embodiment preferably has a 5% weight loss temperature of 250° C. or higher in a nitrogen atmosphere, particularly preferably 270° C. or higher, and further preferably 300° C. or higher. .
- the 5% weight loss temperature is 250° C. or higher, the antistatic agent is difficult to decompose even when heated during kneading or film formation of the material of the base film, and sufficient dust adhesion prevention is achieved. It becomes easy to perform.
- the upper limit of the 5% weight loss temperature is not particularly limited.
- the content of the antistatic agent in the first resin layer is preferably 1% by mass or more, more preferably 3% by mass or more, particularly 5% by mass. It is preferably 10% by mass or more, and more preferably 10% by mass or more.
- the content of the antistatic agent in the first resin layer is preferably 50% by mass or less, particularly preferably 45% by mass or less, further preferably 40% by mass or less.
- the work processing sheet configured using the base film according to the present embodiment tends to exhibit good mechanical properties and has sufficient It becomes easy to exhibit the cutting waste suppression effect.
- the first resin layer in the present embodiment may contain components other than the polyester resin described above.
- the material may contain components used for base films of general work processing sheets.
- Such components include various additives such as flame retardants, plasticizers, lubricants, antioxidants, colorants, infrared absorbers, ultraviolet absorbers, and ion scavengers.
- additives such as flame retardants, plasticizers, lubricants, antioxidants, colorants, infrared absorbers, ultraviolet absorbers, and ion scavengers.
- the content of these additives is not particularly limited, it is preferably within a range in which the base film exhibits the desired functions.
- the layer structure of the base film in the present embodiment may be a single layer or a plurality of layers as long as the first resin layer made of the material containing the polyester resin described above is provided. may be From the viewpoint of reducing manufacturing costs, the base film in the present embodiment is preferably a single layer (only a polyester resin layer).
- a plurality of first resin layers may be laminated, or the first resin layer and other layers may be laminated. In this case, it is possible to achieve both the effect of suppressing shavings by the polyester resin layer and the desired effect of the other layers.
- the surface of the base film on which the pressure-sensitive adhesive layer is laminated may be subjected to surface treatment such as primer treatment, corona treatment, plasma treatment, etc. in order to increase the adhesion with the pressure-sensitive adhesive layer.
- the thickness of the base film in the present embodiment is preferably 20 ⁇ m or more, particularly preferably 40 ⁇ m or more, further preferably 60 ⁇ m or more. Also, the thickness of the base film is preferably 600 ⁇ m or less, particularly preferably 300 ⁇ m or less, further preferably 200 ⁇ m or less. When the thickness of the base film is 20 ⁇ m or more, the work processing sheet tends to have an appropriate strength, and the work fixed on the work processing sheet can be easily supported. As a result, it becomes possible to effectively suppress the occurrence of chipping and the like during dicing. Further, when the thickness of the base film is 600 ⁇ m or less, the base film has better workability.
- Method for producing base film is not particularly limited as long as the material containing the polyester resin described above is used, for example, a melt extrusion method such as a T-die method or a round die method; A calender method; a dry method, a solution method such as a wet method, and the like can be used. Among these, it is preferable to adopt the melt extrusion method or the calendering method from the viewpoint of efficiently producing the base material.
- the substrate material (the material containing the polyester resin described above) is kneaded, and the resulting kneaded product is directly converted into pellets, or once pellets are produced,
- a film may be formed using a known extruder.
- the components constituting each layer are individually kneaded, and the obtained kneaded product is used directly, or once pellets are produced, and then a known extruder is used. Then, a plurality of layers may be simultaneously extruded to form a film.
- the coating liquid containing the material containing the polyester resin described above is applied to one side of a predetermined layer formed in advance in the form of a film, and dried or cured. , may form a first resin layer. Thereby, a substrate film including a predetermined layer and a first resin layer can be obtained.
- the work processing sheet according to this embodiment includes the base film described above and an adhesive layer laminated on one side of the base film.
- Adhesive layer The adhesive constituting the adhesive layer should exhibit sufficient adhesive strength to the adherend (especially sufficient adhesive strength to the work for processing the work) is not particularly limited as long as it is possible.
- adhesives constituting the adhesive layer include acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, polyvinyl ether adhesives, and the like. Among these, it is preferable to use an acrylic pressure-sensitive adhesive from the viewpoint that it is easy to exhibit the desired adhesive strength.
