TW200835763A - Adhesive composition, adhesive film, and production method of the adhesive composition - Google Patents

Abstract

To provide an adhesive composition which has high heat resistance, adhesive strength in high temperature environments, and alkali resistance, and can easily be peeled after a high temperature process. This adhesive composition of the present invention containing a copolymer produced by copolymerizing a monomer composition comprising styrene, a cyclic structure-having (meth)acrylate, and a chain structure-having alkyl (meth)acrylate as a main component is characterized in that the monomer composition further contains an ethylenic double bond carboxylic acid. Heat resistance, adhesive strength under high temperature environments, alkali resistance, and peeling facility after high temperature process can thereby be improved.

Description

200835763 IX. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition, an adhesive film, and a method for producing the adhesive composition. In more detail, the present invention relates to semiconductor wafers and the like. In the step of performing processing such as grinding of a semiconductor product or an optical product, the sheet or the protective substrate is temporarily fixed to the adhesive composition for the semiconductor-made mouth, the film, and the method for producing the adhesive composition. [Prior Art] Recently, with the improvement of functions such as mobile phones and digital audio and video (digital AV) devices, and 1C cards, the semiconductor germanium chips (hereinafter referred to as wafers) mounted thereon have been reduced in size and thickness. The demand for higher density has also increased. For example, a single-package integrated circuit including a CSP (cMp size package) and a vtCP (multi-cliip package) is also required to be thinner. In a system-in-package (SiP) in which a plurality of semiconductor wafer systems can be mounted in a semiconductor package, the size, thickness, and density of the mounted wafers are reduced, and the performance of the electronic device is improved. And lightweight is a very important technology. In order to meet the demand for thinned products, it is necessary to make the wafer thinner than 15 〇/zm. Moreover, for CSP and MCP, the wafer must be thinned to less than 100 /z m; for ic cards, the wafer must be thinned to less than # m. Conventionally, in the case of SiP products, a method of wiring the electric 200835763 bump in each of the stacked layers and the circuit board by wire bonding technology is used. Further, in order to meet the demand for thinning and high density, it is no longer necessary to use a wire bonding technique, and it is necessary to use a through electrode technique in which a wafer having a beton electrode is laminated and an electrode is formed on the back surface of the wafer. The thin wafer is produced, for example, by slicing a high-purity singular crystal or the like into a wafer, and then assembling the integrated wiring 35 by forming a predetermined pattern on the surface of the wafer by etching or the like. The back surface of the obtained semiconductor wafer is ground by a grinding machine, and the semiconductor wafer which has been ground to a predetermined thickness is diced and wafer-formed. At this time, the predetermined thickness is about 1 〇〇: 〇 Further, when the through electrode is formed, it is ground to a thickness of about 5 〇 〇〇 〇〇 μ m. In the manufacture of a semiconductor wafer, when the semiconductor wafer itself is brittle and the film pattern is conveyed to the grinding step and the wafer cutting step, the external force is easily broken. Further, in the grinding step, in order to remove the generated polishing chips and remove the heat generated during the polishing, it is necessary to perform the grinding process while cleaning the back surface of the semiconductor wafer with purified water. At this time, it is necessary to prevent the above-mentioned purified water used for cleaning the circuit pattern surface from being contaminated. Therefore, in order to protect the line pattern surface of the semiconductor wafer and prevent breakage of the semiconductor wafer, the processing adhesive film is attached to the line pattern surface and then subjected to a grinding operation. Further, at the time of dicing, the protective sheet is attached to the back side of the semiconductor wafer, and the semiconductor wafer is diced in the state in which the semiconductor wafer is subsequently fixed, and the obtained wafer is picked up by the film from the side of the film substrate, and Fixed to the lower die (diepad). 200835763 For such processing adhesive films and protective sheets, it is known that polyethylene terephthalate (PET), polyethylene (pE), polypropylene (pp), and ethylene acetate. An adhesive material composed of an adhesive composition is provided on a base film such as (EVA) [for example, Patent Document 1 (Japanese Laid-Open Patent Publication No. 2003-173993, publication date: June 20, 2005) For the purpose of the publication: Document 2 (Japanese Laid-Open Patent Publication No. 2〇〇1_2792〇8, published on October 10, 2013), and Patent Document 3 (Japanese Open Publication No. 2003-292931, publication date: October 15, 2015)]]. Further, a protective substrate obtained by impregnating a sintered body of an aluminum nitride-boron nitride hole with a stepped oxygen oligomer is used instead of a protective film or a protective sheet for processing, and heat is applied to the protective substrate and the semiconductor wafer. The plastic film is used as a result of the following: [Patent Document 4 (Japanese Laid-Open Patent Publication No. 2002-203821, Publication Date: July 19, 2004)] The wafer is substantially hot-expanded _ the same aluminum oxide, aluminum nitride, boron nitride, tantalum carbide and other materials. In addition, the adhesive is used to protect the substrate and the semiconductor wafer, and the thermoplasticity such as polyacid (tetra) can be used. Resin; a method of applying a film having a thickness of 'the film' and spin coating an adhesive composition, and drying: forming a film of 20 #m or less [Patent Document 5 (Japanese Patent Laid-Open Publication) 2001-77304, the publication date: March 23, 2013)]: With the multilayering of the wiring of the semiconductor element, the following process is carried out: the semiconductor composition of the (4) substrate is attached to the (4) substrate Round surface, regrind On the back side of the conductor wafer, the polished surface is mirror-shaped, and a line is formed on the back side of the mirror. In this case, until the formation of the line on the side of the month of 200835763, the protective substrate continues to be followed by the document 6 (Japanese public) The patent gazette is on the +conductor wafer [(Special date: Showa 61 7^5, Kaizhao 61 Gu 5, published [invention]] However, the previous processing + into the through-electrode must be ... /Special film, etc., when used for the shape of the shoulder cup with the warm temperature process is Gu Gu Ru Lian _, has the so-called high temperature environment and then strong: two 'process = the gas generated in the step, resulting in X deficiency, south In the real work environment, when the time is left, the residue remains the same as the above (4) The human g Z is flat, which constitutes the protective tape and is not resistant to the high temperature of the c, and the gas is generated by the agent layer of the layer. Therefore, it is not good. After heating, the above-mentioned 溥-type semiconductor wafer must be peeled off from the 5 蒦 substrate after being ground and cut. However, the adhesive composition of the adhesive layer of the above patent and the protective tape is a ring. Oxygen == into, at high temperature, the ring _ fat will deteriorate,曰 = 曰 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The method for processing a semiconductor substrate used in a semiconductor wafer, and the method for processing a semiconductor substrate described in Patent Document 6, the adhesive used for vacuum-deposited metal film $wafer wafer in 200835763. Since the mirroring process and formation of the etching liquid are performed, heat resistance and releasability are required for the protective substrate and the semi-composite. However, the composition of the adhesive composition is not disclosed. Further, according to the inventor's difficulty, in the semiconductor Processing of wafers and wafers H'Adhesives using propylene-based resin materials have good resistance

