Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • H—ELECTRICITY
  • 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
• • 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

Definitions

• the present invention relates to a pressure-sensitive adhesive composition that can be easily peeled off even after undergoing a high-temperature processing treatment of 250 ° C. or higher for a long time or 300 ° C. or higher with the adherend fixed.
• the present invention also relates to an adhesive tape having an adhesive layer made of the adhesive composition, and a method for treating electronic components using the adhesive tape.
• the electronic components When processing electronic components such as semiconductors, in order to facilitate the handling of the electronic components and prevent them from being damaged, the electronic components are fixed to the support plate via an adhesive composition, or the adhesive tape is electronically attached. It is protected by attaching it to parts. For example, when a thick film wafer cut out from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin film wafer, the thick film wafer can be adhered to a support plate via an adhesive composition. Will be done.
• Patent Document 1 discloses a pressure-sensitive adhesive sheet in which a polyfunctional monomer or oligomer having a radiopolymerizable functional group is bonded to the side chain or main chain of a polymer. Has been done.
• the adhesive strength is lowered by irradiating the polymer with ultraviolet rays at the time of peeling, and the polymer can be peeled without adhesive residue.
• a method of blending a release agent such as silicone oil or silicone diacrylate in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive composition or the pressure-sensitive adhesive tape is also known.
• a metal thin film having more excellent conductivity can be formed by processing at a high temperature of about 300 to 350 ° C.
• thermocompression bonding at a high temperature.
• electronic components protected by using a conventional adhesive composition or adhesive tape whose peelability has been improved by, for example, blending a mold release agent are subjected to high-temperature processing at 250 ° C. or higher for a long time or 300 ° C.
• adhesion may be enhanced and the adhesive strength may not be sufficiently lowered at the time of peeling, or adhesive residue may be generated due to thermal deterioration of the adhesive.
• An object of the present invention is to provide an adhesive composition that can be easily peeled off even after undergoing a long time of 250 ° C. or higher or a high temperature processing treatment of 300 ° C. or higher with the adherend fixed. do.
• Another object of the present invention is to provide an adhesive tape having an adhesive layer made of the adhesive composition, and a method for processing electronic components using the adhesive tape.
• the present invention is a pressure-sensitive adhesive composition containing a silicone-modified polyimide (A) and a curable resin (B) having a double bond.
• A silicone-modified polyimide
• B curable resin
• the present inventors have investigated a pressure-sensitive adhesive composition containing a silicone-modified polyimide (A) and a curable resin (B) having a double bond.
• the present inventors have stated that such a pressure-sensitive adhesive composition has a sufficient initial adhesive strength, but on the other hand, the enhancement of adhesion is suppressed.
• the pressure-sensitive adhesive composition of the present invention contains a silicone-modified polyimide (A).
• the silicone-modified polyimide (A) acts as a release agent and bleeds out to the interface of the adherend to facilitate peeling.
• the silicone-modified polyimide (A) is the main component of the pressure-sensitive adhesive composition
• the pressure-sensitive adhesive composition has a structure derived from silicone at the interface of the adherend, but has adhesiveness. The body can be fixed and can be easily peeled off even after undergoing high-temperature processing.
• the silicone-modified polyimide (A) has an imide skeleton and has a silicone chain, so that it has extremely excellent heat resistance. For this reason, the silicone-modified polyimide (A) is less likely to decompose the main chain even after undergoing a long-time processing of 250 ° C. or higher or a high-temperature processing treatment of 300 ° C. or higher, resulting in enhanced adhesion or glue at the time of peeling. It is possible to prevent the residue from occurring.
• the number of repetitions of the siloxane unit (repeating unit having a siloxane skeleton) in the silicone chain is not particularly limited, but the preferable lower limit is 10 and the preferable upper limit is 100.
• the pressure-sensitive adhesive composition can exhibit more excellent peelability, and the heat resistance of the silicone-modified polyimide (A) is also improved.
• the number of repetitions of the siloxane unit is 100 or less, it is possible to prevent the compatibility between the silicone-modified polyimide (A) and the solvent or other components from being excessively lowered.
• the more preferable lower limit of the number of repetitions of the siloxane unit is 20, the more preferable upper limit is 80, the further preferable lower limit is 30, and the further preferable upper limit is 60.
• the weight average molecular weight of the silicone-modified polyimide (A) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, the preferable lower limit is 1000 and the preferable upper limit is 50,000.
• the weight average molecular weight is 1000 or more, it is possible to prevent the silicone-modified polyimide (A) from bleeding out too much and contaminating the adherend when it acts as a release agent. be able to.
• the silicone-modified polyimide (A) can be sufficiently bleeded out to facilitate peeling.
• the more preferable lower limit of the weight average molecular weight is 3000, the more preferable upper limit is 30,000, the further preferable lower limit is 5000, and the further preferable upper limit is 20,000.
• the weight average molecular weight of the silicone-modified polyimide (A) is preferably a lower limit of 5,000 and a preferred upper limit of 100,000.
• the weight average molecular weight is 5000 or more, it is possible to prevent the silicone-modified polyimide (A) from flowing too much when it is the main component of the pressure-sensitive adhesive composition.
• the weight average molecular weight is 100,000 or less, the compatibility between the silicone-modified polyimide (A) and the solvent or other components can be improved.
• the more preferable lower limit of the weight average molecular weight is 6000, the further preferable lower limit is 7,000, the even more preferable lower limit is 8000, the more preferable lower limit is 9000, and the particularly preferable lower limit is 10,000.
• the more preferable upper limit of the weight average molecular weight is 80,000, and the more preferable upper limit is 50,000.
• the weight average molecular weight is measured as a polystyrene-equivalent molecular weight by a gel permeation chromatography (GPC) method.