- the adhesive that constitutes the adhesive layer in the present embodiment may be an adhesive that does not have active energy ray-curable properties, but an adhesive that has active energy ray-curable properties (hereinafter referred to as "active energy ray-curable adhesive It may be referred to as "agent".) is preferred. Since the pressure-sensitive adhesive layer is composed of an active energy ray-curable pressure-sensitive adhesive, the pressure-sensitive adhesive layer is cured by the irradiation of the active energy ray, and the adhesive force of the work processing sheet to the adherend can be easily reduced. can be done. In particular, by irradiating the active energy ray, it becomes possible to easily separate the work after processing from the work processing sheet.
- the active energy ray-curable adhesive constituting the adhesive layer may be composed mainly of an active energy ray-curable polymer, or may be an active energy ray-incurable polymer (active energy ray-curable ) and a monomer and/or oligomer having at least one active energy ray-curable group.
- the active energy ray-curable polymer is a (meth)acrylic acid ester polymer (hereinafter referred to as “active energy ray-curable may be referred to as "polymer”).
- the active energy ray-curable polymer is obtained by reacting an acrylic copolymer having functional group-containing monomer units with an unsaturated group-containing compound having a functional group that binds to the functional group. is preferred.
- (meth)acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
- the term "polymer” shall also include the concept of "copolymer”.
- the weight average molecular weight of the active energy ray-curable polymer is preferably 10,000 or more, particularly preferably 150,000 or more, further preferably 200,000 or more. Also, the weight average molecular weight is preferably 2,500,000 or less, particularly preferably 2,000,000 or more, and further preferably 1,500,000 or less.
- Mw weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
- the active energy ray-curable pressure-sensitive adhesive is mainly composed of a mixture of an active energy ray non-curable polymer component and a monomer and/or oligomer having at least one active energy ray-curable group
- the active energy ray-curable adhesive As the energy ray non-curable polymer component, for example, the above acrylic copolymer before reacting with the unsaturated group-containing compound can be used.
- the active energy ray-curable monomer and/or oligomer for example, an ester of polyhydric alcohol and (meth)acrylic acid can be used.
- the weight average molecular weight of the acrylic polymer as the active energy ray non-curable polymer component is preferably 10,000 or more, particularly preferably 150,000 or more, and further preferably 200,000 or more. Also, the weight average molecular weight is preferably 2,500,000 or less, particularly preferably 2,000,000 or more, and further preferably 1,500,000 or less.
- the active energy ray-curable adhesive when ultraviolet rays are used as the active energy ray for curing the active energy ray-curable adhesive, it is preferable to add a photopolymerization initiator to the adhesive.
- a photopolymerization initiator for curing the active energy ray-curable adhesive, it is preferable to add a photopolymerization initiator to the adhesive.
- an active energy ray non-curable polymer component or oligomer component, a cross-linking agent, or the like may be added to the adhesive.
- the thickness of the pressure-sensitive adhesive layer in this embodiment is preferably 1 ⁇ m or more, particularly preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more. Also, the thickness of the pressure-sensitive adhesive layer is preferably 50 ⁇ m or less, particularly preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less. When the thickness of the adhesive layer is 1 ⁇ m or more, the work processing sheet according to the present embodiment can easily exhibit desired adhesiveness. Further, when the thickness of the pressure-sensitive adhesive layer is 50 ⁇ m or less, the adherend can be easily separated from the cured pressure-sensitive adhesive layer.
- a release sheet In the work processing sheet according to the present embodiment, until the surface of the adhesive layer opposite to the base film (hereinafter sometimes referred to as "adhesive surface") is attached to the adherend.
- a release sheet may be laminated on the surface for the purpose of protecting the surface during the cleaning.
- the configuration of the release sheet is arbitrary, and examples thereof include plastic films that have undergone a release treatment using a release agent or the like.
- specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; and polyolefin films such as polypropylene and polyethylene.
- the release agent a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, or the like can be used.
- the thickness of the release sheet is not particularly limited, and may be, for example, 20 ⁇ m or more and 250 ⁇ m or less.
- an adhesive layer may be laminated on the surface of the adhesive layer opposite to the base film.
- the work processing sheet according to this embodiment can be used as a dicing/die bonding sheet.
