Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions 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 C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—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
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a polyimide resin, a polyimide varnish, a polyimide film, and a temporary fixing material composition.
• semiconductor electronic components have become lighter and thinner.
• semiconductor chips are made thinner and stacked in multiple layers while being connected using through-silicon vias (TSVs).
• TSVs through-silicon vias
• Technology development is underway.
• semiconductor electronic circuit boards are becoming thinner in order to reduce conduction loss in order to save energy.
• a method for reducing the thickness of a semiconductor electronic circuit forming substrate for example, grinding of the non-circuit-forming surface (back surface) of the semiconductor electronic circuit forming substrate is performed.
• back grind tape (protective tape) is pasted on the opposite side of the grinding surface to prevent damage during grinding, but back grind tape has insufficient heat resistance and is Not suitable for high-temperature processes in the semiconductor field. Therefore, the semiconductor electronic circuit forming substrate is fixed to a supporting substrate such as a silicon wafer or a glass substrate through a temporary fixing material (adhesive layer), and after grinding and backside circuit forming processing, the processed semiconductor A method of peeling a circuit-forming board from a support substrate has been proposed.
• This temporary fixing material is required to have heat resistance, peelability, and low-temperature drying and low-temperature adhesive properties to withstand the manufacturing process of semiconductor electronic components.
• the semiconductor electronic circuit forming substrate and the support substrate can be bonded at low temperatures, can pass through the manufacturing process of semiconductor electronic components that requires heat treatment at 350°C or higher, and can be peeled off with various solvents and laser peeled.
• Temporary fixing materials are required.
• the present invention provides a polyimide resin, a polyimide film, and a polyimide varnish containing the polyimide resin, which has a low elastic modulus, has both low glass transition temperature and heat resistance, has excellent solvent solubility, and has low light transmittance at a wavelength of 355 nm.
• An object of the present invention is to provide a temporary fixing material composition containing the polyimide resin.
• the present inventors have discovered that a polyimide resin containing a combination of structural units derived from a specific tetracarboxylic dianhydride and structural units derived from a specific diamine can solve the above problems, and have completed the invention. .
• X 1 and X 2 are each independently -O-, -C( CH 3 ) 2 -, -C(CF 3 ) 2 -.)
• R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• ⁇ 2> The polyimide resin according to ⁇ 1> above, wherein the ratio of the structural unit (A1) in the structural unit A is 30 to 100 mol%.
• ⁇ 3> The polyimide resin according to ⁇ 1> or ⁇ 2> above, wherein the ratio of the structural unit (B1) in the structural unit B is 30 to 100 mol%.
• ⁇ 4> A group in which the structural unit (A1) is a structural unit (A11) derived from a compound represented by the following formula (a11) and a structural unit (A12) derived from a compound represented by the following formula (a12)
• ⁇ 5> The polyimide resin according to any one of ⁇ 1> to ⁇ 4> above, wherein the structural unit (B1) includes a structural unit (B11) derived from a compound represented by the following formula (b11).
• ⁇ 6> The polyimide resin according to any one of ⁇ 1> to ⁇ 5> above, wherein the structural unit B further includes a structural unit (B2) derived from a compound represented by the following formula (b2). (In the formula, X 3 and X 4 each independently represent -O-, -COO-, -OCO-. n is an integer from 2 to 10.)
• ⁇ 7> The polyimide resin according to any one of ⁇ 1> to ⁇ 6> above, which contains a structural unit represented by the following general formula (3).
• L 1 and L 2 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and m is 1 It is an integer between ⁇ 200.
• a polyimide film comprising the polyimide resin according to any one of ⁇ 1> to ⁇ 7> above.
• a temporary fixing material composition comprising the polyimide resin according to any one of ⁇ 1> to ⁇ 7> above.
• a polyimide resin, a polyimide film, and a polyimide varnish containing the polyimide resin have a low elastic modulus, have both a low glass transition temperature and heat resistance, have excellent solvent solubility, and have a low light transmittance at a wavelength of 355 nm. , and a temporary fixing material composition containing the polyimide resin.
• the polyimide resin of the present invention is a polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, Structural unit A contains a structural unit (A1) derived from a compound represented by the following formula (a1),
• the structural unit B includes a structural unit (B1) derived from a compound represented by the following formula (b1). (wherein, Z is a group represented by the following formula (1) or a group represented by the following formula (2).