Twenty-two factors are better. However, even the use of the binder of these acrylic wax materials has the following problems: (1) When the adhesive layer and the protective substrate are hot, they are absorbed by the adhesive layer. The moisture turns into a gas, causing the bubble to peel off at the interface, so the strength is lowered in the high temperature environment. Dragons, the generation of these gases not only reduces the strength of the subsequent high-temperature environment - but also the conditions of the king process, etc. under vacuum conditions, will also cause troubles in the generation and maintenance of the vacuum environment. s (1) In the case where there is a step of contacting the semiconductor wafer with the secret polishing liquid and the aging liquid, the organic liquid causes the contact surface of the adhesive composition to deteriorate due to peeling, dissolution, dispersion, and the like. (3) When heated to about 200 Å, deterioration of the composition of the adhesive due to low heat resistance and formation of a substance insoluble in the stripping liquid may cause peeling failure. The present invention has the above problems, and therefore its object is to provide an adhesive composition which is in a high temperature environment, particularly 14 〇c>c to fine. C, with high adhesion strength, high heat resistance and durability, and even after high temperature and /200835763 or high-true processing processes (hereinafter, _ "high-temperature process") 'from semiconductor wafers and wafers The stripping is still easy. A first aspect of the present invention is an adhesive composition comprising a monomer composition comprising styrene, a (meth) acrylate having a % structure, and a (meth) acrylate having a chain structure. The copolymerized polymer is used as a main component, and the adhesive composition is characterized in that the monomer composition further contains a carboxylic acid having a bismuth double bond. In the second aspect of the present invention, the amount of the carboxylic acid is 1 to 10 when the total amount of the above-mentioned stupid ethylene, the above (meth) acrylate, and the above (meth)acrylic acid is used as a part by weight. An adhesive composition characterized by a mass of 岌, 里切". The third aspect of the sun and the moon is "the above carboxylic acid is of the following formula (Working R -^COOH) m · · ·... (R1 represents the carbon number of the (meth)propionyl group or the ethylene group. The organic group of 2 to 20, which may also contain an oxygen atom; m represents a carboxylic acid represented by an integer of ^. The fourth aspect of the present invention is "the above carboxylic acid rabbit 4 rose" Is (meth)acrylic acid or the following general formula (2): 200835763 (R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 represents a divalent alkyl group having a carbon number of 1 to 5 or a carbonaceous carbon having a cyclic structure. An adhesive composition characterized by a divalent organic group of 4 to 20, which may also contain a carboxylic acid represented by an oxygen atom. The fifth aspect of the present invention is a film which is characterized by being on a film. There is provided an adhesive layer containing any of the above-described adhesive compositions. The sixth aspect of the present invention is a method for producing an adhesive composition, which is manufactured to contain (meth)acrylic acid having a stupid structure and having a cyclic structure. : a copolymer of a (meth)acrylic acid alkyl ester and a carboxylic acid mixed monomer composition composed of a chain structure The composition is a main component of the adhesive agent group; the manufacturing method is characterized in that the copolymerization reaction of the styrene, the (meth) propylene-I ester and the alkyl (meth) acrylate is terminated before the polymerization reaction is terminated. The seventh aspect of the present invention is to "start the copolymerization reaction after mixing the above carboxylic acid, the above-mentioned stupid ethylene, the above (meth)acrylic acid, and the above (meth)acrylic acid vinegar; The present invention is further described in the following description. The advantages of the present invention will be apparent from the following description with reference to the accompanying drawings. MODE FOR CARRYING OUT THE INVENTION A description of an embodiment of the present invention is as follows. In the present embodiment, (meth)acrylic acid comprising styrene, a (meth)acrylic acid having a cyclic structure, and a chain structure is formed. The polymer obtained by copolymerizing the monomer composition of the sinter is used as the main component of the group 11 200835763. The so-called "in the above single =::" is used. Further, the compound contains styrene. Paragraph technology In the case of the two states, the above-mentioned technical means are added. For example, the object is not limited to the following embodiments, and the WI can be used to read the * means. Then, the strength == under (especially the composition of the adhesive with good properties of w to (b) and the peeling after high-temperature process are easy;) C: the monomer composition of the mat is copolymerized:: substance = and composition of the agent The material has a certain degree of heat resistance and ease of peeling. The alkalinity, high temperature process is slow: by further adding the following olefinic double bond polymer:; = diethylene macromonomer , X, due to the above degree, heat resistance, etc. The failure of "1" can be used in the high temperature environment. The "principal component" in this specification refers to the content of the above-mentioned adhesive group 12 200835763 Any component with more ingredients. In the case of the third embodiment, the amount of the main component of the above-mentioned adhesive composition is not limited, but when the composition of the above-mentioned adhesive composition is the maximum mass, the content of the main component is 5 (the mass of the mass material is preferably 100 or less, more preferably 70 parts by mass or more) 00 parts by mass or more is 50 parts by mass or more. The next high, then the strength and the testability, the high heat,

Easy effect. Also, good peeling (styrene) is contained. The adhesive agent according to this embodiment contains styrene. In the above-mentioned early composition, the ethylene is not deteriorated even at a high temperature of 200 ° C or higher, so that the heat resistance of the above-mentioned adhesive composition can be improved, and the amount of the above-mentioned styrene can be improved. The copolymerization reaction contained in the above monomer composition is not limited. However, when the total amount of the styrene containing the above styrene, the above-mentioned f tiangan, the samarium sulfonate, and the above (meth) propylene daily precursor composition is regarded as the mass fraction, The above phenethylphene 50 parts is preferably used, and more preferably 20 to 40 parts by mass. If it is [〇皙], if it is 50 parts by mass or less or more, the heat resistance can be further improved, and the crack resistance can be suppressed by one knife. (F-type (meth) acrylate having a cyclic structure) The adhesive composition of the present invention comprises a (meth) acrylate having a fluorene structure of 13 200835763 in the above monomer composition. Thereby, the above-mentioned adhesive composition _ heat can be improved. In addition, the amount of the agent (4) acid required and the amount of the (meth) acrylate to be mixed with the above-mentioned (meth) acrylate are contained in the above-mentioned The other compound is subjected to a copolymerization reaction to make the total amount of the monomer composition including the above-mentioned styrene, the above-mentioned (meth)propene, and the above-mentioned oxime-burning as the mass of the base. 40 质量 质量 Τ Τ Τ 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 . The carboxyl group in the hydrogen acrylate '(meth)acrylic acid, which is available below the mass part, is a structure in which the organic group having a cyclic group or the like is substituted. The organic group is not particularly limited as long as it is one of the hydrogen atoms, but an alkyl group substituted with a ruthenium, a s, or a s. The atom and rm ' are counties, naphthalenes, and more than one gas base. The above cyclic group may be earlier than the base group, or may be an aliphatic ring, and may have the following substituents. The ring structure of the basic ring consisting only of a carbon atom and a ^% column may not be limited to a carbon atom = a subunit, and may contain an oxygen atom, and the hydrocarbon group may be == A hydrocarbon group is preferred. Furthermore, it is more preferable to use an aliphatic multi-ring beauty; L, but preferably saturated. Further, for example, 200835763, specific examples of the monocycloalkane, the bicycloalkane, and the above-mentioned aliphatic cyclic group may be: hi: ring appearance, tetracyclic fresh polycyclic group, more than one hydrogen, more specifically 'Can be listed as a job, the ring has been burned, etc. 2) ίί:, ~ Gang 垸, 茨 烧 、, 妓 妓, tricyclic 癸 、, 四 四 十二 衣 clothing to remove more than one hydrogen atom base. Among them, the base of the hydrogen atom on the Lx is removed.