- a work is attached to the surface of the adhesive layer opposite to the adhesive layer, and the adhesive layer is diced together with the work to obtain a chip laminated with the individualized adhesive layer. be able to.
- the chip can be easily fixed to a target on which the chip is mounted by means of the individualized adhesive layer.
- Examples of the material constituting the adhesive layer include those containing a thermoplastic resin and a low-molecular-weight thermosetting adhesive component, those containing a B-stage (semi-cured) thermosetting adhesive component, and the like. It is preferable to use
- a protective film forming layer may be laminated on the adhesive surface of the adhesive layer.
- the work processing sheet according to this embodiment can be used as a protective film-forming and dicing sheet.
- a work is attached to the surface of the protective film-forming layer opposite to the adhesive layer, and the protective film-forming layer is diced together with the work, so that the individualized protective film-forming layer is laminated. you can get the chips
- a protective film-forming layer is usually laminated on the side opposite to the side on which the circuit is formed. By curing the individualized protective film-forming layer at a predetermined timing, a protective film having sufficient durability can be formed on the chip.
- the protective film-forming layer is preferably made of an uncured curable adhesive.
- the method for manufacturing the work processing sheet according to the present embodiment is not particularly limited. For example, after forming a pressure-sensitive adhesive layer on a release sheet, it is preferable to obtain a work processing sheet by laminating one side of a base film on the side of the pressure-sensitive adhesive layer opposite to the release sheet.
- the formation of the adhesive layer described above can be performed by a known method. For example, a coating liquid containing an adhesive composition for forming an adhesive layer and optionally a solvent or dispersion medium is prepared. Then, the coating liquid is applied to the peelable surface of the release sheet (hereinafter sometimes referred to as “release surface”). Subsequently, by drying the obtained coating film, a pressure-sensitive adhesive layer can be formed.
- the application of the coating liquid described above can be performed by a known method, for example, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, or the like.
- the properties of the coating liquid are not particularly limited as long as the coating liquid can be applied, and may contain components for forming the pressure-sensitive adhesive layer as a solute or dispersoid in some cases. .
- the release sheet may be released as a process material, or may protect the pressure-sensitive adhesive layer until it is attached to an adherend.
- the drying conditions (temperature, time, etc.) described above may be changed, or the heat treatment may be separately provided. It is preferable to promote a cross-linking reaction between the polymer component in the film and the cross-linking agent to form a cross-linked structure with a desired existence density in the pressure-sensitive adhesive layer. Furthermore, in order to allow the cross-linking reaction described above to proceed sufficiently, after bonding the pressure-sensitive adhesive layer and the base film together, curing may be performed, for example, by allowing the adhesive layer to stand in an environment of 23° C. and a relative humidity of 50% for several days. good.
- the work processing sheet according to the present embodiment can be used for processing a work such as a semiconductor wafer.
- the work can be processed on the work processing sheet.
- the work processing sheet according to the present embodiment can be used as a work processing sheet such as a back grind sheet, a dicing sheet, an expand sheet, a pick-up sheet, or the like.
- the workpiece include semiconductor members such as semiconductor wafers and semiconductor packages, and glass members such as glass plates.
- the work processing sheet according to the present embodiment is configured using the base film according to the present embodiment, it achieves excellent dust adhesion prevention while achieving a good cutting waste suppression effect. be able to. Therefore, the work processing sheet according to this embodiment is particularly suitable for use as a dicing sheet.
- the work processing sheet according to the present embodiment includes the adhesive layer described above, the work processing sheet can be used as a dicing/die bonding sheet. Furthermore, when the work processing sheet according to the present embodiment includes the protective film forming layer described above, the work processing sheet can be used as a protective film forming and dicing sheet.
- the adhesive layer in the work processing sheet according to the present embodiment is composed of the active energy ray-curable adhesive described above, the following active energy ray should be applied during use. is also preferred. That is, when the processing of the work is completed on the work processing sheet and the work after processing is separated from the work processing sheet, the adhesive layer can be irradiated with an active energy ray before the separation. preferable. As a result, the adhesive layer is cured, the adhesion of the work processing sheet to the work after processing is favorably reduced, and the work after processing can be easily separated.