• GPC gel permeation chromatography
• HR-MB-M manufactured by Waters
• the silicone-modified polyimide (A) preferably has a functional group that can be crosslinked with the curable resin (B) having a double bond.
• the silicone-modified polyimide (A) has the crosslinkable functional group, it chemically reacts with the curable resin (B) having a double bond directly or via a crosslinking agent by irradiation with light or heating. It is incorporated into the curable resin (B) having a double bond. Therefore, it is possible to prevent the silicone-modified polyimide (A) or the curable resin (B) having a double bond from adhering to the adherend and contaminating the adherend.
• the crosslinkable functional group is not particularly limited and is selected according to the curable resin (B) having a double bond, and has, for example, a carboxy group, a hydroxyl group, an amide group, an isocyanate group, an epoxy group and a double bond.
• Examples include functional groups. Of these, a hydroxyl group or a functional group having a double bond is preferable because higher heat resistance can be obtained.
• the functional group having the double bond is not particularly limited, and examples thereof include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, and a (meth) acrylic group which may be substituted.
• a maleimide group that may be substituted is preferable because higher heat resistance can be obtained.
• the silicone-modified polyimide (A) is not particularly limited as long as it has an imide skeleton and has a silicone chain.
• the silicone chain may be present in the main chain of the silicone-modified polyimide (A) or in the side chain.
• Specific examples of the silicone-modified polyimide (A) include a structural unit represented by the following general formula (1a), a structural unit represented by the following general formula (1b), and the following general formula (1c).
• Examples thereof include silicone-modified polyimide (A1) having a structural unit represented (where s1 ⁇ 1, t1 ⁇ 0, u1 ⁇ 0).
• P 1 , P 2 and P 3 independently represent an alicyclic group or an aromatic group, respectively.
• Q 1 is represents a silicone chain
• Q 2 represents a substituted or unsubstituted aliphatic group or an aromatic group
• R represents a substituted or unsubstituted branched-chain aliphatic group or an aromatic group.
• X 3 represents a substituted or unsubstituted aliphatic group, an aromatic group or a functional group having a double bond
• n1 in X 3 n1 represents an integer of 1 or more.
• P 1 , P 2 and P 3 are preferably alicyclic groups or aromatic groups having 5 to 50 carbon atoms, respectively. Since P 1 , P 2 and P 3 are independently alicyclic groups or aromatic groups having 5 to 50 carbon atoms, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance. It is preferable that P 1 , P 2 and P 3 have a structure derived from an acid anhydride described later.
• a silicone chain represented by Q 1 are not particularly limited, for example, a silicone chain or the like having a (repeating unit having a siloxane skeleton) siloxane units having a repeat number of the above-mentioned range and the like.
• the Q 1 is preferably a structure derived from a silicone compound having an amino group at both ends, which will be described later.
• Q 2 is preferably a substituted or unsubstituted aliphatic group or an aromatic group having 2-100 carbon atoms.
• Q 2 is a substituted or unsubstituted aliphatic group or an aromatic group having a carbon number of 2 to 100, by a very particularly aliphatic group, exert a pressure-sensitive adhesive sheet is flexible prepared with an adhesive composition It is possible to exhibit high followability to an adherend having irregularities, and also improve peelability.
• It said Q 2 are preferably a structure derived from the later-described diamine compound is more preferably a structure derived from a dimer diamine, which will be described later.
• R is preferably a substituted or unsubstituted branched chain-like aliphatic group or aromatic group having 2 to 100 carbon atoms. Since R is a substituted or unsubstituted branched chain-like aliphatic group or aromatic group having 2 to 100 carbon atoms, the pressure-sensitive adhesive sheet produced by using the pressure-sensitive adhesive composition can exhibit high flexibility. In addition to being able to exhibit high followability to adherends with irregularities, peelability is also improved.
• the R is preferably a structure derived from a diamine compound described later, and more preferably a structure derived from a diamine compound having a functional group described later.
• both ends are not particularly limited, and examples thereof include a structure derived from an acid anhydride or a diamine compound which is a raw material of the silicone-modified polyimide (A1).
• both ends may have a structure represented by X 1 Q- and X 2-, respectively.
• X 1 Q- is a structural unit represented by the general formula (1a), a structural unit represented by the general formula (1b), or a structural unit represented by the general formula (1c). It combines with an N atom to become the end on the N atom side, and X 2- becomes the end on the opposite side to the N atom.
• Q is the same as Q 1 or Q 2
• X 1 and X 2 each independently represent a substituted or unsubstituted aliphatic group, an aromatic group or a functional group having a double bond.
• X 1 , X 2 and X 3 are independent of each other, for example, an aliphatic group, an alicyclic group, an aromatic group, a structure derived from an acid anhydride, and an amine compound.
• examples thereof include a structure derived from, a functional group having a double bond, and the like.
• Specific examples thereof include a structure derived from an acid anhydride or a one-terminal unreacted product of a diamine compound which is a raw material of the silicone-modified polyimide (A1).
• at least one selected from the group consisting of X 1 , X 2 and X 3 preferably contains a functional group having a double bond.
• the functional group having the double bond is not particularly limited, and examples thereof include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, and a (meth) acrylic group which may be substituted. Of these, a maleimide group that may be substituted is preferable because higher heat resistance can be obtained.
• the silicone-modified in the polyimide (A1), n1 in the X 3 n1 is preferably 10 or less, more preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, particularly preferably 2 or less an integer. In the above silicone-modified polyimide (A1), X 3 a plurality (n1 pieces) included in one of the structural units may each be the same or may be different.
