CN101831261A - Radiation-curable adhesive composition, adhesive film for dicing, method for producing cut sheet - Google Patents
Radiation-curable adhesive composition, adhesive film for dicing, method for producing cut sheet Download PDFInfo
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- CN101831261A CN101831261A CN201010148655A CN201010148655A CN101831261A CN 101831261 A CN101831261 A CN 101831261A CN 201010148655 A CN201010148655 A CN 201010148655A CN 201010148655 A CN201010148655 A CN 201010148655A CN 101831261 A CN101831261 A CN 101831261A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- 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
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- Manufacturing & Machinery (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
本发明提供一种切割用粘着膜，其具有在切割工序中具有高粘着力而可以抑制半导体元件等的切断片的脱离分散、同时在拾起工序中对具有活性面的被加工物也可得到优异的轻剥离性及低污染性的粘着剂层。切割用粘着膜的粘着剂层中使用含有(甲基)丙烯酸系聚合物的放射线固化性粘着剂组合物，该(甲基)丙烯酸系聚合物在分子内至少具有碳数2～8的直链或支链烷基、羟基、碳数14～18的直链烷基及放射线反应性碳-碳双键。
The present invention provides an adhesive film for dicing, which has high adhesive force in the dicing process, can suppress the detachment and dispersion of cut pieces such as semiconductor elements, and can also be processed on the workpiece having an active surface in the pick-up process. Adhesive layer with excellent light peeling property and low staining property. A radiation-curable adhesive composition containing a (meth)acrylic polymer having at least a straight chain having 2 to 8 carbon atoms in the molecule is used in an adhesive layer of an adhesive film for dicing. Or branched chain alkyl, hydroxyl, straight chain alkyl with 14-18 carbons and radiation reactive carbon-carbon double bond.
Description
Technical field
The present invention relates to the radiation-curable adhesion agent composition, use the manufacture method of its cutting with adhesive film and cut off machine.The suitable cutting adhesive film that uses when more specifically, the present invention relates to cut off machined object such as semiconductor wafer with active face and semiconductor packages.
Background technology
At present, use rotating knife such as semi-conductor associated material of semiconductor wafer and semiconductor packages cuts off and is separated into little semiconductor element and IC parts.For example, be after the semiconductor wafer of material is made with large diameter state with silicon, germanium, gallium-arsenic etc., carry out grinding back surface and handle (Back grind processing) until the thickness that reaches regulation, and then, implement the back side as required and handle (etch processes, polished finish etc.).Then, it is die element that semiconductor wafer is cut off separation (cutting), and is used for operation thereafter.In this manufacturing process, carry out that semiconductor wafer is pasted on cutting in advance and be pasted on the cutting action, washing procedure, expansion (Expand) operation that under the state of semiconductor wafer semiconductor wafer are cut into die element with installation (Mount) operation of adhesive film, at this adhesive film, pick up various operations such as operation.And, pick up in the operation above-mentioned, in the following ways: make cutting become stretching, extension state to a certain degree with adhesive film, the cutting of the semiconductor element bottom that needs are picked up is mentioned with point-like or wire with adhesive film, at the state of peeling off that promotes this semiconductor element and cutting with adhesive film, pick up by vacuum suck etc. from top and to obtain semiconductor element.
Above-mentioned cutting has the structure that is formed with the adhering agent layer that contains adhesion agent composition on base materials such as plastic film usually with adhesive film.When making semiconductor element, semiconductor element disperses from the adhesive film disengaging in the cutting action in order to suppress, even require cutting to have the high clinging power of the degree that the hydraulic pressure semiconductor element that is applied in rinse water when the cutting also do not peel off from adhesive film with adhesive film, when simultaneously, also requiring it to have peeling off in picking up operation adhering agent layer have the low clinging power of the degree that is unlikely to damage semiconductor wafer light separability, and on the semiconductor element that has cut off low contaminative such as residual paste not.
As the adhesion agent composition that satisfies aforesaid characteristic, also has the temperature active form adhesion agent composition that reduces by the heating clinging power, but when desiring to give such adhesion agent composition, have in picking up operation semiconductor element and be difficult to the tendency peeled off with adhesive film from cutting with high clinging power.Therefore, also use the cutting adhesive film that is formed with the adhering agent layer that is formed by adhesion agent composition on the base material of radioactive rays perviousness, described adhesion agent composition contains the radiation-curable tackiness agent with the reactive carbon-to-carbon double bond of radioactive rays.Owing to radiation-curable tackiness agent before being cured with radioactive rays has high clinging power, therefore, the disengaging that can suppress semiconductor element in the cutting action disperses with adhesive film in the cutting of this radiation-curable.In addition, because the radiation-curable tackiness agent solidifies and clinging power significantly reduces during to adhering agent layer irradiation radioactive rays, therefore, in picking up operation, semiconductor element easily can be peeled off with adhesive film from cutting.
In recent years, in semi-conductor manufacturing process, for the increase that prevents the productive temp time (tact time) and the breakage that causes by the filming (for example 100 μ m are following) of semiconductor wafer, the grinding back surface of being everlasting will cut with adhesive film at short notice and be pasted on semiconductor wafer after handling back or grinding back surface processing and back side processing end.Carry out after such milled processed overleaf or grinding back surface is handled and the back is handled at the back side, when at short notice the semiconductor wafer of film being pasted with adhesive film mutually with cutting, peel off after the clinging power that produces semiconductor wafer and adhering agent layer uprises, is cured with radioactive rays and become difficult and the such problem of the property picked up reduction.This be presumably because, at the treated side that the grinding back surface that has carried out semiconductor wafer is handled or handle at the back side, natural oxide film is not formed at whole of semiconductor wafer fully, the surface of semiconductor wafer becomes and has the not active face of the active atomic of the state of oxidation (for example Siliciumatom etc.), therefore, when adhesive film is used in this active face stickup cutting, the active atomic of the state of oxidation does not contact with the radiation-curable tackiness agent of adhering agent layer, and the bonding of chemical does not take place between the active atomic of the state of oxidation and the adhering agent layer.
Pick up the semiconductor wafer in the operation and cut the adhesive problem of using adhesive film at aforesaid with active face, for example, proposed a kind of radiation-curable tackiness agent in the patent documentation 1, also proposed a kind of cutting adhesive film simultaneously with the adhering agent layer that contains hydroxyl based compounds such as polyalkylene glycol.Utilize this cutting adhesive film, on having the semiconductor wafer of active face, paste and cut when using adhesive film, owing to there is the hydroxyl based compound of specified amount on the surface of adhering agent layer, therefore, can suppress or prevent the bonding of the chemical between active atomic and the radiation-curable tackiness agent, thus, can guarantee to pick up light separability in the operation.