• X 1 and X 2 are each independently -O-, -C( CH 3 ) 2 -, -C(CF 3 ) 2 -.)
• R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• the polyimide resin of the present invention has a low elastic modulus, a low glass transition temperature and heat resistance, excellent solvent solubility, and a low light transmittance at a wavelength of 355 nm is not clear, but it is as follows.
• Conceivable Contains a structural unit derived from a specific tetracarboxylic dianhydride having an ether skeleton and a bulky skeleton (trifluoromethyl group or cardo skeleton), and has a structural unit derived from a nonlinear aromatic diamine. It is thought that it has both contradictory properties such as heat resistance (high weight loss temperature) and low glass transition temperature, and also has solubility in solvents and light absorption at a specific wavelength.
• the structural unit A is a structural unit derived from tetracarboxylic dianhydride that occupies the polyimide resin.
• the structural unit A includes a structural unit (A1) derived from a compound represented by the following formula (a1).
• Z is a group represented by the following formula (1) or a group represented by the following formula (2).
• R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• the structural unit A contains the structural unit (A1), the glass transition temperature can be lowered while improving the heat resistance of the polyimide resin. Moreover, solvent solubility and light absorption at a wavelength of 355 nm can be improved.
• the compound represented by formula (a1) preferably contains at least one selected from the group consisting of a compound represented by formula (a11) below and a compound represented by formula (a12) below, and more preferably , a compound represented by the following formula (a11), and a compound represented by the following formula (a12). Particularly from the viewpoint of solvent solubility, a compound represented by the following formula (a11) is preferable, and from the viewpoint of light absorption at a wavelength of 355 nm, a compound represented by the following formula (a12) is preferable.
• the structural unit (A1) is preferably a structural unit (A11) derived from a compound represented by the following formula (a11) and a structural unit (A12) derived from a compound represented by the following formula (a12).
• the structural unit (A11) derived from the compound represented by the following formula (a11) and the structural unit (A11) derived from the compound represented by the following formula (a12) are more preferably At least one selected from the group consisting of A12).
• the structural unit (A11) derived from the compound represented by the following formula (a11) is preferable, and from the viewpoint of light absorption at a wavelength of 355 nm, the structural unit represented by the following formula (a12) is preferable.
• a structural unit (A12) derived from a compound is preferred.
• the compound represented by formula (a11) is 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride (6F-BPADA).
• 6F-BPADA 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride
• the glass transition temperature can be lowered while improving the heat resistance of the polyimide resin.
• solvent solubility and light absorption at a wavelength of 355 nm can be improved.
• the compound represented by formula (a12) is 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (BPF-PA).
• BPF-PA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride
• the structural unit (A1) preferably includes the structural unit (A11), and the structural unit (A1) is more preferably the structural unit (A11).
• the structural unit A may consist only of the structural unit (A1) or may contain structural units other than the structural unit (A1), but preferably, the structural unit other than the structural unit (A1) is further represented by the following formula: Contains a structural unit (A2) derived from the compound represented by (a2).
• L 3 , L 4 , L 5 and L 6 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms.
• Z 1 and Z 2 each independently represent a trivalent aliphatic group or a trivalent aromatic group, and m is an integer from 1 to 200.
• the trivalent aliphatic group or trivalent aromatic group in Z 1 and Z 2 may be substituted with a fluorine atom or may contain an oxygen atom.
• an oxygen atom is included as an ether bond
• the number of carbon atoms shown below refers to all the number of carbon atoms contained in the aliphatic group or aromatic group.
• the trivalent aliphatic group include trivalent saturated or unsaturated aliphatic groups having 1 to 20 carbon atoms.
• the trivalent aliphatic group preferably has 4 to 20 carbon atoms.
• 1 to 3 selected from the group consisting of a group consisting of an alkylene group having 1 to 19 carbon atoms and an alkyleneoxy group having 1 to 19 carbon atoms are bonded to a methylidine group.
• the following groups are mentioned.
• the alkylene group include a methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and dodecamethylene group
• examples of the alkyleneoxy group include: Examples include propyleneoxy group and trimethyleneoxy group.
• Examples of the trivalent unsaturated aliphatic group include a group in which at least one alkenylene group having 2 to 19 carbon atoms is bonded to a methylidine group. Furthermore, an alkylene group or an alkyleneoxy group may be bonded to the methylidine group. Examples of the alkenylene group include a vinylene group and a propenylene group.