• s1 is 1 or more, preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• t1 is 0 or 1 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• u1 is 0 or 1 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• the unit may be a block copolymer composed of block components in which each structural unit is continuously arranged.
• each of the structural units represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) is random. It may be a random copolymer arranged in.
• a silicone compound having amino groups at both ends is reacted with an acid anhydride (for example, an aromatic acid anhydride, an acid anhydride having an alicyclic group, etc.). It can be produced by obtaining an imide compound. Further, if necessary, the diamine compounds may be reacted together. Further, as the diamine compound, a diamine compound having a functional group is used, and the functional group in the obtained imide compound has a functional group that reacts with the functional group and a functional group having a double bond (hereinafter referred to as a compound). , A functional group-containing unsaturated compound) can be reacted to introduce a functional group having a double bond in the side chain.
• an acid anhydride for example, an aromatic acid anhydride, an acid anhydride having an alicyclic group, etc.
• the diamine compounds may be reacted together.
• the diamine compound a diamine compound having a functional group is used, and the functional group in the obtained imide compound has a functional group that
• the terminal is made a structure derived from the diamine compound, and the obtained terminal amino group is reacted with the functional group-containing unsaturated compound to have a functional having a double bond at the terminal.
• the group can be introduced.
• silicone compound having amino groups at both ends examples include a silicone compound having an amino group at both ends and a siloxane unit (repeating unit having a siloxane skeleton) having a number of repetitions in the above range. ..
• commercially available products include, for example, KF-8010, X-22-161A, X-22-161B, KF-8012, PAM-E (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
• the diamine compound either an aliphatic diamine compound or an aromatic diamine compound can be used.
• an aliphatic diamine compound as the diamine compound, the adhesive tape produced by using the pressure-sensitive adhesive composition can exhibit high flexibility and can exhibit high followability to an adherend having irregularities. At the same time, the peelability is also improved.
• an aromatic diamine compound as the diamine compound, the heat resistance of the pressure-sensitive adhesive composition is further improved.
• Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimerdiamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, and 1,2-diamino.
• dimer diamine is used from the viewpoint of increasing flexibility and from the viewpoint of increasing compatibility with the solvent and other components of the silicone-modified polyimide (A) and facilitating the production of adhesive tape.
• the diamine diamine is a diamine compound obtained by reducing and aminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and is, for example, a linear type, a monocyclic type, or a polycyclic type. Examples include dimer diamines such as molds.
• the dimer diamine may contain a carbon-carbon unsaturated double bond, or may be a hydrogenated additive to which hydrogen has been added.
• diamine diamine for example, a group represented by the general formula (4-1), a group represented by the general formula (4-2), and a general formula (4-3) as described later.
• examples thereof include a group represented by the diamine and a diamine diamine capable of forming a group represented by the general formula (4-4).
• aromatic diamine compound examples include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, and 3,4-.
• Diaminobenzophenone 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diamino Toluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-kumendiamine, 1,3-bisaminomethylbenzene, 1,3- Bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4
• Examples of the diamine compound having a functional group include a diamine compound having a hydroxyl group, a diamine compound having a carboxyl group, and a diamine compound having a halogen group.
• Examples of the diamine compound having a hydroxyl group include 1,3-diamino-2-propanol, 2,4-diaminophenoxyethanol, 3,5-diaminophenoxyethanol, 2,4-diaminophenol, 3,5-diaminophenol, and 2, , 4-Diaminobenzyl alcohol, 4,6-diaminoresorcin dihydrochloride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and the like.
• Examples of the diamine compound having a carboxyl group include 3,5-diaminobenzoic acid and the like.
• Examples of the diamine compound having a halogen group include 2,4-diaminochlorobenzene and the like.
• aromatic acid anhydride examples include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalene. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-biphenyl ether tetracarboxylic acid, 3, 3', 4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1 -Trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid,
• the functional group-containing unsaturated compound is selected and used according to the functional group at the terminal or side chain of the imide compound.
• a maleimide compound having a carboxyl group can be mentioned.
• the maleimide compound having a carboxyl group include maleimide acetate, maleimide propionic acid, maleimide butyric acid, maleimide hexane acid, trans-4- (N-maleimide methyl) cyclohexane-1-carboxylic acid, and 19-maleimide-17-oxo. -4,7,10,13-tetraoxa-16-azanonadecanic acid and the like can be mentioned.
• vinyl compounds having an ether group such as butyl vinyl ether, allyl compounds having a glycidyl group such as diallyl monoglycidyl isocyanurate, allyl ether compounds having a glycidyl group such as allyl glycidyl ether and glycerin diallyl monoglycidyl ether can be mentioned.
• vinyl ether compounds having a glycidyl group such as glycidyl oxyethyl vinyl ether, glycidyl oxybutyl vinyl ether, glycidyl oxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol monovinyl ether and the like can be mentioned.
• allyl compounds having an isocyanate group such as allyl isocyanate, (meth) acryloyl compounds having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate and the like can be mentioned.
• an allyl compound having a hydroxyl group such as trimethylolpropanediallyl ether or pentaerythritol triallyl ether, or glycidyl such as diallyl monoglycidyl isocyanurate.
• allyl compounds having a group include allyl compounds having a group.
• allyl ether compounds having a glycidyl group such as allyl glycidyl ether and glycerin diallyl monoglycidyl ether can be mentioned.
• vinyl ether compounds having a glycidyl group such as glycidyl oxyethyl vinyl ether, glycidyl oxybutyl vinyl ether, glycidyl oxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol monovinyl ether and the like can be mentioned.
• the functional group at the terminal or side chain of the imide compound is an amino group
• maleic anhydride and the like can be mentioned.
• the content of the silicone-modified polyimide (A) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, it is based on 100 parts by weight of the curable resin (B) having a double bond.