The alumina and the above cyclohexane and dicyclopentane may further have the following substituents. The above substituent may, for example, be a polar group such as a hydroxyl group, a carboxyl group, a cyano group or an oxygen atom, or a linear or branched low carbon group having a carbon number of i 1 4 . The cyclic group may have a substituent, and it is preferable to have the above-mentioned polar group, the above-mentioned low carbon, and the above-mentioned polar group and the above-mentioned low carbon wire. The above-mentioned bribe base is particularly good for oxygen atoms (four). The above-mentioned hydrogen atom is replaced by a cyclic group, and the base is used as a base. In the case of the (fluorenyl) acrylate having such a cyclic structure, for example, it may be cyclohexyl-2-propyl acrylate. ^ = two (meth) acrylate having a cyclic structure, and may be, for example, phenoxyethyl acrylate or phenoxypropyl propyl acrylate. The term "aliphatic" as used in the present specification is a concept relating to aromatic: a group or a compound having no aromaticity, and for example, "aliphatic cyclic group" means a single one having no aromaticity. • A base or a polycyclic group. Further, in the case of the above (mercapto)propionate, a (fluorenyl)acrylic acid s containing one of the following may be used: a ring structure is provided and the ring structure 15 has a substituent on 200835763 (Methyl)acrylic acid vinegar and (meth)-acid having a cyclic structure and having no substituent in the cyclic structure. By (meth)acrylic acid having a structure of a wounded ring structure and having a substituent on the ring structure, and a (meth)acrylic acid having a ring structure and having no substituent on the ring structure Acidity can improve heat resistance and softness. (Alkyl (meth) acrylate composed of a chain structure) The adhesive composition of the present invention contains an alkyl (meth) acrylate composed of a chain structure in the monomer composition. Thereby, the flexibility and crack resistance of the adhesive layer obtained from the adhesive composition can be improved. The amount of the alkyl (meth)acrylate blended is not particularly limited as long as it can be copolymerized with other compounds contained in the above monomer composition, but the above-mentioned styrene and the above (meth)acrylic acid are contained. When the total amount of the monomer composition of the ester and the above (meth)acrylic acid ester is 100 parts by mass, the amount of the alkyl (meth)acrylate blended is preferably 10 to 60 parts by mass. When the amount is 10 parts by mass or more, the flexibility and crack resistance of the resulting layer can be further improved, and if it is 60 parts by mass or less, the heat resistance is lowered, the peeling failure, and the moisture absorption property can be suppressed. In the present specification, the above alkyl (meth)acrylate means an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms and an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms. j. Regarding the above-mentioned acrylic long-chain alkyl ester, the alkyl group may be an η-pentadecyl group, a nh hexa group, an η-^-heptyl group, an η-octadecyl group, an η-h-j-based group, or a η-twenth group. A proprietary acrylic acid ester or a mercapto acrylate. Furthermore, the burnt 16 200835763 base may also be branched. . With respect to the above-mentioned acrylic olefin vinegar having an alkyl group having 1 to 14 carbon atoms, I 歹J exemplifies a conventional acrylic ray used in an existing acryl-based adhesive. For example, the fluorenyl group may be a methyl group or an ethyl group. An alkyl acrylate consisting of propyl, butyl, 2-acetamidine, isooctyl, iso-yl, isodecyl, dodecyl, lauryl, and decyl, or alkoxy methacrylate. (Carboxylic acid having an ethylenic double bond) The above monomer composition is a carboxylic acid having an ethylenic double bond containing ιρ ^ /匕3. By means of the adhesive composition obtained by the temperature of the double key, it can be easily peeled off after the high-temperature process and the high-temperature process.藉 In the above-mentioned adhesive composition, i I-, +, , ># base (polarity h, fruit composition from the above-mentioned tannic acid = composition of the composition and coating with the rubbing rise, Therefore, the polarity of the above-mentioned adhesive composition on the interface of the contact surface is based on the molecular filaments and dissociation in the above-mentioned high-temperature environment, and the above-mentioned monomer composition is broken, and the above-mentioned persimmon and the above-mentioned (Methyl) propylene = di-p-ethyl compound, so high testability can be ensured. 竣, 竣-based poly, 2 = two have a dilute double bond and can be combined with other monomer components = no particular limitation, but Such as the following general formula (1): human knife tobacco

RsfC〇〇H)m. · . (〇~20^ represents an organic group having a (meth)propanyl group or a money of 2 in the county of E. It may also contain an oxygen atom; m represents i~ is < I 17 200835763 The carboxylic acid shown is preferably (mercapto)acrylic acid or as follows (2): " R2

H2C 〇 〇H ---(2)