Patent documentation 1: TOHKEMY 2008-60434 communique
Summary of the invention
But aforesaid hydroxyl based compound self does not have tackiness, and for number-average molecular weight is a low molecular compound below 3000, therefore, and the problem that exists semiconductor wafer and cutting in the cutting action to reduce with the tackiness of adhesive film.Particularly in cutting action, for the heat of friction of removing when cutting and prevent to cut off adhering to of bits sheet, supply with rinse water to being pasted with cutting with the semiconductor wafer of adhesive film, therefore, even require rinse water contact adhering agent layer adhering agent layer also can keep high clinging power, but owing to use aforesaid low-molecular-weight hydroxyl based compound, clinging power reduces such problem easily when therefore existing rinse water to contact with adhering agent layer.And then, in patent documentation 1, in order to ensure the light separability behind the radiation exposure, needing interpolation to become component with respect to the total solids in the adhering agent layer is the hydroxyl based compound of 2～12 quality %, therefore, exist the solidified nature of radiation-curable tackiness agent to reduce easily, the problem of residual such low molecular weight compositions on semiconductor element easily when picking up.
The present invention is the invention that solves above-mentioned problem, the objective of the invention is to, a kind of radiation-curable adhesion agent composition is provided and uses the cutting adhesive film of described radiation-curable adhesion agent composition, wherein, described radiation-curable adhesion agent composition clinging power height before being cured with radioactive rays, and have light separability after being cured with radioactive rays, described cutting disperses with the disengaging that adhesive film has the cut off machine that has high clinging power and can suppress semiconductor element etc. in cutting action, in picking up operation, also can obtain the adhering agent layer of excellent light separability and low contaminative simultaneously to machined object with active face.
The invention provides a kind of radiation-curable adhesion agent composition, described radiation-curable adhesion agent composition contains (methyl) acrylic acid polymer, wherein,
Described (methyl) acrylic acid polymer has straight or branched alkyl, the hydroxyl of carbon number 2～8, the straight chained alkyl and the reactive carbon-to-carbon double bond of radioactive rays of carbon number 14～18 at least at intramolecularly.
Above-mentioned (methyl) acrylic acid series polymeric compounds is preferably by obtaining base polymer (base polymer) and the radioactive ray reactive compounds reaction that contains the reactive carbon-to-carbon double bond of radioactive ray that with respect to described base polymer 100 mass parts is 5～25 mass parts, and it is that (methyl) acrylic monomer copolymerization of the straight chained alkyl that contains carbon number 14～18 of hydroxyl (methyl) acrylic monomer of (methyl) acrylic monomer, 5～20 quality % of the straight or branched alkyl that contains carbon number 2～8 of 30～80 quality % and 10～60 quality % obtains that described base polymer makes with respect to whole comonomer compositions. The content of (methyl) acrylic monomer that especially preferably contains the straight chained alkyl of carbon number 14～18 is (methyl) acrylic acid polymer of 10～15 quality % with respect to whole comonomer compositions.
The present invention also provides a kind of cutting adhesive film, and described cutting has base material and the adhering agent layer at least one face of described base material with adhesive film, wherein,
Described adhering agent layer contains the radiation-curable adhesion agent composition that comprises linking agent, Photoepolymerizationinitiater initiater and above-mentioned (methyl) acrylic acid polymer.
In addition, the present invention also provides a kind of manufacture method of cut off machine, wherein,
On a face of machined object, paste above-mentioned cutting adhesive film,
Cut-out is pasted with described cutting and is separated into cut off machine with the machined object of adhesive film,
To sticking on the adhering agent layer irradiation radioactive rays on the described cut off machine, the clinging power of described adhering agent layer is reduced,
Pick up described cut off machine from the cutting that described clinging power has reduced with adhesive film.Particularly machined object is that the manufacture method of above-mentioned cut off machine is effective when having the semiconductor wafer of active face.
According to the present invention, because adhering agent layer contains above-mentioned radiation-curable adhesion agent composition, therefore, can be provided in and to obtain high clinging power in the cutting action, simultaneously in picking up operation, the machined objects such as semiconductor wafer with active face also had the excellent light separability and the cutting adhesive film of low contaminative.Thus, the disengaging that can reduce cut off machine in the cutting action disperses, in picking up operation, can easily cut off machine be peeled off with adhesive film from cutting simultaneously, and then, can also reduce the pollution after peeling off.
Description of drawings
Fig. 1 is the sectional skeleton diagram of the cutting of expression embodiments of the present invention with an example of adhesive film.
Nomenclature
1 cutting adhesive film
2 base materials
3 adhering agent layers
4 barrier films
Embodiment
The radiation-curable adhesion agent composition of present embodiment contains straight or branched alkyl, hydroxyl, the straight chained alkyl of carbon number 14～18 and (methyl) acrylic acid polymer of the reactive carbon-to-carbon double bond of radioactive rays that has carbon number 2～8 at intramolecularly at least.Preferably side chain and/or the end at (methyl) acrylic acid polymer has these characteristic groups.Such side chain and/or terminal (methyl) acrylic acid polymer with above-mentioned characteristic group can be by behind the synthetic base polymers, base polymer and the radioactive rays reactive compounds reaction that contains the reactive carbon-to-carbon double bond of radioactive rays as the radioactive rays reactive ingredients are synthesized, and described base polymer is to make (methyl) acrylic monomer that comprises the straight or branched alkyl that contains carbon number 2～8 at least, hydroxyl (methyl) acrylic monomer and contain the comonomer composition copolymerization of (methyl) acrylic monomer of straight chained alkyl of carbon number 14～18 and the multipolymer that obtains.Need to prove that in this manual, (methyl) vinylformic acid is meant acrylic or methacrylic acid.
(methyl) acrylic monomer of the straight or branched alkyl that contains carbon number 2～8 of one of comonomer composition that uses during as synthetic base polymer specifically for example can be enumerated: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) ethyl acrylate etc.They can use separately, and also two or more kinds may be used.Wherein, be preferably selected from a kind in the group that constitutes by (methyl) Octyl acrylate of the straight or branched alkyl that contains carbon number 8, (methyl) Isooctyl acrylate monomer, (methyl) ethyl acrylate, more preferably (methyl) ethyl acrylate.