• the preferred lower limit is 0.5 parts by weight and the preferred upper limit is 100 parts by weight.
• the pressure-sensitive adhesive composition can exhibit more excellent peelability without contaminating the adherend.
• the more preferable lower limit of the content of the silicone-modified polyimide (A) is 1 part by weight, the more preferable upper limit is 50 parts by weight, and the more preferable lower limit. Is 3 parts by weight, and a more preferable upper limit is 20 parts by weight. Since the pressure-sensitive adhesive composition of the present invention is excellent in heat resistance, a sufficient effect can be exhibited even if the content of the silicone-modified polyimide (A) is relatively small. Therefore, the possibility of contamination by the silicone-modified polyimide (A) can be further reduced.
• the preferable lower limit of the content of the silicone-modified polyimide (A) is 100 with respect to 100 parts by weight of the curable resin (B) having a double bond.
• the preferred upper limit is 400 parts by weight.
• the content of the silicone-modified polyimide (A) is within this range, the pressure-sensitive adhesive composition can exhibit more excellent peelability without contaminating the adherend.
• the more preferable lower limit of the content of the silicone-modified polyimide (A) is 150 parts by weight, the more preferable upper limit is 300 parts by weight, and the more preferable lower limit.
• A) the total amount of the curable resin (B) having a double bond, etc.), for example, 50% by weight or more, preferably more than 50% by weight.
• the content of the silicone-modified polyimide (A) is usually less than 100% by weight, preferably 90% by weight or less, and more preferably 80% by weight or less of the total amount of the resin components constituting the pressure-sensitive adhesive composition. ..
• the pressure-sensitive adhesive composition of the present invention contains a curable resin (B) having a double bond.
• the curable resin (B) By containing the curable resin (B), the entire pressure-sensitive adhesive composition is uniformly and quickly polymerized and crosslinked by irradiation with light or heating, and the elastic modulus is increased, so that the adhesive strength is greatly reduced. As a result, the enhancement of adhesion is suppressed, so that the adherend can be easily peeled off even after undergoing a long time of 250 ° C. or higher or a high temperature processing treatment of 300 ° C. or higher in a fixed state.
• the curable resin (B) is not particularly limited as long as it has a functional group having a double bond.
• the functional group having the double bond is not particularly limited, and examples thereof include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, and a (meth) acrylic group which may be substituted. Of these, a maleimide group that may be substituted is preferable because higher heat resistance can be obtained.
• the content of the curable resin (B) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, the resin component (for example, the silicone-modified) constituting the pressure-sensitive adhesive composition is used.
• the total amount of polyimide (A), curable resin (B) having a double bond, etc.) is, for example, 50% by weight or more, preferably more than 50% by weight.
• the content of the curable resin (B) is usually less than 100% by weight, preferably 90% by weight or less, based on the total amount of the resin components constituting the pressure-sensitive adhesive composition.
• the content of the curable resin (B) is a resin component (for example, the silicone-modified polyimide (A)) constituting the pressure-sensitive adhesive composition. , 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, based on the total amount of the curable resin (B) having a double bond, etc.).
• the content of the curable resin (B) is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, based on the total amount of the resin components constituting the pressure-sensitive adhesive composition.
• the curable resin (B) examples include a polyimide resin having a double bond and an acrylic resin having a double bond. Of these, a polyimide resin having a double bond is preferable. Since the curable resin (B) is a polyimide resin and has an imide skeleton, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance, so that the generation of residues due to thermal deterioration is further suppressed and peeling is performed. Sex also improves. Among them, the curable resin (B) preferably contains a curable resin (B1) having an imide skeleton in the main chain and a functional group having a double bond in the side chain or the terminal.
• the curable resin (B1) preferably has a functional group equivalent having a double bond (weight average molecular weight / number of functional groups having a double bond) of 4000 or less.
• the functional group equivalent is 4000 or less, the pressure-sensitive adhesive composition can exhibit higher heat resistance. It is considered that this is because the molecule of the curable resin (B1) has a functional group having a double bond at a certain density or higher, so that the distance between crosslinks is shortened and the adhesion enhancement is further suppressed. ..
• the functional group equivalent is more preferably 3000 or less, and further preferably 2000 or less.
• the lower limit of the functional group equivalent is not particularly limited, but is substantially about 600 as the lower limit.
• the curable resin (B1) preferably has a weight average molecular weight of 5000 or more.
• the weight average molecular weight of the curable resin (B1) is 5000 or more, film formation becomes easy and the obtained film exhibits a certain degree of flexibility. It can exhibit high followability and can be easily peeled off from the adherend.
• the weight average molecular weight of the curable resin (B1) is more preferably 10,000 or more, and further preferably 20,000 or more.
• the upper limit of the weight average molecular weight of the curable resin (B1) is not particularly limited, but it is, for example, 300,000, particularly 100,000 because the solubility in a solvent is low.
• the functional group having the double bond may be on either the side chain or the terminal of the curable resin (B1).
• the functional group having the double bond is preferably present at both ends of the curable resin (B1), and more preferably in the side chain in addition to both ends.
• the functional groups having double bonds at both ends of the curable resin (B1) are highly reactive, and the pressure-sensitive adhesive composition can be more sufficiently cured by irradiation with light, heating, or the like. As a result, the enhancement of adhesion can be further suppressed, and the pressure-sensitive adhesive composition can exhibit higher heat resistance. Further, since the side chain of the curable resin (B1) has a functional group having a double bond, the pressure-sensitive adhesive composition can exhibit higher heat resistance.
• the curable resin (B1) preferably further has a hydroxyl group-containing group.