- Example 1 (1) Preparation of substrate film Into a reactor equipped with a stirrer, a distillation tube and a pressure reducing device, 12.90 kg of dimethyl 1,4-cyclohexanedicarboxylate (trans ratio 98%), 1,4-cyclohexanedicarboxylate 11.47 kg of methanol, 0.3 kg of ethylene glycol, and 0.11 kg of an ethylene glycol solution containing 10% Mn acetate tetrahydrate were charged, heated to 200° C. under nitrogen flow, and then raised to 230° C. over 1 hour. I warmed up.
- the polyester resin pellets thus obtained were dried at 85°C for 4 hours or longer. After that, 70 parts by mass of the dried pellets and a polyetheresteramide-based antistatic agent as an antistatic agent (manufactured by Sanyo Chemical Industries, Ltd., product name "Pelectron AS”, "Polyetheresteramide-based antistatic agent” in Table 1 30 parts by mass of "agent A”) were kneaded in a twin-screw kneader. The pellets thus obtained were put into a hopper of a single-screw extruder equipped with a T-die. Then, under conditions of a cylinder temperature of 220° C. and a die temperature of 220° C., the melt-kneaded pellets are extruded from a T-die and cooled with a cooling roll to form a sheet-like base film having a thickness of 80 ⁇ m. Obtained.
- a polyetheresteramide-based antistatic agent as an antistatic agent manufactured by Sany
- the polyester resin contains about 50 mol% of 1,4-cyclohexanedimethanol, about 40.5 mol% of dimethyl 1,4-cyclohexanedicarboxylate, and a dimer derived from erucic acid as monomers constituting the resin. It contained 9.5 mol % of acid. The ratio of the dimer acid to all dicarboxylic acid units constituting the polyester resin was 19.1 mol %. Furthermore, when the heat of fusion of the polyester resin was measured by the method described later, it was 20 J/g.
- melt flow rate of the polyether ester amide antistatic agent was measured by the method described later, it was 69 g/10 min.
- 5% weight loss temperature of the above polyetheresteramide antistatic agent was measured by the method described later and found to be 340°C under an air atmosphere and 358°C under a nitrogen atmosphere.
- Adhesive Composition 95 parts by mass of n-butyl acrylate and 5 parts by mass of acrylic acid were polymerized by a solution polymerization method to obtain a (meth)acrylate polymer.
- Mw weight average molecular weight
- the heat of fusion of the polyester resin described above is measured using a differential scanning calorimeter (DSC, manufactured by TA Instruments, product name "DSC Q2000") in accordance with JIS K 7121:2012. did. Specifically, first, the temperature is heated from room temperature to 250°C at a temperature increase rate of 20°C/min, held at 250°C for 10 minutes, cooled to -60°C at a temperature decrease rate of 20°C/min, and then cooled to -60°C for 10 minutes. held for a minute. Thereafter, the mixture was heated again to 250°C at a heating rate of 20°C/min to obtain a DSC curve and measure the melting point.
- DSC differential scanning calorimeter
- melt flow rate of the polyether ester amide antistatic agent described above was measured according to JIS K 7210-1:2014 under the following changed test conditions. ⁇ Test temperature: 230°C ⁇ Load: 5kg ⁇ Die: hole shape ⁇ 2.0mm, length 5.0mm ⁇ Cylinder diameter: 11.329mm
- the 5% weight loss temperature of the polyether ester amide-based antistatic agent described above uses a differential thermal/thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, product name "DTG-60") and is based on JIS K7120: 1987. I did. Specifically, the temperature was raised from 40° C. to 550° C. at a gas inflow rate of 100 ml/min and a temperature increase rate of 20° C./min using air or nitrogen as an inflow gas, and thermogravimetry was performed. From the obtained thermogravimetric curve, the temperature at which the mass decreases by 5% with respect to the mass at a temperature of 100° C. (5% weight loss temperature) was determined.
- DTG-60 differential thermal/thermogravimetric simultaneous measurement device
- the weight average molecular weight (Mw) mentioned above is the weight average molecular weight of standard polystyrene conversion measured on the following conditions using a gel permeation chromatography (GPC) (GPC measurement).