The content of (methyl) acrylic monomer of the straight or branched alkyl that contains carbon number 2～8 in the base polymer, preferably the comonomer composition total amount with respect to the formation base polymkeric substance is 30～80 quality %, more preferably 40～80 quality %.The content of (methyl) acrylic monomer of straight or branched alkyl that contains carbon number 2～8 is during less than 30 quality %, and the clinging power of (methyl) acrylic acid polymer trends towards reducing.On the other hand, the content of (methyl) acrylic monomer of straight or branched alkyl that contains carbon number 2～8 is during greater than 80 quality %, reduces as the content of hydroxyl (methyl) acrylic monomer of other comonomer composition.Therefore, needed hydroxyl value reduces when importing (methyl) acrylic acid polymer with radiation-curable compound reaction and with the reactive carbon-to-carbon double bond of radioactive rays, and solidified nature reduces.In addition, because the import volume of the straight chained alkyl of carbon number 14～18 also reduces therefore light separability variation.
In addition, base polymer contains hydroxyl (methyl) acrylic monomer as one of comonomer composition.By using hydroxyl (methyl) acrylic monomer, can make the hydroxyl of importing and the reaction of radioactive rays reactive compounds and obtain having (methyl) acrylic acid polymer of radioreaction carbon-to-carbon double bond at intramolecularly as one of comonomer composition.As such hydroxyl (methyl) acrylic monomer, specifically for example can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) vinylformic acid-own ester of 6-hydroxyl etc.They can use separately, and also two or more kinds may be used.
The content of the hydroxyl in the base polymer (methyl) acrylic monomer is 5～20 quality % with respect to the comonomer composition total amount of formation base polymkeric substance preferably, more preferably 5～10 quality %.The content of hydroxyl (methyl) acrylic monomer because the hydroxy number in the base polymer tails off, therefore, the import volume of the reactive carbon-to-carbon double bond of radioactive rays is increased, thereby solidified nature reduces after a little while.In addition, when increasing the import volume of the reactive carbon-to-carbon double bond of radioactive rays in order to make the solidified nature raising, use under the situation of linking agent in order to realize polymer to quantize, the hydroxyl that reacts with this linking agent tails off, the remained unreacted composition pollutes thereby paste takes place easily.On the other hand, the content of hydroxyl (methyl) acrylic monomer is during greater than 20 quality %, active atomic in the active face of semiconductor wafer etc. and hydroxyl bonding, promptly use radioactive rays to be cured and to reduce clinging power fully, its result, when light separability reduces, paste takes place on the cut off machine after peeling off easily pollute.
And then base polymer contains (methyl) acrylic monomer of the straight chained alkyl with carbon number 14～18 as one of comonomer composition.In order to obtain high clinging power, preferred (methyl) acrylic monomer of the short-chain alkyl that contains carbon number 2～8 that uses as the comonomer composition more, but in order to guarantee solidified nature as mentioned above, (methyl) acrylic acid polymer that uses in the adhering agent layer of cutting with adhesive film must have hydroxyl, therefore, the clinging power with active face after this hydroxyl can cause promptly using radioactive rays to be cured also uprises.Research according to inventor etc., find, (methyl) acrylic monomer of straight chained alkyl that use contains carbon number 14～18 is during as one of comonomer composition, even can obtain being formed on to guarantee sufficient clinging power before being cured with radioactive rays, use the machined object with active face also to have (methyl) acrylic acid polymer of the adhering agent layer of excellent light separability and low contaminative being cured the back with radioactive rays simultaneously.The intramolecularly that imports (methyl) acrylic acid polymer by the straight chained alkyl that this is had carbon number 14～18 obtains the reason of above-mentioned characteristic may not be clear, but be presumed as follows.At first, when making above-mentioned each (methyl) acrylic monomer copolymerization for synthetic base polymer, if be (methyl) acrylic monomer with straight chained alkyl of carbon number 14～18, then can not hinder the polyreaction of this (methyl) acrylic monomer and other comonomer compositions such as (methyl) acrylic monomer of straight or branched alkyl that contains carbon number 2～8 and hydroxyl (methyl) acrylic monomer largely, and contain (methyl) acrylic monomer of straight or branched alkyl of carbon number 2～8 and the polyreaction between hydroxyl (methyl) acrylic monomer, therefore, can suppress the adhesiveness such as reduction of clinging power are produced the growing amount of dysgenic low-molecular-weight monomer component and oligomer composition, obtain the high-molecular weight base polymer.Think that in addition if the straight chained alkyl of carbon number 14～18 is imported the intramolecularly of (methyl) acrylic acid polymer, then the hydrophobicity of (methyl) acrylic acid polymer improves, and also can suppress the clinging power reduction even tackiness agent contacts with rinse water.And then, when using linking agent,, can seriously not hinder the hydroxyl of (methyl) acrylic acid polymer and the reaction of linking agent if be the straight chained alkyl of carbon number 14～18 yet.Therefore, in cutting action, can obtain having the radiation-curable adhesion agent composition of high clinging power.On the other hand, the separability variation of the machined object such as semiconductor wafer with active face and (methyl) acrylic acid polymer is considered to that the bonding of the hydroxyl that had by (methyl) acrylic acid polymer and esteratic site isopolarity position and the active atomic on the surface that is exposed to active face causes.Therefore think, if (methyl) acrylic acid polymer is at intramolecular side chain or terminal straight chained alkyl with carbon number 14～18, then chain alkyl exists with state freely at intramolecularly, hydroxyl isopolarity position is sheltered by this alkyl, therefore, can suppress contacting of polar fraction and active atomic.Therefore, before being cured with radioactive rays, machined objects such as semiconductor wafer had high clinging power, in cutting action, even rinse water contacts with tackiness agent, the reduction of clinging power is also few, in picking up operation, by being cured with radioactive rays, the curing of (methyl) acrylic acid polymer is fully carried out, cut off machine and adhesive film such as stripping semiconductor element easily simultaneously, can reduce adhesion agent composition residual on cut off machine.Only use and contain carbon number less than (methyl) acrylic monomer of 14 alkyl during as the comonomer composition, may be owing to can not shelter hydroxyl isopolarity position fully, promptly use radioactive rays be cured the back clinging power reduction also insufficient, the property picked up reduction.On the other hand, carbon number tails off greater than the selection of the monomer self of (methyl) acrylic monomer of 18, and the synthetic change of high-molecular weight (methyl) acrylic acid polymer is difficult.(methyl) acrylic monomer as such straight chained alkyl that contains carbon number 14～18, preferred simple function (methyl) acrylic monomer specifically for example can be enumerated: (methyl) vinylformic acid tetradecyl ester ((methyl) vinylformic acid myristin), (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl etc.They can use separately, and also two or more kinds may be used.Wherein, more preferably (methyl) vinylformic acid stearyl.