• the trivalent aromatic group one to three selected from the group consisting of an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms are used for the arylysine group and methylidine group having 6 to 20 carbon atoms. Included are bonded groups.
• arylene group examples include o-phenylene group, m-phenylene group, p-phenylene group, 4,4'-biphenylylene group, and 2,6-naphthylene group.
• Z 1 and Z 2 are preferably a group in which a trimethylene group and a methylene group are bonded to a methylidine group, a group in which a p-phenylene group or a methylene group is bonded to a methylidine group, and a group in which a trimethylene group and a methylene group are bonded to a methylidine group.
• a group in which a and a methylene group are bonded is more preferable.
• monovalent aliphatic hydrocarbons having 1 to 5 carbon atoms in L 3 to L 6 include monovalent saturated or unsaturated aliphatic groups.
• monovalent saturated aliphatic groups include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, and propyl groups. As the monovalent saturated aliphatic group, a methyl group is preferred.
• monovalent unsaturated aliphatic groups include alkenyl groups having 2 to 5 carbon atoms, such as vinyl groups and propenyl groups. These groups may be substituted with a fluorine atom.
• the monovalent aromatic group having 6 to 10 carbon atoms in L 3 to L 6 of formula (a2) includes an aryl group having 6 to 10 carbon atoms, an aryl group substituted with an alkyl group having 7 to 10 carbon atoms, Examples include aralkyl groups having 7 to 10 carbon atoms.
• an aryl group is preferable, and a phenyl group is more preferable.
• L 3 , L 4 , L 5 and L 6 are preferably at least one selected from the group consisting of a monovalent saturated aliphatic group and a monovalent aromatic group, and are preferably selected from the group consisting of a methyl group and a phenyl group. At least one type is more preferable, and a methyl group is even more preferable.
• m is an integer from 1 to 200, preferably from 10 to 100.
• the compound represented by the following formula (a21) is preferable.
• L 31 and L 41 are each independently a methyl group or a phenyl group, m has the same meaning as m in formula (a2), and the preferred range is also the same.
• m is an integer from 1 to 200, preferably from 10 to 100.
• L 31 and L 41 are each independently a methyl group or a phenyl group, preferably a methyl group. It is preferable that a methyl group is bonded to a silicon atom as L 41 to which a methyl group is bonded as L 31 , and a phenyl group is preferably bonded to a silicon atom as L 41 to a silicon atom to which a phenyl group is bonded as L 31 .
• the functional group equivalent of the compound represented by formula (a2) is preferably 50 to 3,000 g/mol, more preferably 100 to 1,000 g/mol, and even more preferably 150 to 700 g/mol. Note that the functional group equivalent means the mass of the compound represented by formula (a2) per 1 mole of the functional group (carboxy group).
• examples of those that are commercially available include the "X-22-168" series manufactured by Shin-Etsu Chemical Co., Ltd.
• the structural unit A By containing the structural unit (A2), the structural unit A can lower the elastic modulus, and can achieve both a low glass transition temperature and heat resistance.
• the molar ratio [(A1)/(A2)] of the structural unit (A1) and the structural unit (A2) in the structural unit A is preferably 70/30 to 100/0, more preferably 80/20 to 100. /0, more preferably 85/15 to 100/0, even more preferably 85/15 to 99/1, even more preferably 85/15 to 97/3, even more preferably It is from 85/15 to 95/5.
• the structural unit A does not contain the structural unit (A2). By setting this molar ratio, the elastic modulus can be lowered, and both a low glass transition temperature and heat resistance can be achieved.
• the ratio of the structural unit (A1) in the structural unit A is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more from the viewpoint of heat resistance and solvent solubility. and even more preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and still more preferably is 100 mol% or less.
• the structural unit A may consist only of the structural unit (A1).
• the ratio of the structural unit (A2) in the structural unit A is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, still more preferably 0 to 15 mol%, even more preferably The content is 1 to 15 mol%, more preferably 3 to 15 mol%, even more preferably 5 to 15 mol%.
• the total ratio of the structural unit (A1) and the structural unit (A2) in the structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. , and preferably 100 mol% or less.
• the structural unit A may consist only of the structural unit (A1) and the structural unit (A2).