- GPC gel permeation chromatography
- ⁇ Measurement conditions> ⁇ Measuring device: HLC-8320 manufactured by Tosoh Corporation ⁇ GPC column (passed in the following order): TSK gel superH-H manufactured by Tosoh Corporation TSK gel super HM-H TSK gel super H2000 ⁇ Measurement solvent: tetrahydrofuran ⁇ Measurement temperature: 40°C
- Example 2 The workpiece was processed in the same manner as in Example 1, except that an acrylic antistatic agent (an ethylene-methacrylic acid copolymer ionomer, manufactured by Mitsui Dow Polychemicals, product name "Entira MK400”) was used as the antistatic agent. I got a sheet for an acrylic antistatic agent (an ethylene-methacrylic acid copolymer ionomer, manufactured by Mitsui Dow Polychemicals, product name "Entira MK400”) was used as the antistatic agent. I got a sheet for
- the melt flow rate of the acrylic antistatic agent was measured by the method described above and found to be 21 g/10 min. Furthermore, when the 5% weight loss temperature of the acrylic antistatic agent was measured by the method described above, it was 415°C under an air atmosphere and 429°C under a nitrogen atmosphere.
- Example 3 As an antistatic agent, a polyetheresteramide antistatic agent different from that used in Example 1 (manufactured by Sanko Kagaku Kogyo Co., Ltd., product name “Sanconol TBX-65”, “Polyetheresteramide antistatic agent” in Table 1) A work processing sheet was obtained in the same manner as in Example 1, except that the inhibitor B" was used.
- the melt flow rate of the polyether ester amide-based antistatic agent was measured by the method described above and found to be 69 g/10 min. Furthermore, when the 5% weight loss temperature of the polyether ester amide antistatic agent was measured by the method described above, it was 304° C. under an air atmosphere and 373° C. under a nitrogen atmosphere.
- Example 1 A work processing sheet was obtained in the same manner as in Example 1, except that no antistatic agent was used.
- Example 2 A work processing sheet was obtained in the same manner as in Example 1, except that a polyvinyl chloride resin sheet having a thickness of 80 ⁇ m was used as the base film.
- Test Example 1 Measurement of surface resistivity
- the surface resistivity of one side of the substrate films produced in Examples and Comparative Examples was measured. Specifically, a sample obtained by cutting the base film into a size of 100 mm ⁇ 100 mm was measured using a digital ultra-high resistance/micro current meter 5450 (manufactured by ADC Co., Ltd.) under the conditions of an applied voltage of 100 V and an applied time of 60 sec.