• the hydroxyl group reacts with, for example, a maleimide group of another component by heating or the like, and the elastic modulus of the pressure-sensitive adhesive composition is further increased to provide adhesive strength. Is further reduced. As a result, the increase in adhesion of the pressure-sensitive adhesive composition is further suppressed, and the peelability is also improved.
• the hydroxyl group-containing group is not particularly limited, and may have an alcoholic hydroxyl group or a phenolic hydroxyl group. Among them, it is preferable to have a phenolic hydroxyl group because of its high reactivity.
• Examples of the hydroxyl group-containing group having an alcoholic hydroxyl group include an aliphatic group or an aromatic group having an alcoholic hydroxyl group having 3 to 18 carbon atoms.
• hydroxyl group-containing group having a phenolic hydroxyl group examples include an aromatic group having a phenolic hydroxyl group having 6 to 24 carbon atoms, and more specifically, for example, phenol, bisphenol A, bisphenol F, biphenol, 2 , 2'-bis (4-hydroxyphenyl) hexafluoropropane and the like. Of these, 2,2'-bis (4-hydroxyphenyl) hexafluoropropane is preferable because it has good peelability.
• the curable resin (B1) preferably has a functional group equivalent (weight average molecular weight / number of hydroxyl group-containing groups) of hydroxyl group-containing groups of 5000 or less.
• a functional group equivalent weight average molecular weight / number of hydroxyl group-containing groups
• the functional group equivalent is more preferably 3000 or less, and further preferably 1000 or less.
• the lower limit of the functional group equivalent is not particularly limited, but is substantially about 500 as the lower limit.
• the curable resin (B1) has a structural unit represented by the following general formula (1d), a structural unit represented by the following general formula (1e), and the following general formula (1f). has a structural unit represented (however, s2 ⁇ 1, t2 ⁇ 0 , u2 ⁇ 0), both ends X 4 respectively - it is a curable resin represented (B1-1) - and X 5 Is preferable.
• P 4, P 5 and P 6 are each independently, an alicyclic group or an aromatic group.
• Q 3 are substituted or unsubstituted, straight, represents a branched or cyclic aliphatic group,
• Q 4 represents a substituted or unsubstituted aromatic radical,
• R is a substituted or unsubstituted branched-chain Represents an aliphatic group or an aromatic group.
• At least one selected from the group consisting of X 4 , X 5 and X 6 represents a functional group having a double bond, and n2 in X 6 n2 represents an integer of 1 or more.
• P 4, P 5 and P 6 are each independently is preferably a cycloaliphatic group or an aromatic group having 5 to 50 carbon atoms. Since P 4 , P 5 and P 6 are independently alicyclic groups or aromatic groups having 5 to 50 carbon atoms, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance.
• Q 3 is a substituted or unsubstituted, straight, is preferably a branched or cyclic number 2-100 aliphatic group having a carbon of.
• Q 3 is substituted or unsubstituted, straight, by a branched-chain or cyclic number 2-100 aliphatic group having a carbon of exerting a pressure sensitive adhesive sheet is flexible prepared with an adhesive composition It is possible to exhibit high followability to an adherend having irregularities, and also improve peelability.
• Q 3 is preferably an aliphatic group derived from a diamine compound as described above.
• Q 3 is a dimer diamine It is preferably an aliphatic group from which it is derived.
• the aliphatic group derived from the dimer diamine is not particularly limited, but is a group represented by the following general formula (4-1), a group represented by the following general formula (4-2), and the following general formula (4-3). ) And at least one selected from the group consisting of the groups represented by the following general formula (4-4). Among them, the group represented by the following general formula (4-2) is more preferable.
• R 1 to R 8 and R 13 to R 20 independently represent linear or branched hydrocarbon groups. Note that * represents a bond. That is, * is combined with N in the above general formulas (1d) to (1f).
• the hydrocarbon groups represented by R 1 to R 8 and R 13 to R 20 are not particularly limited and may be saturated hydrocarbon groups. It may be an unsaturated hydrocarbon group. Among them, R 1 and R 2, R 3 and R 4, R 5 and R 6, R 7 and R 8, R 13 and R 14, R 15 and R 16, R 17 and R 18, and, with R 19 It is preferable that the total number of carbon atoms of R 20 is 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the adhesive tape produced by using the pressure-sensitive adhesive composition can exhibit higher flexibility, and the solvent of the curable resin (B1-1) can be exhibited. The compatibility with other ingredients is further increased.
• the total number of carbon atoms is more preferably 9 or more, still more preferably 12 or more, and even more preferably 14 or more.
• the total number of carbon atoms is more preferably 35 or less, still more preferably 25 or less, and even more preferably 18 or less.
• the optical isomerism of the group represented by 4) is not particularly limited, and any optical isomerism is included.
• Q 4 is preferably an aromatic group substituted or unsubstituted C 5-50.
• Q 4 is an aromatic group substituted or unsubstituted 5 to 50 carbon atoms, can exhibit particularly high heat resistance adhesive composition.
• the curable resin (B1) has the hydroxyl group-containing group is preferably Q 4 are the hydroxyl group-containing group
• R is preferably a substituted or unsubstituted branched chain-like aliphatic group or aromatic group having 2 to 100 carbon atoms. Since R is a substituted or unsubstituted branched chain-like aliphatic group or aromatic group having 2 to 100 carbon atoms, the pressure-sensitive adhesive sheet produced by using the pressure-sensitive adhesive composition can exhibit high flexibility. In addition to being able to exhibit high followability to adherends with irregularities, peelability is also improved.
• R is the an aromatic group having an aromatic ester group or an aromatic ether group, aromatic ester or aromatic ether groups in R is bonded to X 6 Is preferable.