(R2 represents a hydrogen atom or an alkyl group having a carbon number of i to 4; R3 represents a mussel burnt group having a carbon number of 1 to 5, or a divalent organic group having a ring structure of 4 to 2 carbon atoms; A carboxylic acid represented by an oxygen atom is more preferred. Specific examples of the carboxylic acid represented by the above formula (2) include R3 having two hydrogen atoms removed from cyclohexane, norbornane, tricyclodecane or tetracyclododecane. Base. These components may be used singly or in combination of two or more. Among these components, (meth)acrylic acid is more preferred. The copolymerization of these carboxylic acids with the other components in the above monomer composition can be smoothly carried out, and the structure of the polymer obtained by the copolymerization becomes stable. Therefore, the dissociation of the molecular chains from each other can be prevented, and the heat resistance and the bonding strength in a high temperature environment are also improved. The amount of the carboxylic acid to be blended may be appropriately set depending on the target properties of the adhesive composition such as the strength of the adhesive, but the total amount of the above styrene, the above (comparable) acrylate, and the above (alkyl) acrylate may be used. When it is 1 part by mass, it is preferably 1 to 10 parts by mass, more preferably 丨 to 5 parts by mass. When the amount is 1 part by mass or more, the resulting adhesive composition <heat resistance and adhesion strength in a south temperature environment can be further improved. Further, when the mass of the adhesive is 18 200835763, the moisture absorption of the adhesive composition and the prevention of gelation can be suppressed, and the carboxyl group content of the adhesive composition can be reduced, and the alkali resistance is also improved. When the carboxylic acid is mixed, the carboxylic acid may be copolymerized with the age of the carboxylic acid in the monomer composition. ~. The carboxylic acid is previously mixed into the precursor composition before the start of the copolymerization reaction; the carboxylic acid may be mixed after the initiation of the copolymerization of the other components and before the end of the copolymerization reaction. • However, it is preferred to start the reaction by mixing the above carboxylic acid, the above styrene, and the above (methacrylic acid 13⁄4 and the above (meth)acrylic acid alkyl ester in advance, by preliminarily mixing the above-mentioned carboxylic acid. The body composition and the substance are co-reacted, and the carboxylic acid may be randomly copolymerized with other components. By this, since the above polar group will be present evenly in the adhesive composition, the polarity of the upper v-side intermediate composition will be Further improvement, and the high temperature ring should further inhibit the dissociation of the molecular chains from each other in the composition of the adhesive, so that the strength is further improved. In the present specification, "starting the copolymerization reaction" means When the above-mentioned K and the compounds other than the compound which are mixed in the K reaction are mixed, the above-mentioned monomer composition starts to undergo the copolymerization reaction. In the case where the above-mentioned adhesive composition is produced, For the purpose, the compound constituting the monomer composition may be mixed and finally taken as the time point of the above-mentioned "copolymerization reaction start". The point is that the copolymerization reaction is carried out by using a combination of all kinds of compounds for the purpose of premixing, and the other parts are supplied to the reactor as a point of time to start the disturbance; 19 200835763 The reaction temperature of the reaction may be the time at which the heating is started to the temperature; in the case where the polymerization initiator is used, it may be the time at which the polymerization initiator is added. Since the above-mentioned point is used as the "copolymerization start" In the present invention, the effect of the present invention can be obtained. Therefore, the appropriate "copolymerization start" can be set according to the manufacturing equipment and conditions of the above-mentioned adhesive composition to control the subsequent steps. Tanabata, in this specification, The term "terminating the copolymerization reaction" means the time at which the desired copolymerization reaction is achieved. Specifically, the above-mentioned adhesive composition can be produced at a point when the stirring is stopped or when the reaction temperature starts to be cooled. Difunctional monomer): The above monomer composition may further contain a difunctional monomer. By containing a difunctional monomer, The constituent molecules in the subsequent composition can be crosslinked via the difunctional monomer. By crosslinking into a three-dimensional structure, the mass average molecular weight of the adhesive composition becomes large. In the technical field, if the mass average molecular weight of the constituent molecules is increased, the internal energy of the adhesive composition is also increased, and it is understood that the internal energy is also an important factor in the high-low temperature in the high-temperature environment. (1) The mass average molecular weight of the composition of the adhesive becomes large, the glass transition is exhibited, and the temperature also rises. Thus, the strength is also increased. In other words, the above-mentioned early composition contains a difunctional monomer by further steps. The mass average molecular weight of the junction is increased, and the strength is also increased under the high temperature environment. 200820763 Further, the above monomer composition contains the difunctional monomer, and the above-mentioned adhesive composition 27 in the high temperature environment Dissociation can be suppressed. Therefore, the strength is increased at a high temperature, and even after a high temperature process, it can be easily peeled off. Further, since the effect of improving the heat resistance and the like can be obtained by reducing the amount of use of the above-mentioned retarding acid, the alkali resistance of the above-mentioned adhesive composition containing the main component can be improved. Therefore, it is possible to provide an adhesive composition which has high heat resistance, alkali resistance and high temperature environment (especially 140 c to 200 c) and has high adhesion strength and is easily peeled off after a high temperature process. The difunctional monomer in the present specification means a compound having two functional groups. In other words, the above-mentioned difunctional monomer is not particularly limited as long as it has a compound: & energy base 1, but is selected from the following formula: X1-R4 to X2 · (3) ( R4 represents a divalent silk having a carbon number of 2 to 20 or a divalent organic group having a hetero structure and a number of 6 to 20, which may also contain an oxygen atom; X1 and X2 are each independently, and represent a (meth)acrylic group, ethylene. It is preferred that at least one of the difunctional monomers in the group consisting of the compounds shown in the group) is preferred. Examples of the compound represented by the above formula (3) include di-methyl-tricyclic tert-doped diacrylate, neopentyl glycol diacrylate, 1>9-nonanediol acrylate, and naphthalene.

The acrylate and the compound of the following formula (4): .0 (R5 and R6 each independently represent an ethoxy or propenoxy group; and η and 21 200835763 s are each independently, an integer of 0 to 4). These compounds may be used singly or in combination of two or more. Among these compounds, selected from the group consisting of dihydroxyindenyl-tricyclodecane diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol acrylate, naphthalene diacrylate, and the above formula (4) The at least one difunctional monomer selected from the group consisting of the compounds shown is more preferred. These difunctional monomers are easily crosslinked with other components of the monomer composition, and the crosslinked structure is also stabilized. Thereby, an adhesive composition in which the bonding strength and heat resistance in a high temperature environment are further improved can be obtained. The amount of the above-mentioned difunctional monomer can be appropriately set depending on the properties of the adhesive composition for the purpose of adhesion strength, etc., but the above styrene, the above (mercapto) acrylate, and the above (fluorenyl) acrylate are used. When the total amount of the alkyl ester is 100 parts by mass, it is preferably 0.1 to 0.5 part by mass, more preferably 0.1 to 0.3 part by mass. When it is 0.1 to 0.5 parts by mass, the adhesive strength and heat resistance of the obtained adhesive composition in a high-temperature environment are further improved, and further, since the hygroscopic property is suppressed, the gel of the adhesive composition can be prevented. Chemical. Further, the above difunctional monomer is preferably mixed in the remaining monomer composition before the start of the copolymerization reaction, but a part or all of the difunctional monomer is in the remaining monomer composition. After the copolymerization reaction is started, it is mixed, and about the same effect can be obtained. (Styrene Giant Monomer) The above monomer composition may further contain a styrene macromonomer. The average molecular weight of the adhesive composition obtained by this means 22 200835763 becomes large. Further, the dissociation of the molecular chains in the above-mentioned adhesive composition is suppressed in a high temperature environment. Therefore, the heat resistance of the subsequent composition, the adhesion strength in a high temperature environment (especially ~2 〇〇 ° C), and the ease of peeling after a high temperature process can be further improved.