The content of (methyl) acrylic monomer of the straight chained alkyl that contains carbon number 14～18 in the base polymer is 10～60 quality % with respect to the comonomer composition total amount of formation base polymkeric substance preferably, more preferably 10～50 quality %.The content of (methyl) acrylic monomer of straight chained alkyl that contains carbon number 14～18 is during less than 10 quality %, may be because sheltering of hydroxyl isopolarity position is insufficient, when adhesive film is used in machined objects such as the semiconductor wafer stickup cutting with active face, being cured the back clinging power with radioactive rays does not fully reduce, peeling off of cut off machine becomes difficult, the property picked up reduction.On the other hand, the content of (methyl) acrylic monomer of straight chained alkyl that contains carbon number 14～18 is during greater than 60 quality %, and the polyreaction when base polymer is synthetic can not be carried out smoothly, is difficult to obtain high-molecular weight (methyl) acrylic acid polymer, therefore, paste taking place easily pollutes.Thus, so far also do not find: the alkyl number and the structure thereof that are conceived to the comonomer composition of formation base polymkeric substance, use contains makes (methyl) acrylic monomer of comprising a large amount of straight chained alkyls with carbon number 14～18 base polymer as the comonomer composition, react the adhesion agent composition that obtains (methyl) acrylic acid polymer with the radioactive rays reactive compounds, the inhibition that contacts the clinging power reduction that causes of adhering agent layer before concrete research is cured with radioactive rays and rinse water, have the light separability after being cured of machined objects such as semiconductor wafer of active face and the example of low contaminative relatively with radioactive rays.
In the present embodiment, be purpose with cohesive force and thermotolerance etc., base polymer can contain other comonomer composition as required.As other such comonomer composition, specifically for example can enumerate: (methyl) glycidyl acrylate etc. contains the epoxy group(ing) monomer; (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan, iso-crotonic acid etc. contain carboxylic monomer; Maleic anhydride, itaconic anhydride etc. contain the anhydride group monomer; (methyl) acrylamide, N, acid amides such as N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide are monomer; (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid-N, N-dimethylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester etc. contains amino monomers; Cyano-containing monomers such as (methyl) vinyl cyanide; Ethylene series monomers such as ethene, propylene, isoprene, divinyl, iso-butylene; Styrenic monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; Vinyl ester such as vinyl acetate, propionate is a monomer; Vinyl ether such as methylvinylether, ethyl vinyl ether is a monomer; Halogen atom such as vinylchlorid, vinylidene chloride monomer; (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester etc. contain the alkoxyl group monomer; N-vinyl-2-Pyrrolidone, N-methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinyl piperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-Yi Xi Ji oxazole, N-vinyl morpholine, N-caprolactam, N-(methyl) acryloyl morpholine etc. have the monomer of nitrogen atom ring; (methyl) acrylate such as (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate etc.In addition, as the comonomer composition, be purpose with crosslinked grade, can also use multi-functional monomer as required.As so multi-functional monomer, specifically for example can enumerate: 1,6-hexylene glycol (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, glycerine two (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, carbamate (methyl) acrylate, Vinylstyrene, two (methyl) butyl acrylate, two (methyl) Ethyl acrylate etc.And then, as the comonomer composition, as required, can also use ethylene-vinyl acetate copolymer and vinyl acetate polymer etc.These other comonomer compositions can use separately, and also two or more kinds may be used.But when the content of these other comonomer compositions was too much, clinging power reduced easily, and light separability and the low easy variation of contaminative.
As the polymerization process that is used for synthetic base polymer, can enumerate present known solution polymerization process, emulsion polymerization method, mass polymerization, suspension polymerization etc., wherein, the solution polymerization process that evenly carries out of the polymerization of the comonomer composition of preferred present embodiment.Organic solvent when carrying out solution polymerization specifically for example can be enumerated: the organic solvent of ketone system, ester system, alcohol system, fragrant family.These organic solvents can use separately, and also two or more kinds may be used.Wherein, preferred toluene, vinyl acetic monomer, Virahol, phenmethyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone etc. are good solvent and the organic solvent with boiling point of 60～120 ℃ to base polymer usually.In addition,, can enumerate as polymerization starter: α, α '-azos such as Diisopropyl azodicarboxylate two (Azobis) are; Free radical generating agents such as organo-peroxide system such as benzoyl peroxide etc.During polymerization, as required, can also use catalyzer, stopper etc.
(methyl) acrylic acid polymer of present embodiment can be by making as above operation base polymer that obtains and the radioactive rays reactive compounds reaction that contains the reactive carbon-to-carbon double bond of radioactive rays, synthesizing at the reactive carbon-to-carbon double bond of intramolecularly importing radioactive rays.
As the radioactive rays reactive compounds, can use have the reactive carbon-to-carbon double bond of radioactive rays and can with the compound of the functional group of the hydroxyl reaction of base polymer.Specifically for example can enumerate: (methyl) vinylformic acid, TRANSCINNAMIC ACID, methylene-succinic acid, fumaric acid, phthalic acid etc. contain carboxylic monomer; (methyl) vinylformic acid isocyanato ethyl etc. contains isocyanate group monomer etc.These radioactive rays reactive compounds can use separately, and also two or more kinds may be used.Wherein, preferably with the reactive excellent isocyanate group monomer that contains of hydroxyl.In addition, base polymer contains epoxy group(ing) monomer, (methyl) Acrylic Acid Monomer, when containing anhydride group monomer etc. as the comonomer composition, can also use have can with hydroxyl monomers such as (methyl) 2-Hydroxy ethyl acrylate of the functional group that imports functional group reactionses such as intramolecular epoxy group(ing), carboxyl, anhydride group by these comonomer compositions, (methyl) Hydroxyethyl Acrylate; (methyl) glycidyl acrylate, (methyl) glycidyl acrylate etc. contain the epoxy group(ing) monomer; (methyl) acrylic-amino ethyl ester etc. contains amino monomers etc.
The content of radioactive rays reactive compounds is 5～25 mass parts with respect to base polymer 100 mass parts preferably, more preferably 6～23 mass parts.The content of radioactive rays reactive compounds is during less than 5 mass parts, and the import volume of the reactive carbon-to-carbon double bond of radioactive rays reduces, and solidified nature reduces.The content of the reactive cured article of radioactive rays is during greater than 25 quality %, and solidified nature is saturated, and the flowability of the tackiness agent after being cured with radioactive rays simultaneously reduces, and the gap between the cut off machine after the stretching is insufficient.Therefore, when picking up, be difficult to recognize the image of each cut off machine sometimes.In addition, the stability of (methyl) acrylic acid polymer reduces sometimes, makes to become difficult.
In addition, the content of radioactive rays reactive compounds preferably lacks than synthetic middle hydroxyl (methyl) acrylic monomer that uses of base polymer.If the content of radioactive rays reactive compounds lacks than the content of hydroxyl (methyl) acrylic monomer, when then using linking agent for polymer quantizes, can guarantee the hydroxyl with the reaction of this linking agent, thus the reduction of the clinging power when adhering agent layer contacts with rinse water before can further suppressing to solidify.