• the structural unit A may contain a structural unit other than the structural unit (A1) and the structural unit (A2).
• the tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but examples thereof include aromatic tetracarboxylic dianhydrides other than the compound represented by formula (a1), alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
• aromatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more aromatic rings
• alicyclic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more alicyclic rings but no aromatic rings
• aliphatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural unit optionally contained in the structural unit A may be of one type, or of two or more types.
• Structural unit B is a structural unit derived from diamine that occupies the polyimide resin.
• Structural unit B includes a structural unit (B1) derived from a compound represented by the following formula (b1). (In the formula, X 1 and X 2 each independently represent -O-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -.)
• X 1 and X 2 each independently represent -O-, -C(CH 3 ) 2 -, or -C(CF 3 ) 2 -.
• X 1 is preferably at least one selected from the group consisting of -O-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 -, and more preferably -O-.
• X 2 is preferably at least one selected from the group consisting of -O-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 -, and more preferably -O-.
• the compound represented by formula (b1) include 1,3-bis(3-aminophenoxy)benzene (TPE-M), 1,3-bis[2-(3-aminophenyl)-2- propyl]benzene, and 1,3-bis[2-(3-aminophenyl)-2-hexafluoropropyl]benzene, more preferably 1,3-bis(3- aminophenoxy)benzene (TPE-M).
• the structural unit (B1) contains a structural unit (B11) derived from a compound represented by the following formula (b11), and more preferably, the structural unit (B1) is represented by the following formula (b11). This is a structural unit (B11) derived from a compound.
• the ratio of the structural unit (B1) in the structural unit B is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% from the viewpoint of heat resistance, colorlessness, and strength.
• the content is more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less.
• the structural unit B may consist only of the structural unit (B1).
• the structural unit B may consist only of the structural unit (B1) or may contain structural units other than the structural unit (B1), but preferably, the structural unit other than the structural unit (B1) is further represented by the following formula: Contains a structural unit (B2) derived from the compound represented by (b2). (In the formula, X 3 and X 4 each independently represent -O-, -COO-, -OCO-. n is an integer from 2 to 10.)
• X 3 and X 4 each independently represent -O-, -COO-, or -OCO-.
• X 3 is preferably at least one selected from the group consisting of -O-, -COO-, and -OCO-, more preferably -O-.
• X 4 is preferably at least one selected from the group consisting of -O-, -COO-, and -OCO-, more preferably -O-.
• the group represented by -OCO- represents a group (carboxylate group) in which the aromatic ring and the carbon atom of X 3 are directly bonded.
• n is an integer of 2 to 10, preferably an integer of 3 to 6, more preferably an integer of 4 to 6.
• the structural unit (B2) is a structural unit (B21) derived from a compound represented by the following formula (b21), a structural unit (B22) derived from a compound represented by the following formula (b22), and a structural unit (B23) derived from the following formula (b23).
• a structural unit (B23) derived from a compound represented by the following formula (B24), a structural unit (B24) derived from a compound represented by the following formula (b24), and a structural unit derived from a compound represented by the following formula (b25) It is preferable to contain at least one structural unit selected from the group consisting of B25), and more preferably to contain a structural unit (B21) derived from a compound represented by the following formula (b21).
• the compound represented by formula (b21) is 4,4'-hexamethylenebisoxyaniline (DA6MG), and the compound represented by formula (b22) is 4,4'-pentamethylenebisoxyaniline (DA5MG).
• the compound represented by formula (b23) is 4,4'-trimethylenebisoxyaniline (DA3MG)
• the compound represented by formula (b24) is hexamethylenebis(4-aminobenzoate).
• the compound represented by formula (b25) is trimethylene bis(4-aminobenzoate).
• the structural unit B includes the structural unit (B2), the elastic modulus can be reduced.
• the molar ratio [(B1)/(B2)] of the structural unit (B1) and the structural unit (B2) in the structural unit B is preferably 30/70 to 100/0, more preferably 40/60 to 100. /0, and from the viewpoint of reducing the elastic modulus and improving laser releasability, the range is more preferably 40/60 to 80/20, even more preferably 40/60 to 60/40.
• the structural unit B does not contain the structural unit (B2).
• the ratio of the structural unit (B2) in the structural unit B is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 20 to 60 mol%, even more preferably It is 40 to 60 mol%.