Further, since the effect of improving the heat resistance can be obtained by reducing the amount of use of the above carboxylic acid, the durability of the adhesive composition can be improved as a main component. The above styrene giant monomer, as long as it has a stupid ethylene block structure in its structure and can be copolymerized with other components in the above monomer composition, will not be specially set, but is constructed by the styrene block and located in the benzene. The ethylene block is composed of organic groups at both ends, and at least one organic odorant carbon-carbon double bond of the above organic styrene macromonomer is preferred, and more preferably is CH-CH of the following formula:

• (5) (and R independently) denotes a benzoquinone macromonomer represented by at least one carbon-carbon double bond I having an organic group having 1 to 10 carbon atoms, which may also contain an oxygen atom. The above styrene macromonomer is easily copolymerized with other compounds contained in the above monomer composition. Therefore, the average molecular enthalpy/step of the obtained adhesive composition becomes large, and the molecular chains in the above-mentioned adhesive composition are mutually unpleasant. 23 200835763 To suppression. Benzene styrene block structure of benzene selected to contact the wire (4) (four) local self-heating heat resistance, preferably 50 to 70 is better. One of 20 to 100 is made of the above-mentioned styrene-based macromonomer, which is manufactured by 亚@. aq 7歹]. The giant body (manufactured by Higashi Co., Ltd., HS-(6), giant monomer (East Asia Synthetic also It is possible to mix two or more kinds of two early, and to use the other components in the composition alone - the copolymerization of the present ethylene macromonomer with the above-mentioned monomer hemp knife can smoothly become a polymer structure and also The disengagement of the after-sales service, the introduction of fr::; the second mistake can prevent the molecular bond from each other - the second A 〉 裱 裱 裱 的 裱 裱 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 本 本 本Then, when the total amount of the monomer group f is appropriately taken as (10) parts by mass according to the properties of the adhesive composition such as strength, resistance, and the like, the total I of the above-mentioned styrene and the above-mentioned ethylene macromonomer is 3. 〇~9〇 parts by mass, 40~6〇 parts by mass ^^ The amount of the above styrene macromonomer, in the total amount range, 5~40 Berry injury is better 'Better condition is · - the amount of the above styrene and the above styrene macromonomer is 30, f parts, the amount of the above styrene macromonomer, in the range of = total amount In the range of 1 to 2 parts by mass, it is said that the above-mentioned adhesive composition has an appropriate ratio of styrene to styrene macromonomer. That is, the above-mentioned adhesive composition can be simultaneously obtained. · The heat-resisting effect of styrene and the effect of the subsequent strength increase in the high temperature environment generated by the above styrene giant monomer. 24 200835763 The above-mentioned styrene giant monomer and the above monomer The composition requires τ to cause the copolymerization reaction of the upper oxime, and the components other than the other components are mixed into the monomer composition before the start of the copolymerization reaction, and m, (9) The above-mentioned benzene_ is in the above-mentioned phenethyl amide macromonomer to & _, and later, remixing the material of the bismuth monomer early =; after the silk reaction begins, the second time, the person, (10) is good, The copolymerization reaction is carried out according to the following: or a plurality of rounds of mixing is better. According to the mixing and mixing, the above q is also a pheno-styrene structure of the giant monomer; Ethylene is inhibited in one step, and the result is high temperature environment II According to the present embodiment, the above-mentioned polymer which can contain a benzene stellate-like segment, which is a main component of the product, can be prevented from being composed of a compound which is a main component of the composition. The ...^ ...1:::agent' and the peeling of the product, so that the adhesive composition of the high-temperature coat & the lower strength can be obtained. Also, the above-mentioned adhesive composition can be suppressed in a high temperature environment. The dissociation of the molecular chains from each other' thus prevents deterioration of the adhesive composition 25 200835763 in a high temperature environment. Therefore, the strength is increased, and even after a high temperature process, it can be easily peeled off. Moreover, even if the above carboxylic acid is reduced In some applications, the heat resistance can be improved, and the durability of the adhesive composition containing the main component can be further improved. Therefore, heat resistance, adhesion strength in a high temperature environment (especially 140 ° C to 200 ° C), and ease of peeling after a high temperature process can be further improved. In addition, the "styrene block" as used in the present specification means a site in which copolymerization is carried out in the above-mentioned polymer in the form of block units of styrene. Therefore, if styrene is added after the initiation of the polymerization, since the copolymerization of the other components is completed, a block body composed only of the styrene is formed. Therefore, the styrene block is a block copolymer obtained by polymerizing only styrene added after the polymerization of other monomer components is started. The formation of the styrene block from the above styrene is carried out by: adding all or a part of the above styrene to the residual portion of the styrene, the above (meth) acrylate and the above The (mercapto)alkyl acrylate is mixed into the copolymerization reaction system, that is, the reactor in which the copolymerization reaction is carried out, after the initiation of the copolymerization reaction and before the termination of the copolymerization reaction, all at once or in plural. The amount of styrene forming the styrene block is adjusted by the amount of styrene added after the start of the copolymerization reaction. Further, the amount thereof may be appropriately set depending on the nature of the adhesive composition such as strength and heat resistance, and the total amount of styrene used for producing the adhesive composition of the present embodiment is regarded as 26 200835763 100 In the case of parts by mass, the amount is preferably 5 to 80 parts by mass, more preferably 10 to 30 parts by mass. Further, styrene added after the start of the above copolymerization reaction is preferably added all at once in the styrene. Further, it is preferred to add it before the half time is required in the time required for the copolymerization reaction. If so, the styrene block can be suitably formed in the above-mentioned adhesive composition by dense styrene and copolymerization. (Component other than the main component in the adhesive composition) In the adhesive composition of the present embodiment, other additive components such as acrylamide such as dimercaptopropeneamine may be blended; or acrylonitrile may be scared. ^ Wait for the class. With the incorporation of these components, heat resistance and adhesion are expected to improve at the same time. In the adhesive composition of the present embodiment, an additive φ agent having a miscibility, for example, an additive resin for improving the performance of the adhesive, may be further added, within a range not impairing the essential properties of the present invention. Conventional additives such as plasticizers, auxiliaries, stabilizers, colorants, surfactants, and the like. Further, the adhesive composition may be diluted with an organic solvent for adjusting the viscosity within a range not impairing the essential characteristics of the present invention. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, and two #乙二Alcohol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, k dipropylene glycol or dipropylene glycol monoacetic acid g, monodecyl ether, monoethyl ether, monopropyl ether, monobutyl ether or Polyols such as monodecyl ether and derivatives thereof; 2 27 200835763 cyclic ethers such as decane; and methyl lactate, ethyl lactate, decyl acetate, ethyl acetate, butyl acetate, decyl pyruvate, An ester such as ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate. These components may be used singly or in combination of two or more. Especially monomethyl groups of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate Polyols such as ether, monoethyl ether, monopropyl ether, monobutyl ether or monopentyl ether and derivatives thereof are preferred. The amount of the organic solvent used is appropriately set depending on the film thickness obtained by applying the adhesive composition. The composition of the subsequent composition is not particularly limited as long as it is a concentration that can be applied to a support such as a semiconductor wafer. In general, the solid content concentration of the adhesive composition is used in the range of 20 to 70% by mass, preferably 25 to 60% by mass. As described above, in the above-mentioned adhesive composition for solving the conventional adhesive problem, a component of the monomer composition, a preferred structure of a polymer obtained by copolymerizing the same, and the like have been described. These can be appropriately combined, and by combining these modifications, it is needless to say that higher heat resistance and alkali resistance, easiness of peeling, and reduction in the amount of gas generated during heating and vacuum can be exhibited. [Copolymerization reaction] The copolymerization reaction of the above monomer composition can be carried out by a conventionally known method, and is not particularly limited. For example, the adhesive composition of the present invention can be obtained by stirring the above monomer composition using an existing stirring device. Although the temperature conditions in the copolymerization reaction can be appropriately set without particular limitation, it is preferably 60 to 150 C, and is preferably 7 to 12 Torr. It is better. Further, in the copolymerization reaction, a solvent can be used as appropriate. The above organic solvent can be used for the above solvent, and propylene glycol hydrazone acetate (hereinafter referred to as "PGMEA") is preferred. Further, in the copolymerization reaction of the present embodiment, a polymerization initiator may be used as appropriate. Regarding the polymerization initiator, it can be 2,2,-azobisisobutyl guess (A side), 2,2,-azobis(2_methylbutyl guess), 2,2,-azo double