- the surface resistivity ( ⁇ / ⁇ ) was measured with Table 1 shows the results.
- the number of shavings generated on the kerf line (the cutting line generated by passing the dicing blade) while the chip formed by singulating the silicon wafer is stuck on the work processing sheet.
- a digital microscope manufactured by Keyence Corporation, product name "VHX-5000", magnification: 500 times.
- the kerf lines count the number of chips present on three lines near the center in the vertical direction and on three lines near the center in the horizontal direction among a plurality of kerf lines in the vertical direction and the horizontal direction. did. Table 1 shows the results of the counting.
- the base film of the present invention can be suitably used as a base film constituting a work processing sheet used for processing a work such as a semiconductor wafer.
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Abstract
Description
ことが好ましい(発明13)。
〔基材フィルム〕
本実施形態に係る基材フィルムは、ポリエステル樹脂を含有する第1の樹脂層を備える。そして、上記ポリエステル樹脂は、脂環構造を有するとともに、示差走査熱量測定により昇温速度20℃/minで測定された融解熱量が2J/g以上である。
(1)ポリエステル樹脂
上記ポリエステル樹脂の具体的な組成は、脂環構造を有し、且つ、ポリエステル樹脂が上述した融解熱量を示すという条件を満たす限り、特に限定されない。
本実施形態における第1の樹脂層は、前述した表面抵抗率を達成し易いという観点から、帯電防止剤を含むことが好ましい。当該帯電防止剤としては、前述した表面抵抗率を達成できる限り限定されず、例えば、イオン伝導型帯電防止剤であってもよく、または、電子伝導型帯電防止剤であってもよい。しかしながら、前述した切削屑抑制効果を維持しやすく、また、ダイシングブレードの破損も防ぎ易いという観点からは、イオン伝導型帯電防止剤を使用することが好ましい。
本実施形態における第1の樹脂層は、上述したポリエステル樹脂以外のその他の成分を含有してもよい。特に、当該材料には、一般的なワーク加工用シートの基材フィルムに用いられる成分を含有させてもよい。
本実施形態における基材フィルムの層構成としては、前述したポリエステル樹脂を含有する材料からなる第1の樹脂層を備える限り、単層であってもよく、複数層であってもよい。製造コストを低減できる観点からは、本実施形態における基材フィルムは、単層(ポリエステル樹脂層のみ)であることが好ましい。
本実施形態における基材フィルムの厚さは、20μm以上であることが好ましく、特に40μm以上であることが好ましく、さらには60μm以上であることが好ましい。また、基材フィルムの厚さは、600μm以下であることが好ましく、特に300μm以下であることが好ましく、さらには200μm以下であることが好ましい。基材フィルムの厚さが20μm以上であることで、ワーク加工用シートが適度な強度を有し易いものとなり、ワーク加工用シート上に固定されるワークを良好に支持し易いものとなる。その結果、ダイシングの際におけるチッピングの発生等を効果的に抑制することが可能となる。また、基材フィルムの厚さが600μm以下であることで、基材フィルムがより良好な加工性を有するものとなる。
本実施形態における基材フィルムの製造方法は、前述したポリエステル樹脂を含有する材料を用いる限り、特に限定されず、例えば、Tダイ法、丸ダイ法等の溶融押出法;カレンダー法;乾式法、湿式法等の溶液法などを使用することができる。これらの中でも、効率良く基材を製造する観点から、溶融押出法またはカレンダー法を採用することが好ましい。
本実施形態に係るワーク加工用シートは、前述した基材フィルムと、当該基材フィルムの片面側に積層された粘着剤層とを備える。
以下、本実施形態に係るワーク加工用シートを構成する部材のうち、前述した基材フィルム以外の構成について説明する。