• aromatic ester group means a group in which an ester group is directly bonded to an aromatic ring
• aromatic ether group means a group in which an ether group is directly bonded to an aromatic ring. ..
• a functional group having a double bond crosslinking unsaturated bond
• at least one is selected from the group consisting of X 4, X 5 and X 6
• At least X 6 is preferably a functional group having a double bond.
• the pressure-sensitive adhesive composition can exhibit higher heat resistance.
• any of the above X 4 , X 5 and X 6 is a functional group other than a functional group having a double bond (a functional group having no double bond), the functional group does not have the double bond.
• n2 in X 6 n2 is preferably an integer of 10 or less, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. be.
• X 6 a plurality (n2 pieces) included in one of the structural units may each be the same or may be different.
• s2 is 1 or more, preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• t2 is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• u2 is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
• the structural unit may be a block copolymer composed of block components in which each structural unit is continuously arranged, or may be a random copolymer in which each structural unit is randomly arranged.
• the curable resin (B1-1) can be produced, for example, by reacting a diamine compound with an aromatic acid anhydride to obtain an imide compound.
• a diamine compound having a functional group is used as the diamine compound, and the functional group in the obtained imide compound has a functional group that reacts with the functional group and a functional group having a double bond (a compound having a functional group having a double bond).
• a functional group having a double bond in the side chain can be introduced.
• the diamine compound, the aromatic acid anhydride and the functional group-containing unsaturated compound are not particularly limited, and the diamine compound, the aromatic acid anhydride and the functional group used for obtaining the silicone-modified polyimide (A) described above are not particularly limited. Examples thereof include compounds similar to the containing unsaturated compounds.
• the content of the curable resin (B1) in the entire curable resin (B) is not particularly limited, but the preferable lower limit is 30% by weight. When the content of the curable resin (B1) is 30% by weight or more, the increase in adhesion of the pressure-sensitive adhesive composition is further suppressed, and the peelability is also improved. A more preferable lower limit of the content of the curable resin (B1) is 50% by weight.
• the upper limit of the content of the curable resin (B1) in the entire curable resin (B) is not particularly limited and may be 100% by weight.
• the curable resin (B) includes, for example, a polyfunctional monomer or polyfunctional oligomer (B2) having at least two or more maleimide groups, a polyfunctional monomer having at least two or more vinyl ether groups or allyl groups, or Polyfunctional oligomers (B3) and the like can also be mentioned. These polyfunctional monomers or polyfunctional oligomers are preferably used in combination with the curable resin (B1). By using these polyfunctional monomers or polyfunctional oligomers in combination with the curable resin (B1), the three-dimensional reticulation of the pressure-sensitive adhesive composition by irradiation with light or heating can be performed more efficiently, and the pressure-sensitive adhesive can be obtained. The enhancement of adhesion of the agent composition is further suppressed, and the peelability is also improved.
• the polyfunctional monomer or polyfunctional oligomer (B2) is not particularly limited, but a polyfunctional monomer or polyfunctional oligomer having at least two or more maleimide groups having a molecular weight of 5000 or less is preferable.
• a polyfunctional monomer or polyfunctional oligomer having at least two or more maleimide groups having a molecular weight of 5000 or less is preferable.
• Examples of the bismaleimide having a structure derived from the diamine diamine include a group represented by the general formula (4-1), a group represented by the general formula (4-2), and a group represented by the general formula (4-3). It is preferable to have a structure derived from at least one diamine diamine selected from the group consisting of the group represented by and the group represented by the above general formula (4-4). Of these, the group represented by the above general formula (4-2) is more preferable.
• These polyfunctional monomers or polyfunctional oligomers (B2) may be used alone or in combination of two or more.
• the pressure-sensitive adhesive sheet produced by using the pressure-sensitive adhesive composition can exhibit high flexibility and has high followability to an adherend having irregularities. And also improve the peelability.
• the polyfunctional monomer or polyfunctional oligomer (B3) is not particularly limited, but a polyfunctional monomer or polyfunctional oligomer having at least two or more vinyl ether groups or allyl groups having a molecular weight of 10,000 or less is preferable. Specific examples thereof include triallyl isocyanurate, cyclohexane divinyl ether, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, and Crosmer U (trade name, vinyl ether-terminated polyester). These polyfunctional monomers or polyfunctional oligomers (B3) may be used alone or in combination of two or more.
• the total content of the curable resin (B2) and the curable resin (B3) in the entire curable resin (B) is not particularly limited, but the preferable lower limit is 20% by weight. When the total content of the curable resin (B2) and the curable resin (B3) is 20% by weight or more, the adhesion enhancement of the pressure-sensitive adhesive composition is further suppressed and the peelability is also improved. A more preferable lower limit of the total content of the curable resin (B2) and the curable resin (B3) is 50% by weight.
• the upper limit of the total content of the curable resins (B2) and (B3) in the entire curable resin (B) is not particularly limited and may be 100% by weight. Only one of the curable resin (B2) and the curable resin (B3) may be contained in the pressure-sensitive adhesive composition, or both may be contained in the pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive composition of the present invention preferably further contains a photopolymerization initiator.
• the photopolymerization initiator include those that are activated by irradiating light having a wavelength of 250 to 800 nm.
• the photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, and phosphine oxide derivative compounds. And so on.
• photoradical polymerization of bis ( ⁇ 5-cyclopentadienyl) titanosen derivative compound, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexylphenylketone, 2-hydroxymethylphenylpropane, etc. was started. Agents can be mentioned.
• These photopolymerization initiators may be used alone or in combination of two or more.
• the content of the photopolymerization initiator is not particularly limited, but the preferable lower limit is 0.1 parts by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin (B).