As the reaction of the base polymer and the radioactive rays reactive compounds that are used to synthesize (methyl) acrylic acid polymer, can be set forth under the reactive state of the radioactive rays of keeping carbon-to-carbon double bond and make them carry out the method for condensation reaction or addition reaction.In these reactions,, preferably use stopper in order to keep the radioactive rays reactivity of carbon-to-carbon double bond.As such stopper, quinones such as preferred hydroquinone monomethyl ether are stopper.The amount of stopper is not particularly limited, and is generally 0.01～0.1 mass parts with respect to the total amount of base polymer and radioactive rays reactive compounds.
As above the weight-average molecular weight of (methyl) acrylic acid polymer of obtaining of operation is preferably 300,000～2,000,000, and more preferably 400,000～1,500,000.Weight-average molecular weight was less than 300,000 o'clock, and cut off machine paste takes place easily pollutes.In addition, the cohesive force of (methyl) acrylic acid polymer reduces, and the position skew of machined object takes place during cutting easily.On the other hand, weight-average molecular weight is greater than 2,000,000 o'clock, when synthetic and on base material during the coating adhesion agent composition, and adhesion agent composition gelation sometimes.Need to prove that above-mentioned weight-average molecular weight is measured the polystyrene conversion weight-average molecular weight (solvent: tetrahydrofuran (THF)) that obtains for utilizing GPC (gel permeation chromatography).In addition, (methyl) acrylic acid polymer preferably has the second-order transition temperature more than-60 ℃.
For the polymer quantification of above-mentioned (methyl) acrylic acid polymer, the radiation-curable adhesion agent composition of present embodiment preferably further contains linking agent.Linking agent as such is not particularly limited, and can use known linking agent.Specifically for example can enumerate: polymeric polyisocyanate is that linking agent, epoxy are that linking agent, aziridine are that linking agent, melamine resin are that linking agent, urea resin are that linking agent, anhydride compound are that linking agent, polyamines are that linking agent, carbonyl bearing polymer are linking agent etc.These linking agents can use separately, and also two or more kinds may be used.The use level of linking agent is 0.01～5 mass parts with respect to (methyl) acrylic acid polymer 100 mass parts preferably.When the use level of linking agent was too much, according to the difference of the kind of (methyl) acrylic acid polymer, the clinging power when pasting cutting with adhesive film sometimes on machined object reduced, or uncrosslinked composition is attached to cut off machine and paste takes place and pollutes.
When the radiation-curable adhesion agent composition of present embodiment uses ultraviolet ray as radioactive rays, preferably further contain Photoepolymerizationinitiater initiater.As such Photoepolymerizationinitiater initiater, specifically for example can enumerate: st-yrax alkyl oxide series initiators such as benzoin methyl ether, Benzoin ethyl ether, st-yrax propyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, benzoylbenzoic acid, 3, benzophenone series initiators such as 3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone; Alpha-hydroxy cyclohexyl phenyl ketone, 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, methoxyacetophenone, 2,2 '-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy acetophenone, 2-methyl isophthalic acid-[4-(methyl sulfo-)-phenyl]-aromatic ketone series initiators such as 2-morpholino propane-1; Aromatic series ketal series initiators such as benzil dimethyl ketal; Thioxanthone, 2-clopenthixal ketone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-dodecyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2, thioxanthone series initiators such as 4-di-isopropyl thioxanthone; Benzil series initiators such as benzil; Bitter almond oil camphor series initiators such as bitter almond oil camphor; 2-methyl-α-ketal based compounds such as 2-hydroxypropiophenonepreparation; Aromatic sulfonyl based compounds such as 2-naphthalic sulfonic chloride; 1-benzophenone-1, photolytic activity oxime compounds such as 1-propanedione-2-(neighbour-ethoxy carbonyl) oxime; The camphorquinone based compound; Halogenation ketone based compound; The acylphosphine oxide based compound; Acyl phosphonate based compound etc.They can use separately, and also two or more kinds may be used.The use level of Photoepolymerizationinitiater initiater is 0.01～5 mass parts with respect to (methyl) acrylic acid polymer 100 mass parts preferably.
When the radiation-curable adhesion agent composition of present embodiment has above-mentioned (methyl) acrylic acid polymer, the purpose that rises to other characteristic, as required, can also further contain known additives such as adhesion imparting agent, protective agent, weighting agent, tinting material, fire retardant, static inhibitor, tenderizer, UV light absorber, antioxidant, softening agent, tensio-active agent etc.But it is the least possible preferably to have low molecular compounds (for example number-average molecular weight is below 3000) such as the radioactive rays reactive compounds of the reactive carbon-to-carbon double bond of radioactive rays and polyoxyethylene glycol, is more preferably less than 2 quality %, does not most preferably contain in fact.When the radiation-curable adhesion agent composition of present embodiment contains such low molecular compound, not only can become the reason of polluting machined object, and the clinging power in the cutting action reduces easily, the solidified nature of picking up in the operation reduces easily.
The cutting of present embodiment can be made by above-mentioned radiation-curable adhesion agent composition being utilized known method be coated at least one face of base material with adhesive film.In addition, when using barrier film described later (Separator), behind coating radiation-curable adhesion agent composition on the membranous face, can on adhering agent layer, paste base material.Need to prove, when using linking agent, contain the adhering agent layer of radiation-curable adhesion agent composition in formation after, can further heat.As base material, just can be not particularly limited use so long as have the base material that sees through the characteristic of radioactive rays (X ray, ultraviolet ray, electron rays etc.) to small part.As such base material, can enumerate plastics system, metal system, base material such as made of paper, wherein, preferred plastics system base material.As such plastics system base material, specifically can enumerate for example by polyolefin-based resins (new LDPE (film grade), the straight chain shaped polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, polymethylpentene etc.), ethylene-vinyl acetate copolymer, ionomer is a resin, ethene-its polymers of (methyl) vinylformic acid, ethene-(methyl) acrylate copolymer (random copolymers, alternating copolymer etc.), ethylene-butene copolymer, ethene-hexene copolymer, polyurethane series resin, polyester based resin (polyethylene terephthalate, PEN, polybutylene terephthalate, PBN etc.), polyimide is a resin, polyamide-based resin, polyetherketone is a resin, polyethers is a resin, polyethersulfone is a resin, polystyrene resin (polystyrene etc.), the polyvinyl chloride resin, polyvinylidene chloride is a resin, polyvinyl alcohol resin, polyvinyl acetate (PVA) is a resin, vinyl chloride-vinyl acetate copolymer, polycarbonate-based resin, fluorine resin, the silicone-based resin, the base material that the constituent materials such as crosslinked body of cellulose-based resin and these resins constitute.These constituent materials can use separately, and also two or more kinds may be used.Above-mentioned constituent material can also have functional group as required.In addition, can also be in constituent material grafting functional monomer and modified monomer.And then, for improve with adjacency the layer adaptation, known surface treatment method can also be implemented in the surface of plastics system base material.As such surface treatment, specifically for example can enumerate: Corona discharge Treatment, ozone exposure are handled, high-voltage electric shock exposes processing, the processing of ionization radioactive rays etc.In addition, can also implement to utilize the coating processing, Cement Composite Treated by Plasma, tarnish (Matt) processing, crosslinking Treatment etc. of silane coupling agent to base material.