• the total ratio of the structural unit (B1) and the structural unit (B2) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. , and preferably 100 mol% or less.
• the structural unit B may consist only of the structural unit (B1) and the structural unit (B2).
• the structural unit B may include structural units other than the structural unit (B1) and the structural unit (B2).
• Diamines that provide such structural units include, but are not particularly limited to, aromatic diamines excluding compounds represented by formula (b1) and excluding compounds represented by formula (b2), alicyclic diamines, and Examples include aliphatic diamines.
• aromatic diamine means a diamine containing one or more aromatic rings
• alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring
• Group diamine means a diamine containing neither aromatic ring nor alicyclic ring.
• the number of structural units other than the structural unit (B1) and the structural unit (B2) optionally included in the structural unit B may be one or two or more types.
• the structural unit (B3) derived from the compound represented by the following formula (b3) is preferable.
• L 7 , L 8 , L 9 and L 10 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms.
• Z 3 and Z 4 each independently represent a divalent aliphatic group or a divalent aromatic group, and m is an integer from 1 to 200.
• the divalent aliphatic group or divalent aromatic group in Z 3 and Z 4 may be substituted with a fluorine atom or may contain an oxygen atom.
• the number of carbon atoms shown below refers to all the number of carbon atoms contained in the aliphatic group or aromatic group.
• the divalent aliphatic group include divalent saturated or unsaturated aliphatic groups having 1 to 20 carbon atoms.
• the divalent aliphatic group preferably has 3 to 20 carbon atoms.
• Examples of the divalent saturated aliphatic group include an alkylene group having 1 to 20 carbon atoms and an alkyleneoxy group.
• Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexane group.
• Examples of the alkylene group include a methylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.
• Examples of the alkyleneoxy group include a propyleneoxy group and a trimethyleneoxy group.
• Examples of the divalent unsaturated aliphatic group include alkenylene groups having 2 to 20 carbon atoms, such as vinylene groups, propenylene groups, and alkylene groups having an unsaturated double bond at the end.
• Examples of the divalent aromatic group include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms.
• Specific examples of the arylene group having 6 to 20 carbon atoms in Z 4 and Z 5 include o-phenylene group, m-phenylene group, p-phenylene group, 4,4'-biphenylylene group, 2,6-naphthylene group, etc. can be mentioned.
• Z 3 and Z 4 trimethylene group and p-phenylene group are particularly preferable, and trimethylene group is more preferable.
• monovalent aliphatic hydrocarbons having 1 to 5 carbon atoms in L 7 to L 10 include monovalent saturated or unsaturated aliphatic groups.
• monovalent saturated aliphatic groups include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, and propyl groups.
• monovalent unsaturated aliphatic group include alkenyl groups having 2 to 5 carbon atoms, such as vinyl groups and propenyl groups. These groups may be substituted with a fluorine atom.
• a methyl group is preferred.
• the monovalent aromatic group having 6 to 10 carbon atoms in L 7 to L 10 of formula (b3) includes an aryl group having 6 to 10 carbon atoms, an aryl group substituted with an alkyl group having 7 to 10 carbon atoms, Examples include aralkyl groups having 7 to 10 carbon atoms.
• an aryl group is preferable, and a phenyl group is more preferable.
• L 7 , L 8 , L 9 and L 10 are preferably at least one selected from the group consisting of a monovalent saturated aliphatic group and a monovalent aromatic group, and are preferably selected from the group consisting of a methyl group and a phenyl group. At least one type is more preferable, and a methyl group is even more preferable.
• m is an integer from 1 to 200, preferably from 10 to 100.
• the compound represented by the following formula (b31) is preferable.
• L 71 and L 81 are each independently a methyl group or a phenyl group, m has the same meaning as m in formula (b3), and the preferred range is also the same.
• m is an integer from 1 to 200, preferably from 10 to 100.
• L 71 and L 81 are each independently a methyl group or a phenyl group, preferably a methyl group. Note that it is preferable that a methyl group is bonded as L 81 to a silicon atom to which a methyl group is bonded as L 71 , and it is preferable that a phenyl group is bonded to a silicon atom as L 81 to a silicon atom to which a phenyl group is bonded as L 71 .