An azo compound such as dimethyl isobutyrate, 1,1'-azobis(cyclohexane-1-carbonitrile), 4,4i-azobis(4-cyanovaleric acid); Oxide, lauryl peroxide, alum-based peroxide, bis(3,5,5-trimethylhexanoate) peroxide, succinate peroxide, tertiary butyl oxo An organic peroxide such as 2-ethylhexan, tert-butylperoxypenta-, (1), 3-tetramethylperoxy-2-ethylhexyl. These ingredients may be used alone or in combination of two or more.单体 The monomer composition (4) and the reaction strip are determined, and the sub-layer is not particularly limited. The binder composition of the present invention can be used as the above-mentioned adhesive composition. For example, it can be used in a liquid form for various applications such as use. After the formation of the adhesive layer = '· is applied to the adhesive film of the semiconductor wafer invention, (4) before the second can be used to form the "::: thin residual" of the composition of the second embodiment of the present invention This film (following the film) was attached to the object to be processed 29 200835763 (following the film method). =, the adhesive film of the present invention is provided with an adhesive layer of any of the above-mentioned carrier compositions. Therefore, the monomer composition can be introduced into the above-mentioned adhesive by using a polar group: when: the above-mentioned carboxylic acid is obtained, the heat resistance and the high temperature environment are obtained, and the high resistance is obtained, and then the peeling degree can be easily peeled off and Testability, and when subjected to high temperature production, the second body is further composed of the above-mentioned difunctional monomer, and further crosslinked in the above monomer group. In other words, it constitutes the above-mentioned === the size of the stupid female giant monomer, and the average molecular weight of the composition of the sputum is increased, and the connector layer has a segment structure. Thereby, the dissociation of the present vinyl hydrazines in the precursors is suppressed by the above: the upper part of the molecular chain in the composition of the agent = the main component of the above-mentioned adhesive layer, and the presence of the present ethylene block can prevent The above-mentioned production: the interface between the body and the surface to which the composition of the adhesive is applied can serve a strong heat resistance, a high temperature environment, a strong base, and excellent ease of separation. Then the film. The upper return film and the coating layer (4). 》^“Into the step, the protective film is coated on the above I, m, and Μ ant, by splicing the protective film on the adhesive layer -= weighs 4 after being applied to the body, 'will (4) t When peeling off, it is easy to provide an adhesive layer on the object to be processed. 30 200835763 Compared with the direct coating on the object to be processed, it is possible to form a uniform film thickness, and if the above-mentioned adhesive film is used, a cloth adhesive is formed. The layer of the adhesive layer - the layer of the surface and the flatness is relatively good.

★ €Next;! The film used for the production of the film may be a release film which can be used to peel the adhesive layer formed on the film from the film, and can transfer the adhesive layer to the surface to be processed such as the substrate and the wafer. The infinite 疋^ can be exemplified by a polyethylene terephthalate, a polyethylene, a polypropylene, a polycarbonate, a polychlorophthalic acid, and a film having a thickness of 15 to 125 μm. Flexible film. It is preferable that the above-mentioned film is easy to transfer in order to carry out the release treatment in a necessary day. The method of forming the adhesive layer on the above-mentioned film can be specifically defined according to the desired film thickness and uniformity of the desired carrier layer, and for example, an applicator or a stick can be used. An applicator, a wire applicator, a newspaper applicator, a curtain coating H, or the like, so that the film thickness of the above-mentioned adhesive layer on (4) is 10 to 1 mm, and the present invention is applied. The method of things. Among them, the roll coater is preferred because it can be efficiently and uniformly uniform and has a thick film. In the case of using the above-mentioned protective film, the protective film is not particularly limited as long as it can be peeled off from the above-mentioned adhesive layer, but for example, a film of a terephthalic acid, a polypropylene film, or a polyethylene is used. A film is preferred. Further, it is preferable that each of the above protective films is coated or sintered. Because the peeling from the above two agent layers is easy. The thickness of the above protective film is preferably 15 to 125 μm although it is not particularly = 疋'. @ is to ensure the flexibility of the above-mentioned adhesive film having the protective film. 31 200835763 The method of using the above-mentioned adhesive film is not particularly limited. For example, when a protective film is used, the protective film is peeled off, and the adhesive layer of the exposed layer is superposed on the object to be processed. The adhesive layer is heat-pressed on the surface of the body to be cured by moving the pure film on the enamel film (the surface on which the surface of the adhesive layer is formed). At this time, it is rolled into a roll shape by the (4) __ protective film **, and can be transferred and reused. The adhesive composition of the present invention is preferably used as a substrate for precision machining of a semiconductor wafer, and is preferably used for a substrate such as a semiconductor wafer. The composition of the receiver. The composition of the present invention is particularly suitable for the purpose of cutting a substrate such as a semiconductor crystal H into a sheet for the purpose of attaching the substrate to the branch board (4) (Minute, Japanese Laid-Open Patent Publication No. 191550) ).幵[Peeling liquid] The removal of the subsequent filament __ liquid of the present embodiment can be carried out using a usual peeling liquid, from the viewpoint of environmental load and peelability, brain EA and acetic acid, methyl ethyl _ The night which is the main component is particularly good. <Examples> Hereinafter, examples of the adhesion strength and the like of the adhesive composition of the present invention will be described. Further, the evaluation of the adhesive composition of the following examples and comparative examples was carried out by measuring the heat resistance, hygroscopicity, flexibility, and the subsequent strength under different temperature conditions and gas at 200 ° C by 32 200835763. The amount (hereinafter, expressed as "generating gas") is performed. The measurement methods of these are described below. ^ (Method for measuring the heat, moisture absorption, and gas generation) After applying the respective adhesive compositions of the following examples and comparative examples to the Shihwa wafer, the temperature of each coating film was increased by 4 generations. To 2 thieves, the amount of detached gas of the film was measured, and the amount of the gas was evaluated. The reason for the heat and hygroscopicity in the evaluation of the amount of the released gas is as follows: the amount of the degassed gas measured by the ～ to 〇〇c is derived from the water H gas or its conjugate. Since the water vapor or its azeotropic gas system is dehydrated and the binder composition absorbs moisture, the hygroscopicity can be evaluated based on the amount of the degassed gas measured in the first generation. Further, the amount of the released gas measured by the force HKTC or higher is derived from the gas generated by the thermal decomposition of the adhesive composition itself. Therefore, above 100 ° C, especially the program. The detachment gas at the temperature near c • The amount can be used to evaluate the heat resistance of the adhesive composition. The above-mentioned amount of liberated gas was measured by a TDS method (Desorption SpeCtr〇scopy). The TDs measuring device (release gas measuring device) is an EMD-WA1000 manufactured by Electronic Science Co., Ltd. The measurement conditions of the TDS device were 'width: 1 〇〇, center mass number: 5 〇, I added value (Gain): 9' scanning speed: 4, electron multiplier acceleration voltage (4) and r Volt): 1.3 KV. Evaluation of heat resistance: In the case of TC (in the case of TC, the intensity (In(jensity)) of the device was measured by the above-mentioned TDS measurement 33 200835763, and the residue was not observed in the metal microscope. In the case of 100,000 or more, the case where the residue is not observed by the metal microscope is denoted by Δ, and the case where the metal microscope observes the residue is denoted by x. The evaluation of the hygroscopicity is the above-mentioned strength at 100 ° C (Intensity) In the case of 10000 or less, it is referred to as 〇, and in the case of 10000 or more, it is referred to as X. In addition, when the gas is evaluated, the intensity (Indensity) obtained by the TDS measuring apparatus at 200 ° C is 100000 or less. In the case of 〇, 100000 or more is referred to as X. (Essential strength at each temperature) The adhesive compositions of the respective examples and comparative examples were applied onto a ruthenium wafer, and then dried at 150 C for 3 minutes. After the glass substrate was placed at a weight of 2 〇〇C and a weight of 1 kg, the glass substrate was stretched, and then the vertical electric measuring platform "Μχ-5_" (manufactured by Imada Yuesei Co., Ltd.) was used for calculation. Stone Adhesive strength at the time of wafer peeling. (Evaluation of flexibility) Each adhesive composition was applied to a 6-turn circle at 1 rpm for 25 seconds using a spinner, and then placed on a hot plate. 2〇(rc heating for 3 minutes, a coating layer can be obtained on the above-mentioned tantalum wafer. Then, the presence or absence of cracks in the coating film layer is visually observed. 'The cracked film layer is marked as a flaw, and the crack-free film is formed. The layer is recorded as 〇. In addition, the thickness of the Shixi wafer used is 200835763 (Evaluation of alkali resistance). Regarding the testability, after the composition of the 奋 奋 奋 奋 , , on the 矽 wafer, at 20 (TC dry 烊3/2 and the quality of the comparative example τ_ (Whether the film prepared by the hydrogen-oxygen solution coating was dissolved. The coating = 〇 was visually confirmed, and it was confirmed that the transfer was recorded as X.