上記粘着剤層を構成する粘着剤としては、被着体に対する十分な粘着力(特に、ワークの加工を行うために十分となるような対ワーク粘着力)を発揮することができる限り、特に限定されない。粘着剤層を構成する粘着剤の例としては、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ポリエステル系粘着剤、ポリビニルエーテル系粘着剤等が挙げられる。これらの中でも、所望の粘着力を発揮し易いという観点から、アクリル系粘着剤を使用することが好ましい。
本実施形態に係るワーク加工用シートでは、粘着剤層における基材フィルムとは反対側の面(以下、「粘着面」という場合がある。)を被着体に貼付するまでの間、当該面を保護する目的で、当該面に剥離シートが積層されていてもよい。
本実施形態に係るワーク加工用シートでは、粘着剤層における基材フィルムとは反対側の面に接着剤層が積層されていてもよい。この場合、本実施形態に係るワーク加工用シートは、ダイシング・ダイボンディングシートとして使用することができる。当該シートでは、接着剤層における粘着剤層とは反対側の面にワークを貼付し、当該ワークとともに接着剤層をダイシングすることで、個片化された接着剤層が積層されたチップを得ることができる。当該チップは、この個片化された接着剤層によって、当該チップが搭載される対象に対して容易に固定することが可能となる。上述した接着剤層を構成する材料としては、熱可塑性樹脂と低分子量の熱硬化性接着成分とを含有するものや、Bステージ(半硬化状)の熱硬化型接着成分を含有するもの等を用いることが好ましい。
本実施形態に係るワーク加工用シートの製造方法は特に限定されない。例えば、剥離シート上に粘着剤層を形成した後、当該粘着剤層における剥離シートとは反対側の面に基材フィルムの片面を積層することで、ワーク加工用シートを得ることが好ましい。
本実施形態に係るワーク加工用シートは、半導体ウエハ等のワークの加工のために使用することができる。この場合、本実施形態に係るワーク加工用シートの粘着面をワークに貼付した後、ワーク加工用シート上にてワークの加工を行うことができる。当該加工に応じて、本実施形態に係るワーク加工用シートは、バックグラインドシート、ダイシングシート、エキスパンドシート、ピックアップシート等のワーク加工用シートとして使用することができる。ここで、ワークの例としては、半導体ウエハ、半導体パッケージ等の半導体部材、ガラス板等のガラス部材が挙げられる。
(1)基材フィルムの作製
撹拌機、留出管および減圧装置を装備した反応器内に、1,4-シクロヘキサンジカルボン酸ジメチル(trans体比率98%)12.90kg、1,4-シクロヘキサンジメタノール11.47kg、エチレングリコール0.3kg、および10%酢酸Mn四水和物を含むエチレングリコール溶液0.11kgを仕込み、窒素フロー下で200℃まで加熱した後、230℃まで1時間かけて昇温した。そのまま2時間保持してエステル交換反応を行った後、エルカ酸由来ダイマー酸(炭素数44,クローダ社製,製品名「PRIPOL1004」)10.30kg、10%トリメチルホスフェートを含むエチレングリコール溶液0.11kgを系内に投入し、引き続き230℃で1時間エステル化反応を行った。続いて、重縮合触媒として二酸化ゲルマニウム300ppmを添加撹拌後、1時間で133Pa以下まで減圧し、この間に内温を230℃から270℃へと引き上げ、133Pa以下の高真空下で所定の粘度となるまで撹拌して重縮合反応を行った。得られたポリマーをストランド状に水中に押出してカットし、ペレット状にした。
アクリル酸n-ブチル95質量部と、アクリル酸5質量部とを、溶液重合法により重合させて、(メタ)アクリル酸エステル重合体を得た。このアクリル系重合体の重量平均分子量(Mw)を後述する方法により測定したところ、50万であった。
上記工程(2)で得られた粘着性組成物を、厚さ38μmのポリエチレンテレフタレートフィルムの片面がシリコーン系剥離剤により剥離処理された剥離シート(リンテック株式会社製,製品名「SP-PET381031」)の剥離処理面に塗布し、得られた塗膜を100℃で1分間乾燥させた。これにより、剥離シートにおける剥離面上に、厚さ10μmの粘着剤層が形成されてなる積層体を得た。
上記工程(1)で得られた基材フィルムの片面と、上記工程(3)で得られた積層体における粘着剤層側の面とを貼り合わせることで、ワーク加工用シートを得た。
前述したポリエステル樹脂の融解熱量は、JIS K 7121:2012に準じて、示差走査熱量計(DSC,ティー・エイ・インスツルメンツ社製,製品名「DSC Q2000」)を用いて測定した。具体的には、まず、昇温速度20℃/minで常温から250℃まで加熱し、250℃で10分間保持し、降温速度20℃/minで-60℃まで低下させ、-60℃で10分間保持した。その後、再び昇温速度20℃/minで250℃まで加熱してDSC曲線を得て、融点を測定した。
・試験温度:230℃
・荷重:5kg
・ダイ:穴形状φ2.0mm、長さ5.0mm
・シリンダー径:11.329mm
<測定条件>
・測定装置:東ソー株式会社製,HLC-8320
・GPCカラム(以下の順に通過):東ソー株式会社製
TSK gel superH-H
TSK gel superHM-H
TSK gel superH2000
・測定溶媒:テトラヒドロフラン
・測定温度:40℃
帯電防止剤として、アクリル系帯電防止剤(エチレン・メタクリル酸共重合体のアイオノマー,三井・ダウポリケミカル社製,製品名「エンティラMK400」)を使用した以外、実施例1と同様にしてワーク加工用シートを得た。