Base material can have the form of individual layer, also can have stacked form.In addition, in base material, as required, can also contain for example known additives such as weighting agent, fire retardant, protective agent, static inhibitor, tenderizer, UV light absorber, antioxidant, softening agent, tensio-active agent.The thickness of base material is not particularly limited, preferred 10～300 μ m, more preferably 30～200 μ m.
The thickness of adhering agent layer is not particularly limited, preferred 3～50 μ m, more preferably 5～20 μ m.The thickness of adhering agent layer is 3 μ m when above, when cutting, semiconductor wafer can be remained on cutting reliably with on the adhesive film.In addition, in cutting action, machined object such as semiconductor wafer vibration sometimes.Therefore, when Oscillation Amplitude was big, cut off machines such as semiconductor element were easy to generate breach (tipping).But the thickness of adhering agent layer is 50 μ m when following, and the Oscillation Amplitude of the vibration that produces in the time of can suppressing to cut becomes excessive, thereby can reduce above-mentioned breach.
The semiconductor wafer (silicon mirror wafer) that use has an active face is during as machined object, to the adhering agent layer of this semiconductor wafer utilize radioactive rays to be cured before clinging power (peel angle: 180 °, draw speed: 300mm/sec, temperature: 23 ± 3 ℃) more than preferred 0.5 (N/10mm is wide), more preferably more than 1.0 (N/10mm is wide).With the clinging power of radioactive rays before being cured is 0.5 (N/10mm is wide) when above, can suppress fully or prevent that the disengaging of the semiconductor element in the cutting action from dispersing.In addition, to the adhering agent layer of semiconductor wafer (silicon mirror wafer) with active face utilize radioactive rays to be cured after clinging power (peel angle: 180 °, draw speed: 300mm/sec, temperature: 23 ± 3 ℃) below preferred 0.15 (N/10mm is wide), more preferably 0.02～0.15 (N/10mm is wide).When having the adhering agent layer of low like this clinging power after being cured with radioactive rays, the property picked up change is good, and can reduce paste residual (tackiness agent composition residual).
Fig. 1 is the sectional skeleton diagram of the cutting of expression present embodiment with an example of the formation of adhesive film.As shown in Figure 1, the cutting of present embodiment has the formation that is formed with adhering agent layer 3 on a face of base material 2 with adhesive film 1.In addition, as shown in Figure 1, on adhering agent layer 3, as required, barrier film 4 can also be set.As barrier film 4, be not particularly limited, can use known barrier film.As the constituent material of such barrier film 4, specifically for example can enumerate: stationery; Synthetic resins such as polyethylene, polypropylene, polyethylene terephthalate etc.In addition, on the surface of barrier film 4,, as required, can implement processing such as silicone-treated, chain alkyl processing, fluorine processing in order to improve the separability of adhering agent layer 3.The thickness of barrier film 4 is not particularly limited, and is generally 10～200 μ m.Adhering agent layer 3 can be 1 layer, also can be for more than 2 layers.Need to prove, in Fig. 1, only on a face of base material 2, adhering agent layer 3 is set, but also can on two faces of base material 2, adhering agent layer 3 be set.In addition, though also not shown, according to using form, can replace barrier film 4, on another face of base material 2, form other adhering agent layer, demoulding processing layer etc.As the adhesion agent composition that is used to form other adhering agent layer, can use specifically that for example to contain acrylic acid series tackiness agent, rubber be that tackiness agent, carbamate are that tackiness agent, silicone-based tackiness agent, polyester are that tackiness agent, polyamide-based tackiness agent, epoxy are that tackiness agent, vinyl alkyl ethers are that tackiness agent, fluorine are the adhesion agent composition of known tackiness agents such as tackiness agent.Need to prove, be formed at the adhesion agent composition on another face of above-mentioned base material, can also contain various additives, radiation-curable composition and whipping agent etc. as required.In addition, the demoulding treatment agent (stripper) as being used to form demoulding processing layer, specifically for example can use: silicone-based demoulding treatment agent, chain alkyl are that demoulding treatment agent, fluorine are known demoulding treatment agents such as demoulding treatment agent.Cutting can also have the form that is wound into the roller shape with adhesive film or be laminated with the shape of the sheet material of wide cut.In addition, can also have sheet or the zonal form that they cut-outs is processed into specified dimension.
When can making cut off machine at the cutting machined object with adhesive film, the cutting of present embodiment uses.Particularly can when having the machined object of active face and make cut off machine, cutting preferably use.As such machined object, specifically for example can enumerate: semiconductor wafer, semiconductor packages, glass, pottery etc.These machined objects are made of compounds such as silicon based compound, germanium based compound, gallium-arsenic compounds, handle (Back grind) etc. by grinding back surface, on the face that exposes, have the active silicon atom (Si) of a plurality of not states of oxidation, not active germanium atom (Ge), the active atomic of the state of oxidation not such as active gallium atom (Ga) of the state of oxidation not of the state of oxidation.Therefore, to cut when sticking on the machined object in order to cut such machined object with adhesive film with active atomic, the hydroxyl isopolarity position and the active atomic bonding that import in (methyl) acrylic acid polymer that comprises as main component in the adhering agent layer, after promptly using radioactive rays to be cured, also show high clinging power, be difficult to peel off cut off machine and cutting adhesive film.But, utilize the cutting adhesive film of present embodiment, even have stickup cutting adhesive film on the machined object of active face, with cut off machine when cutting is peeled off with adhesive film, irrelevant with the stickup time, also can the clinging power to active face fully be reduced, can cut off machine be peeled off.Therefore, utilize the cutting adhesive film of present embodiment, for example, handle the grinding back surface processing and back side processing of back or semiconductor wafer at the grinding back surface of semiconductor wafer after, use adhesive film even on the active face of exposing, paste cutting at short notice, also can be used for the cutting action of implementing thereafter effectively and pick up operation etc.