[Examples 1 to 5, Comparative Example 1] (Meth) propylene ester having olefinic examples 1 to 5), and a composition (comparatively used styrene, an acid ester having a cyclic structure, and a chain structure) The nature of the adhesive composition of the monomer composition of the (meth)acrylic acid alkyl double bond and the use of the adhesive composition of the monomer composition containing no such acid-removing agent. 5. The composition of the monomer composition in Comparative Example 1 and the amount of the above-mentioned adhesive composition obtained by polymerizing the monomer composition are shown in Table 1. [Table 1] Composition (parts by mass) Example 1 Implementation Example 2 Example 3 Example 4 1 Example 5 Comparison of one Α, τ 1 methyl methacrylate 15 15 15 15 WJ w / 15 1 1 1J 丄 1 ^ n-butyl methacrylate 13 13 13 13 13 丄D 1 styrene 52 52 52 52 52 Phenoxyethyl acrylate 20 20 20 20 20 O jL OA Acrylic acid (mixed after the start of copolymerization) 5 5 0 0 ΖΛ) 0 Acrylic acid (mixed before the start of copolymerization) 0 0 5 10 15 0 Average molecular weight 87000 105000 105000 105000 J05000 86000 35 200835763 Examples 1 and 2 of the adhesive compositions obtained in the following method. PGMEA 53.85g was mixed as a solvent in a four-necked flask equipped with a reflux condenser, a stirrer, a thermometer, a nitrogen inlet tube and a 300 ml aliquot. As the monomer, phenoxyethyl acrylate 2 such as methyl methacrylate 15 g, n-butyl methacrylate 13 g, styrene 52 g, and acrylic acid 5 g were shown, and then nitrogen gas was started to be blown. The polymerization was started by starting the stirring, and the temperature was raised to 9 Torr while stirring. After the crucible, a mixture of pGMEA 3 8 · 4 5 g and tertiary butyl peroxy-2-ethylhexanoate as a polymerization initiator was continuously added dropwise by a dropping nozzle for 2 hours. Keep ❿ sure. Further, according to the average molecular weight of the adhesive composition corresponding to each of the examples described in Table 1, the addition amount of the tertiary butylperoxy-2-ethylhexanoate was adjusted so that the adhesive composition of each example was It has the average 'molecular weight' as stated in Table i. The polymerization reaction solution obtained after the completion of the dropwise addition was aged at 90 ° C for 1 hour, and then a mixture of 25.30 g of PGMEA and 0.3 g of tertiary butyl peroxy-2-ethylhexanoate was added. The solution was added dropwise over one hour. After that, the reaction solution was kept in the original state, and after aging at 9 ° C for 1 hour, i, ΐ, 3, 3-tetradecyl butyl peroxy-2-ethylhexanoate i. Og - all the inputs. Then, the polymerization reaction solution was allowed to stand at 9 Torr for 3 hours, and then the polymerization reaction solution was heated until the reflux of the solvent was observed, and the mixture was aged for 1 hour to terminate the polymerization. The adhesive compositions of Examples 3 to 5 were obtained in the following manner. In a four-pot beaker with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube and a capacity of 300 ml, pgmea 36 200835763 4〇g ' as a solvent and as shown in Table 1; Tian Ganzhi as a monomer Phenyl acrylate 20g, methyl methacrylate! &lt; 9 g, 13 g of n-butyl methacrylate, 52 g of styrene, acrylic acid, and μ·g were then blown with nitrogen. The mixture was stirred and the temperature was raised to 90 ° C while stirring, and then a mixture of PGMEA 17.3 g #available as acrylic acid was used (in the case of 3, 5 g, Λ^4, 1 () &amp;; 15g in Example 5, and by PGMEA 17.3g. The mixture of the initiator ternary butyl peroxy-2-ethylhexanoate l. 〇g was continuously added dropwise for 2 hours from the mouth, and the dropping rate was kept constant. After the dropping reaction, the resulting polymerization reaction solution was maintained in the original state, and after ripening at 9 ° C for 1 hour, 'PGMEA 79.9 g and tertiary butyl peroxy-2-ethylhexanoic acid were used. The mixture formed by G.2g was added dropwise over one hour. Thereafter, the reaction mixture was aged for another hour, and all of the tetramethylbutylperoxy-2·ethylhexanoate h〇g was added all at once. Then, the polymerization reaction solution was kept in the original state, and after the TC was aged to 3, the polymerization reaction solution was heated until the reflux of the solvent was observed, and after further aging for 1 hour, the polymerization was terminated. The carrier composition of Example 1 was obtained in the same manner as in Example 1 except that it did not contain propionic acid. Therefore, the phrase "mixing before the start of copolymerization" in Table 1 means methyl methacrylate, N-butyl methacrylate, styrene, phenoxyethyl acrylate, and acrylic acid were all mixed in an amount shown in Table 1 to initiate copolymerization. Further, in Table 1, "mixing after the start of copolymerization reaction" means 37,37,35,763, Methyl methacrylate, n-butyl methacrylate, styrene, and phenoxyacetic acid acrylate described in the above-described respective examples of the method for producing an adhesive composition are mixed according to the amounts shown in Table 1. After the temperature was raised to 卯^, acrylic acid was mixed in an amount shown in Table 1. For the above Examples 1 to 5 and Comparative Example 1, the bonding strength at 140 ° C, gas generation, heat resistance, flexibility, and moisture absorption were compared. Sex and alkali resistance The results are shown in Table 2.