• the content of the photopolymerization initiator is within this range, the entire pressure-sensitive adhesive composition is uniformly and quickly polymerized and crosslinked by irradiation with light, and the elastic modulus is increased, so that the adhesive strength is greatly reduced. Then, it can be easily peeled off.
• the more preferable lower limit of the content of the photopolymerization initiator is 0.3 parts by weight, and the more preferable upper limit is 3 parts by weight.
• the pressure-sensitive adhesive composition of the present invention may further contain a gas generating agent that generates a gas by irradiating with light.
• a gas generating agent that generates a gas by irradiating with light.
• gas generating agent examples include a tetrazole compound or a salt thereof, a triazole compound or a salt thereof, an azo compound, an azide compound, xanthone acetic acid, a carbonate and the like.
• the tetrazole compound or a salt thereof is not particularly limited, and examples thereof include a monotetrazole compound, a bistetrazole compound, an azobistetrazole compound, and salts thereof.
• the monotetrazole compound or a salt thereof specifically, for example, as a monotetrazole compound, 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1- Methyl-5-mercaptotetrazole, 1-methyl-5-ethyl-tetrazole, 1- (dimethylaminoethyl) -5-mercaptotetrazole, 1H-5 hydroxy-tetrazole, 1-methyl-5-ethyltetrazole, 1-propyl- 5-Methyl-tetrazole, 1-phenyl-5-hydroxytetrazole, 1-phenyl-5-mercap
• bistetrazole compound or a salt thereof include 5,5'-bistetrazole diammonium salt, 5,5'-bistetrazole disodium salt, 5,5'-bistetrazole dipiperadium salt and the like.
• azobistetrazole compound include 5,5-azobis-1H-tetrazole, a compound of 5,5-azobis-1H-tetrazole and guanidine, and 5,5-1H-azobistetrazole and methylguanidine.
• These gas generators may be used alone or in combination of two or more. Among them, a bistetrazole compound or a salt thereof is preferable because it is particularly excellent in heat resistance.
• the content of the gas generating agent is not particularly limited, but the preferable lower limit is 5 parts by weight and the preferable upper limit is 50 parts by weight with respect to a total of 100 parts by weight of the silicone-modified polyimide (A) and the curable resin (B). ..
• the content of the gas generating agent is within this range, the pressure-sensitive adhesive composition can exhibit particularly excellent peelability.
• the more preferable lower limit of the content of the gas generating agent is 8 parts by weight, and the more preferable upper limit is 30 parts by weight.
• the pressure-sensitive adhesive composition of the present invention contains, for example, known additives such as a photosensitizer, a heat stabilizer, an antioxidant, an antistatic agent, a plasticizer, a resin, a surfactant, a wax, and a fine particle filler. It may be.
• known additives such as a photosensitizer, a heat stabilizer, an antioxidant, an antistatic agent, a plasticizer, a resin, a surfactant, a wax, and a fine particle filler. It may be.
• the fine particle filler includes an inorganic filler consisting of at least one selected from the group consisting of silicon, titanium, aluminum, calcium, boron, magnesium, cerium and zirconia oxides, talc, mica, and composites thereof. Agents can be mentioned. Of these, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, silica-titania composite oxide or talc is preferable.
• the average particle size of the inorganic filler is not particularly limited, but a preferable lower limit is 0.1 ⁇ m and a preferable upper limit is 30 ⁇ m.
• the content of the inorganic filler is not particularly limited, but the preferable lower limit is 5 parts by weight and the preferable upper limit is 100 parts by weight with respect to a total of 100 parts by weight of the silicone-modified polyimide (A) and the curable resin (B). It is a department.
• the more preferable lower limit of the content of the inorganic filler is 10 parts by weight, and the more preferable upper limit is 50 parts by weight.
• the pressure-sensitive adhesive composition of the present invention preferably has a weight loss rate of 5% by weight or less after heating at 300 ° C. measured at a heating rate of 10 ° C./min after curing, preferably 3% by weight or less. Is more preferable.
• the weight reduction rate is within the above range, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance, so that the increase in adhesion is further suppressed and the peelability is also improved.
• thermogravimetric measuring device STA7200 manufactured by Hitachi High-Tech Science Co., Ltd.
• an ultrahigh pressure mercury lamp is used to irradiate an ultraviolet ray of 365 nm at an intensity of 20 mW / cm 2 for 150 seconds.
• the method for adjusting the weight reduction rate within the above range is not particularly limited, and examples thereof include a method of selecting and using a silicone-modified polyimide (A) or a curable resin (B) having higher heat resistance. Be done.
• Examples of the method for increasing the heat resistance of the silicone-modified polyimide (A) include a method for increasing the content of aromatic groups, a method for lowering the molecular weight of the silicone chain in the constituent unit, and the like.
• the method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, and for example, the silicone-modified polyimide (A), the curable resin (B), and an additive to be blended as necessary are mixed in a bead mill or an ultrasonic wave. Examples thereof include a method of mixing using a sound wave dispersion, a homogenizer, a high-power disperser, a roll mill, and the like.
• An adhesive tape having an adhesive layer made of the adhesive composition of the present invention is also one of the present inventions.
• the pressure-sensitive adhesive tape of the present invention may be a support tape having an pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one or both surfaces of a base material, or a non-support tape having no base material. May be good.
• the base material examples include sheets made of transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, and polyimide. Further, a sheet having a mesh-like structure, a sheet having holes, and the like can also be used.
• transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, and polyimide.
• the pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape of the present invention have an initial adhesive strength, but on the other hand, the adhesion is suppressed, and after the adherend is fixed and subjected to a high-temperature processing treatment of 250 ° C. or higher for a long time or 300 ° C. or higher. Even if it is, it can be easily peeled off. Therefore, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape of the present invention can be suitably used for protecting or temporarily fixing an adherend that is subjected to a high-temperature processing treatment of 250 ° C. or higher for a long time or 300 ° C. or higher.