In the present embodiment, make the method for cut off machine as the cutting machined object, can preferably use the manufacture method that has following operation at least: on a face of machined object, paste the operation of cutting with adhesive film; Cut off and be separated into the cutting action of cut off machine with the machined object of adhesive film with being pasted with cutting; To being pasted on the adhering agent layer irradiation radioactive rays on the cut off machine, the clinging power of adhering agent layer is reduced, reduced from clinging power and cut the operation of picking up of picking up cut off machine with adhesive film.
Be to paste on the face of machined object cutting with in the operation of adhesive film, usually, machined object such as semiconductor wafer and cutting is overlapping with the form that a face of machined object contacts with adhering agent layer with adhesive film, by the known squeezing devices such as squeezing device that use crimping roller they are pushed, on machined object, paste the cutting adhesive film.In addition, also can be in the container that can pressurize (for example autoclave etc.), with machined object and cutting with adhesive film with overlapping with above-mentioned same form, by to pressurizeing in the container, on machined object, paste the cutting adhesive film.And then, can also in negative pressure chamber's (vacuum chamber), operate equally with above-mentioned situation of pasting by pressurization, on machined object, paste the cutting adhesive film.
Then, in cutting action, use cutting unit cutting such as blade to stick on cutting with the machined objects such as semiconductor wafer on the adhesive film, make the cut off machine of machined object.In such cutting action, usually, in order to remove heat of friction and to prevent to cut off adhering to of bits sheet, supply with rinse water to being pasted with cutting with the machined objects such as semiconductor wafer of adhesive film, with the blade of high speed rotating machined object is cut to the size of regulation simultaneously.Therefore, the clinging power of adhering agent layer reduces easily, but for the cutting adhesive film of present embodiment, even adhering agent layer contacts with rinse water, also can keep excellent clinging power, therefore, can reduce cut off machine and disperse with the disengaging of adhesive film from cutting.As cutting unit, be not particularly limited, can use present known cutting unit.Need to prove, as required, behind cutting action, can also carry out washing procedure, expansion operation etc.
In picking up operation, after with the adhering agent layer of adhesive film irradiation radioactive rays the clinging power of adhering agent layer being reduced, pick up cut off machine with adhesive film from cutting to cutting.As radioactive rays, for example can enumerate: X ray, electron rays, ultraviolet ray etc.Wherein, preferred ultraviolet ray.Various conditions such as exposure intensity during the irradiation radioactive rays and irradiation time are not particularly limited, and can suitably set.As picking up method, be not particularly limited, can adopt the known various methods of picking up at present.For example can enumerate: with each cut off machine with pin from cutting with adhesive film side jack-up, then with picking up method that device picks up the cut off machine of jack-up etc.The cutting of present embodiment can make clinging power fully reduce with adhesive film by the curing of radioactive rays, therefore, even use machined object with active face, pick up in the operation aforesaid, also cut off machine easily can be peeled off with adhesive film from cutting, simultaneously, can also reduce and peel off adhering to of the tackiness agent composition of back on the cut off machine.
Below, the present invention will be described in more detail by embodiment, but the present invention is not limited to these embodiment.Need to prove that in the following description, " part " is meant " mass parts ".
Embodiment
Synthesizing of＜(methyl) acrylic acid polymer 〉
As the comonomer composition, prepare to contain the straight chained alkyl of carbon number 2 ethyl propenoate (EA), contain the branched-chain alkyl of carbon number 8 ethyl acrylate (EHA), contain hydroxyl 2-Hydroxy ethyl acrylate (HEA), contain the straight chained alkyl of carbon number 14 vinylformic acid myristin (MA), contain carbon number 18 straight chained alkyl vinylformic acid stearyl (STA) and contain the dodecylacrylate (LA) of the straight chained alkyl of carbon number 12.These comonomer compositions are mixed with the proportioning shown in the table 1, carry out solution free radical polymerization, synthetic each base polymer.Need to prove that when polymerization, the reaction that utilizes GPC to carry out the comonomer composition is followed the trail of, and stops polymerization in the moment that the comonomer composition disappears.
Then, make 100 parts of this each base polymers and methacrylic acid-2-isocyano that contains the reactive carbon-to-carbon double bond of radioactive rays and ethyl ester (IEM) reaction, synthetic each (methyl) acrylic acid polymer with each proportioning shown in the table 1.Need to prove, when carrying out above-mentioned reaction, use 0.05 part of hydroquinone monomethyl ether (MEHQ) as stopper.(solvent: tetrahydrofuran (THF)) measuring the respectively result of the weight-average molecular weight of (methyl) acrylic acid polymer of synthetic, is 500,000～800,000 to utilize GPC.
＜cutting the making of adhesive film 〉
Each 100 parts of (methyl) acrylic acid polymer that as above operation is obtained, as polyisocyanate compounds (the Japanese polyurethane corporate system of linking agent, trade(brand)name: コ ロ ネ one ト L) 0.1 part and as 1-hydroxy-cyclohexyl phenyl ketone (the Ciba corporate system of Photoepolymerizationinitiater initiater, trade(brand)name: Irgacure 184) 0.5 part of mixing prepares each radiation-curable adhesion agent composition.
Then, be that the mode of 10 μ m is coated on polyethylene terephthalate system barrier film (thickness: 38 μ m), form adhering agent layer, heated 3 minutes with 100 ℃ then with as above each radiation-curable adhesion agent composition of obtaining of operation with thickness.On adhering agent layer paste polyolefine system film (thickness: 100 μ ms) that single face implemented Corona discharge Treatment thereafter.The sample that pastes was preserved 72 hours in 40 ℃ thermostatic bath, made each cutting adhesive film.
Adhesive film is used in each cutting of using as above operation to make, carries out following evaluation.The composition and the evaluation result of each (methyl) acrylic acid polymer together are shown in Table 1.
[evaluation]
(being cured preceding clinging power) with radioactive rays
With the cutting that cuts into the wide short strip shape of 25mm with adhesive film sticking under 23 ℃ the atmosphere on 5 inches silicon mirror wafers that just carry out after mirror ultrafinish is handled, it was left standstill under the room temperature atmosphere 30 minutes, make working sample.Measure the clinging power of this working sample, the clinging power before solidifying with following benchmark evaluation.The condition determination of clinging power is set at: peel angle: 180 °, peeling rate: 300mm/ minute, temperature: 23 ± 3 ℃.
Zero: the measured value of clinging power is more than the 1.0N/10mm
△: the measured value of clinging power is more than the 0.5N/10mm and less than 1.0N/10mm
*: the measured value of clinging power is less than 0.5N/10mm
(be cured with radioactive rays after clinging power)
Make with the mensuration that is cured preceding clinging power with radioactive rays in the identical working sample of working sample that uses.Use the base material side irradiation ultraviolet radiation (exposure intensity: 300mJ/cm of adhesive film from the cutting of this working sample
2), operate equally with the clinging power of radioactive rays before being cured with above-mentioned, measure postradiation clinging power, the clinging power after solidifying with following benchmark evaluation.