【Table 2】

For Examples 1 to 5 and Comparative Example 1, the comparison was made equal to 233⁄4 12 (TC, 14 (rc, 200X; the subsequent strength. The results are shown in Table 3 and the figure. And, in the first figure, the horizontal The axis indicates each temperature condition, and the vertical direction indicates the strength of the joint (kgf/cm2).

[Table 3] Adhesion strength under remote conditions (kgfcm2) 23〇C 140°C _ Comparative Example 1 4.2 8.4 Example 1 3.9 9.8 __Example 2___ 5.2 9.8 -_ Example 3 4.8 112 A Example 4 5.6 11.0 ^ Example 5 A 5.4 11.0

38 200835763 The adhesive composition of the present invention is a monomer composition containing styrene, a (meth)acrylic acid having a cyclic structure, and a (meth)acrylic acid alkyl ester composed of a chain structure. A polymer composition obtained by copolymerization, wherein the monomer composition further contains (4) an olefinic double bond. Therefore, in the above-mentioned adhesive composition, the polar group is increased, and thus the polarity of the above-mentioned adhesive composition in the above-mentioned adhesive composition and the interface of the adhesive layer coated with the adhesive composition is increased upward, and __environment The dissociation of the molecular chains in the composition of the adhesive agent is inhibited, and the above monomer composition is obtained by containing the above styrene, the above-mentioned propylene riding and the above (曱基) A compound such as money that does not have a carboxyl group ensures durability. Therefore, it is possible to exhibit an "adhesive composition which provides a heat resistance, a high-temperature environment (especially S 14 (TC to 200t:) with high bonding strength and durability, and can be subjected to (four) peeling after a high-temperature process" Further, the film of the present invention, as described above, may be on the film - an adhesive layer having the above-mentioned adhesive composition. Thus, the above-mentioned precursor composition ' further contains the above carboxylic acid The polar group can be introduced into the coating, the agent: medium. Thus, it is possible to provide a bonding film which has high heat resistance, high temperature from the bottom, high strength and durability, and easy peeling after high-temperature processing. s X, this In the same manner as described above, in the above, the above-mentioned styrene, the above (meth)acrylic acid vinegar, and the above-mentioned (mercapto) 1 (10) Weiji S are finally reacted. Therefore, the above-mentioned ship's and the above-mentioned monomer composition are subjected to a copolymerization reaction of a component other than the above-mentioned acid-protecting agent, whereby the above-mentioned polar group is uniformly present in the 'X' local temperature environment of the adhesive composition. then The dissociation of the molecular chains of the constituent tissues is suppressed. Therefore, the polarity of the above-mentioned interface is increased, and then the strength is increased. The text can be used to provide a heat-resistant and high-temperature environment (special *14 (rc~200). The effect of the adhesive composition having high strength and durability, and which can be easily peeled off after the temperature treatment process. The specific embodiment or embodiment described in the detailed description of the invention has been clarified. The technical content of the present invention is not limited to the specific embodiments, and various modifications can be made within the spirit of the present invention and the scope of the appended claims. Further, the composition of the adhesive of the present invention And the film has high heat resistance, high sensitivity, low hygroscopicity, little gas generated during heating, and easy peeling by the stripping solution. Therefore, it is suitable for various chemicals such as high temperature process, high vacuum process, and use. The processing steps of the semiconductor wafer or wafer of the process. [Simplified description of the drawings] The figure shows that in the embodiment of the present invention, it will contain ethylene double + Comparison of the adhesion strength of the composition of the adhesive obtained by adding the monomer composition under different conditions. [Explanation of main component symbols] Benefit.

Claims (1)

200835763 X. Patent application scope: An adhesive (four) of a monomer composition containing fine styrene, a cyclic structure, (= hexyl acrylate, and a (meth) acrylate composed of a chain structure The core polymer is used as a binder composition of the main component, which is characterized by further carboxylic acid of the double bond of the monomer composition. 2. If you apply for the age-old product of the 乡 围 丨 , , , , , , , , , , , , , 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该The amount of the carboxylic acid is 丨 to 忉 parts by mass. 3. According to the remainder of the patent application, the remainder is the following formula (1): ^ R1 - fc 〇 OH ) m · · · (1) (Rl represents a (meth) acrylonitrile group or The carboxylic acid having a vinyl group having a carbon number of 2 to 20 and which may contain an oxygen atom; m represents an integer of 3). 4. The adhesive composition of claim 1, wherein the slit acid is (meth)acrylic acid or the following formula (2): R2 I H2C=C · · · - (2) (R2 represents a hydrogen atom or a carbon number of 1 to 4 fluorenyl; R3 represents a post-number! 41 200835763 〜5 of a divalent alkyl group, or a divalent alkyl group having a cyclic structure of 4 to 20 carbon atoms An organic group which may contain a carboxylic acid represented by an oxygen atom). A film which is characterized in that an adhesive layer is provided on the film, and the adhesive layer contains the adhesive composition according to any one of claims 1 to 4. a method for producing an adhesive composition, which comprises producing a styrene, a (meth) acrylate having a cyclic structure, an alkyl (meth) acrylate and a carboxylic acid An adhesive composition comprising a polymer obtained by copolymerizing a bulk composition as a main component, the method of manufacturing characterized in that the copolymerization reaction of the styrene, the (meth) acrylate and the alkyl (meth) acrylate is terminated The carboxylic acid is mixed before. 7. The method for producing an adhesive composition according to claim 6, wherein the copolymerization is started after the carboxylic acid, the styrene, the (meth) acrylate, and the alkyl (meth) acrylate are mixed. reaction. 42