• the electronic components when processing electronic components such as semiconductors, in order to facilitate the handling of the electronic components and prevent them from being damaged, the electronic components may be fixed to the support plate via an adhesive composition or an adhesive tape.
• the adhesive tape can be suitably used for affixing an adhesive tape to an electronic component to protect it.
• a method for processing electronic components is also one of the present inventions.
• the step (2) of curing the adhesive layer of the adhesive tape of the present invention may be performed immediately before the step (4) of peeling the adhesive tape of the present invention from the electronic component, but it may be performed on the adhesive tape of the present invention. It is preferable to perform this after the step (1) of temporarily fixing the electronic component and before the step (3) of heat-treating the electronic component. As a result, the adhesive tape of the present invention can exhibit more excellent heat resistance.
• an adhesive composition that can be easily peeled off even after undergoing a long time of 250 ° C. or higher or a high temperature processing treatment of 300 ° C. or higher with the adherend fixed. can. Further, according to the present invention, it is possible to provide an adhesive tape having an adhesive layer made of the adhesive composition, and a method for processing an electronic component using the adhesive tape.
• Silicone-modified polyimides (A) having the structures shown in Table 1 were prepared according to the following procedures of Synthesis Examples 1 to 11.
• a Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain a silicone-modified polyimide (A) (Synthesis Example 1).
• the obtained silicone-modified polyimide (A) (Synthesis Example 1) was measured by a gel permeation chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters) as a column.
• the average molecular weight was 6000.
• a Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain a silicone-modified polyimide (A) (Synthesis Example 2).
• the obtained silicone-modified polyimide (A) (Synthesis Example 2) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column. The average molecular weight was 10,000.
• silicone-modified polyimide (A) (Synthesis Example 4).
• the obtained silicone-modified polyimide (A) (Synthesis Example 4) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column. The average molecular weight was 3000.
• silicone-modified polyimide (A) (Synthesis Example 5).
• the obtained silicone-modified polyimide (A) (Synthesis Example 5) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column. The average molecular weight was 50,000.
• a Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize a polyimide having an amine at the end.
• After cooling the reaction mixture to room temperature or lower 2.0 g (0.02 mol) of maleic anhydride was added, and then 35 g (0.35 mol) of methanesulfonic acid anhydride was added.
• the reaction mixture was refluxed for another 12 hours, the reaction mixture was cooled to room temperature, and then filtered through a glass frit funnel filled with silica gel to obtain a silicone-modified polyimide (A) (Synthesis Example 6).
• the obtained silicone-modified polyimide (A) (Synthesis Example 6) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column.
• the average molecular weight was 7000.
• the mixture was cooled to room temperature to obtain a silicone-modified polyimide (A) (Synthesis Example 7).
• the obtained silicone-modified polyimide (A) (Synthesis Example 7) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column.
• the average molecular weight was 8000.
• silicone-modified polyimide (A) (Synthesis Example 9).
• the obtained silicone-modified polyimide (A) (Synthesis Example 9) was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column. The average molecular weight was 5000.
• silicone-modified polyimide (A) (Synthesis Example 10).
• the obtained silicone-modified polyimide (A) (Synthesis Example 10) was measured by a gel permeation chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters) as a column.
• the average molecular weight was 50,000.
• a Dean-Stark tube and a condenser were attached to the flask and the mixture was refluxed for 2 hours to synthesize polyimide. After cooling the reaction mixture to room temperature, 12.8 g (0.13 mol) of maleic anhydride was added, and then 5 g (0.05 mol) of methanesulfonic acid anhydride was added. The reaction mixture was refluxed for another 12 hours, cooled to room temperature, 300 mL of toluene was added to the flask, and impurities were precipitated and removed by standing. The obtained solution was filtered through a glass frit funnel filled with silica gel to obtain a bifunctional maleimide represented by the following formula (11).
• the obtained bifunctional maleimide was measured by a gel permeation chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters) as a column, and the weight average molecular weight was 15,000.
• GPC gel permeation chromatography
• Example 1 300 mL of toluene was prepared.
• 3 parts by weight of Omnirad 819 (manufactured by IGM Resin) was added as a photopolymerization initiator
• 10 parts by weight of silica Leoloseal MT-10, manufactured by Tokuyama Corporation
• the obtained toluene solution of the pressure-sensitive adhesive composition was applied to a corona-treated surface of a 25 ⁇ m-thick polyimide film (Kapton, manufactured by Ube Industries, Ltd.) having a corona treatment on one side so that the thickness of the dry film was 40 ⁇ m.
• it was statically cured at 40 ° C. for 3 days to obtain an adhesive tape.
• the obtained adhesive tape was irradiated with ultraviolet rays of 365 nm at an intensity of 20 mW / cm 2 for 150 seconds using an ultra-high pressure mercury lamp.
• Example 2 Comparative Examples 1 to 2
• An adhesive tape was obtained in the same manner as in Example 1 except that each compounding component was changed as shown in Table 2. Details of the materials shown in Table 2 are shown below.
• -NK Ester A-9300 Ethoxylation Isocyanuric Acid Triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
• Bitetrazole-disodium salt manufactured by Masuda Chemical Co., Ltd.
• an adhesive composition that can be easily peeled off even after undergoing a long time of 250 ° C. or higher or a high temperature processing treatment of 300 ° C. or higher with the adherend fixed. can. Further, according to the present invention, it is possible to provide an adhesive tape having an adhesive layer made of the adhesive composition, and a method for processing an electronic component using the adhesive tape.

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