帯電防止剤として、実施例1で使用したものとは異なるポリエーテルエステルアミド系帯電防止剤(三光化学工業株式会社製,製品名「サンコノールTBX-65」,表1中「ポリエーテルエステルアミド系帯電防止剤B」と表記)を使用した以外、実施例1と同様にしてワーク加工用シートを得た。
帯電防止剤を使用しなかった以外、実施例1と同様にしてワーク加工用シートを得た。
厚さ80μmのポリ塩化ビニル樹脂シートを基材フィルムとして用いた以外は、実施例1と同様にしてワーク加工用シートを得た。
実施例および比較例で製造した基材フィルムについて、その片面の表面抵抗率を測定した。具体的には、基材フィルムを100mm×100mmのサイズに切り出してなるサンプルについて、デジタル超高抵抗/微小電流計5450(株式会社エーディーシー製)を用いて、印加電圧100V、印加時間60secの条件で表面抵抗率(Ω/□)を測定した。結果を表1に示す。
実施例および比較例で製造したワーク加工用シートから剥離シートを剥離し、露出した粘着剤層の露出面を、厚さ40μmのシリコンウエハの片面に貼付した後、ワーク加工用シートにおける上記露出面の周縁部(シリコンウエハとは重ならない位置)に、ダイシング用リングフレームを付着させた。次いで、ダイシングソー(株式会社ディスコ社製,製品名「DFD6362」)を用いて以下の条件にて、当該シリコンウエハのダイシングを行った。
・ワーク(被着体):シリコンウエハ
・ワークサイズ:直径6インチ,厚さ40μm
・ダイシングブレード:株式会社ディスコ社製,製品名「27HECC」,ダイヤモンドブレード
・ブレード回転数:50,000rpm
・ダイシングスピード:100mm/sec
・切り込み深さ:基材表面より、20μmの深さまで切り込み
・ダイシングサイズ:8mm×8mm
実施例および比較例で製造したワーク加工用シートをA4サイズに裁断することで、サンプルを得た。当該サンプルを、その基材側の面が上方となるように水平な台に載置した後、温度23℃、相対湿度50%の環境下で1時間静置した。その後、上記サンプルにおける基材側の面に付着した埃の量を目視により確認した。その結果、実施例に係るサンプルでは、比較例に係るサンプルに比べて、明確に埃の量が少なかった。そのため、実施例については、ごみ付着防止性を「良好」と判断し、比較例については「不良」と判断した。これらの結果を表1にも記載する。
Claims (17)
- ポリエステル樹脂を含有する第1の樹脂層を備える基材フィルムであって、
前記ポリエステル樹脂が、脂環構造を有するとともに、示差走査熱量測定により昇温速度20℃/minで測定された融解熱量が2J/g以上であり、
前基材フィルムの少なくとも片面における表面抵抗率が、1×106Ω/□以上、1×1015Ω/□以下である
ことを特徴とする基材フィルム。 - 前記第1の樹脂層は、帯電防止剤を含有することを特徴とする請求項1に記載の基材フィルム。
- 前記第1の樹脂層中における前記帯電防止剤の含有量は、1質量%以上、50質量%以下であることを特徴とする請求項2に記載の基材フィルム。
- 前記帯電防止剤は、イオン伝導型帯電防止剤であることを特徴とする請求項2または3に記載の基材フィルム。
- 前記帯電防止剤は、高分子型帯電防止剤であることを特徴とする請求項2~4のいずれか一項に記載の基材フィルム。
- 前記帯電防止剤は、エーテル系帯電防止剤、エステル系帯電防止剤、ポリアミド系帯電防止剤およびアクリル系帯電防止剤の少なくとも1種であることを特徴とする請求項5に記載の基材フィルム。
- 前記帯電防止剤は、温度210℃および荷重5.0kgにおけるメルトフローレートが1g/10min以上、100g/10min以下であることを特徴とする請求項2~6のいずれか一項に記載の基材フィルム。
- 前記帯電防止剤は、大気雰囲気下における5%重量減少温度が250℃以上であることを特徴とする請求項2~7のいずれか一項に記載の基材フィルム。
- 前記帯電防止剤は、窒素雰囲気下における5%重量減少温度が250℃以上であることを特徴とする請求項2~8のいずれか一項に記載の基材フィルム。
- 前記ポリエステル樹脂は、当該ポリエステル樹脂を構成するモノマー単位として、前記脂環構造を有するジカルボン酸を含むことを特徴とする請求項1~9のいずれか一項に記載の基材フィルム。
- 前記ポリエステル樹脂は、当該ポリエステル樹脂を構成するモノマー単位として、前記脂環構造を有するジオールを含むことを特徴とする請求項1~10のいずれか一項に記載の基材フィルム。
- 前記脂環構造は、環を構成する炭素数が6以上、14以下であることを特徴とする請求項1~11のいずれか一項に記載の基材フィルム。
- 前記ポリエステル樹脂は、当該ポリエステル樹脂を構成するモノマー単位として、不飽和脂肪酸を二量化してなるダイマー酸を含み、
前記不飽和脂肪酸の炭素数は、10以上、30以下である
ことを特徴とする請求項1~12のいずれか一項に記載の基材フィルム。 - 前記ポリエステル樹脂を構成するモノマー単位としての全ジカルボン酸に対する、前記ポリエステル樹脂を構成するモノマー単位としての前記ダイマー酸の割合は、2モル%以上、25モル%以下であることを特徴とする請求項13に記載の基材フィルム。
- 前記基材フィルムの厚さは、20μm以上、600μm以下であることを特徴とする請求項1~14のいずれか一項に記載の基材フィルム。
- 請求項1~15のいずれか一項に記載の基材フィルムと、
前記基材フィルムの片面側に積層された粘着剤層と
を備えることを特徴とするワーク加工用シート。 - 前記ワーク加工用シートは、ダイシングシートであることを特徴とする請求項16に記載のワーク加工用シート。
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