Zero: the measured value of clinging power is below the 0.15N/10mm
△: the measured value of clinging power surpasses 0.15N/10mm
(property picked up)
5 inches silicon mirror wafers of thickness 100 μ m are carried out pasting the cutting adhesive film immediately after mirror ultrafinish handles under 23 ℃ atmosphere on abrasive surface.Then, supply with rinse water, simultaneously wafer is cut entirely (Full Cut) and be the size of 3mm * 3mm to the wafer that is pasted with this adhesive film.
Then, from the base material side irradiation ultraviolet radiation (exposure intensity: 300mJ/cm of cutting with adhesive film
2), after expanding, semiconductor element is peeled off from adhesive film, pick up.When picking up arbitrarily 50 of semiconductor elements,, be zero with the average evaluation of successfully picking up whole semiconductor elements as the property picked up, with the average evaluation beyond it be *.
Table 1
As shown in Table 1, the cutting of embodiment has high clinging power with adhesive film before curing, and clinging power significantly reduces after curing.In addition, when adhesive film is used in the cutting of use embodiment, in picking up operation, has excellent light separability.When particularly relatively the comonomer composition total amount of the formation base polymkeric substance content of (methyl) acrylic monomer that contains the straight chained alkyl of carbon number 14 is 10～30 quality % and the content of (methyl) acrylic monomer that contains the straight chained alkyl of carbon number 18 when being 10～50 quality %, before being cured, can obtain high clinging power, after being cured, can obtain low clinging power simultaneously with radioactive rays with radioactive rays.
With respect to this, adhering agent layer only contain use do not contain chain alkyl (methyl) acrylic monomer as comonomer and synthetic (methyl) acrylic acid polymer or (methyl) acrylic monomer of using the alkyl that contains carbon number about 12 as the comonomer composition and the cutting of synthetic (methyl) acrylic acid polymer adhesive film, when use has the semiconductor wafer of active face, even after being cured, also show high clinging power with radioactive rays.Therefore, when using these cuttings to use adhesive film, the property picked up variation.
Claims (6)
1. radiation-curable adhesion agent composition, it contains (methyl) acrylic acid polymer, wherein,
Described (methyl) acrylic acid polymer has straight or branched alkyl, the hydroxyl of carbon number 2～8, the straight chained alkyl and the reactive carbon-to-carbon double bond of radioactive rays of carbon number 14～18 at least at intramolecularly.
2. radiation-curable adhesion agent composition as claimed in claim 1, wherein, described (methyl) acrylic acid polymer is by base polymer and the radioactive rays reactive compounds reaction that contains the reactive carbon-to-carbon double bond of radioactive rays that is 5～25 mass parts are obtained with respect to described base polymer 100 mass parts, described base polymer makes the copolymerization of comonomer composition and obtains, and it is (methyl) acrylic monomer of the straight or branched alkyl that contains carbon number 2～8 of 30～80 quality % that described comonomer composition contains at least with respect to whole comonomer compositions, (methyl) acrylic monomer of the straight chained alkyl that contains carbon number 14～18 of the hydroxyl of 5～20 quality % (methyl) acrylic monomer and 10～60 quality %.
3. radiation-curable adhesion agent composition as claimed in claim 2, wherein, with respect to described whole comonomer compositions, the content of (methyl) acrylic monomer of the described straight chained alkyl that contains carbon atom 14～18 is 10～50 quality %.
4. cutting adhesive film, it has base material and the adhering agent layer at least one face of described base material, wherein,
Described adhering agent layer contains the radiation-curable adhesion agent composition that comprises each described (methyl) acrylic acid polymer in linking agent, Photoepolymerizationinitiater initiater and the claim 1～3.
5. the manufacture method of a cut off machine, wherein,
On a face of machined object, paste the described cutting adhesive film of claim 4,
Cut-out is pasted with described cutting and is separated into cut off machine with the machined object of adhesive film,
To sticking on the adhering agent layer irradiation radioactive rays on the described cut off machine, the clinging power of described adhering agent layer is reduced,
Pick up described cut off machine from the cutting that described clinging power has reduced with adhesive film.
6. the manufacture method of cut off machine as claimed in claim 5, wherein, described machined object is the semiconductor wafer with active face.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009-048854 | 2009-03-03 | ||
| JP2009048854 | 2009-03-03 | ||
| JP2009208981A JP5656379B2 (en) | 2009-03-03 | 2009-09-10 | Dicing adhesive film and method for manufacturing semiconductor element |
| JP2009-208981 | 2009-09-10 |
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| CN101831261A true CN101831261A (en) | 2010-09-15 |
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| CN108884368A (en) * | 2016-03-17 | 2018-11-23 | 王子控股株式会社 | Adhesive composition and adhesive sheet |
| CN109005665A (en) * | 2016-03-30 | 2018-12-14 | 琳得科株式会社 | Semiconductor processing sheet |
| CN109082241A (en) * | 2017-06-13 | 2018-12-25 | 麦克赛尔控股株式会社 | The laminated body of double-sided adhesive tape and thin film component and bearing part |
| CN111164737A (en) * | 2017-12-07 | 2020-05-15 | 琳得科株式会社 | Sheet for processing workpiece and method for manufacturing processed workpiece |
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| KR101580544B1 (en) * | 2015-11-24 | 2015-12-28 | 정찬수 | UV curable dicing film |
| JP6350845B1 (en) * | 2018-01-29 | 2018-07-04 | サイデン化学株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and method for producing pressure-sensitive adhesive |
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| CN109005665A (en) * | 2016-03-30 | 2018-12-14 | 琳得科株式会社 | Semiconductor processing sheet |
| CN109005665B (en) * | 2016-03-30 | 2020-12-25 | 琳得科株式会社 | Semiconductor processing sheet |
| CN109082241A (en) * | 2017-06-13 | 2018-12-25 | 麦克赛尔控股株式会社 | The laminated body of double-sided adhesive tape and thin film component and bearing part |
| CN111164737A (en) * | 2017-12-07 | 2020-05-15 | 琳得科株式会社 | Sheet for processing workpiece and method for manufacturing processed workpiece |
| CN111164737B (en) * | 2017-12-07 | 2023-08-29 | 琳得科株式会社 | Workpiece processing sheet and method for manufacturing processed workpiece |
Also Published As
| Publication number | Publication date |
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| KR20100099658A (en) | 2010-09-13 |
| KR101353331B1 (en) | 2014-01-17 |
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