• the functional group equivalent (amine equivalent) of the compound represented by formula (b3) is preferably 100 to 5,000 g/mol, more preferably 400 to 4,000 g/mol, and still more preferably 500 to 3,000 g/mol. It is.
• a functional group equivalent means the mass of the compound represented by Formula (b3) per 1 mol of functional groups (amino groups).
• those available as commercial products include “X-22-9409”, “X-22-1660B”, and “X-22” manufactured by Shin-Etsu Chemical Co., Ltd. -161A” and “X-22-161B”.
• the structural unit B can lower the elastic modulus and achieve both a low glass transition temperature and heat resistance.
• the molar ratio of the sum of the structural unit (B1) and the structural unit (B2) in the structural unit B and the structural unit (B3) [((B1)+(B2))/(B3)] is preferably 70/30. -100/0, more preferably 80/20 - 100/0, still more preferably 85/15 - 100/0, even more preferably 85/15 - 99/1, even more preferably is from 85/15 to 97/3, more preferably from 85/15 to 95/5.
• the structural unit B does not contain the structural unit (B3). By setting this molar ratio, the elastic modulus can be lowered, and both a low glass transition temperature and heat resistance can be achieved.
• the ratio of the structural unit (B3) in the structural unit B is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, and still more preferably 0 to 15 mol%.
• the ratio of the compound providing the structural unit (B3) in the structural unit B is preferably 1 to 30 mol%, more preferably 3 to 20 mol%. , more preferably 5 to 15 mol%.
• the total ratio of the structural unit (B1), the structural unit (B2), and the structural unit (B3) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably It is 90 mol% or more, and preferably 100 mol% or less.
• the structural unit B may consist only of the structural unit (B1), the structural unit (B2), and the structural unit (B3).
• the number average molecular weight of the polyimide resin is preferably 5,000 to 300,000 from the viewpoint of mechanical strength of the resulting polyimide film. Note that the number average molecular weight of the polyimide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) equivalent value measured by gel filtration chromatography.
• PMMA polymethyl methacrylate
• the polyimide resin may include a structure other than a polyimide chain (a structure formed by imide bonding of structural unit A and structural unit B). Structures other than polyimide chains that may be included in the polyimide resin include, for example, structures containing amide bonds. It is preferable that the polyimide resin contains a polyimide chain (a structure formed by imide bonding of structural unit A and structural unit B) as a main structure. Therefore, the proportion of polyimide chains in the polyimide resin is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 99% by mass or more. It is. Moreover, it is preferably 100% by mass or less. Even more preferably, it is 100% by mass, and the polyimide resin may consist only of polyimide chains.
• the polyimide resin contains a structural unit represented by the following general formula (3).
• L 1 and L 2 are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and m is 1 It is an integer between ⁇ 200.
• monovalent aliphatic hydrocarbons having 1 to 5 carbon atoms in L 1 and L 2 include monovalent saturated or unsaturated aliphatic groups.
• monovalent saturated aliphatic groups include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, and propyl groups.
• a methyl group is preferred.
• monovalent unsaturated aliphatic group include alkenyl groups having 2 to 5 carbon atoms, such as vinyl groups and propenyl groups. These groups may be substituted with a fluorine atom.
• the monovalent aromatic group having 6 to 10 carbon atoms in L 1 and L 2 of formula (3) includes an aryl group having 6 to 10 carbon atoms, an aryl group substituted with an alkyl group having 7 to 10 carbon atoms, Examples include aralkyl groups having 7 to 10 carbon atoms.
• an aryl group is preferable, and a phenyl group is more preferable.
• L 1 and L 2 are preferably at least one selected from the group consisting of a monovalent saturated aliphatic group and a monovalent aromatic group, and more preferably at least one selected from the group consisting of a methyl group and a phenyl group. , methyl group is more preferred.
• m is an integer from 1 to 200, preferably from 10 to 100.
• the structural unit represented by formula (3) may be introduced into the polyimide resin by any method, and may be present in either the structural unit A or the structural unit B, and the structural unit represented by the formula (3) may be introduced into the polyimide resin without intervening an imide bond. Although it may be combined with the structural unit, it is preferably present in either or both of the structural unit A and the structural unit B, and more preferably in the structural unit A.
• the structural unit represented by formula (3) is present in the structural unit A
• the structural unit is preferably the structural unit (A2).
• the structural unit represented by formula (3) is present in the structural unit B
• the structural unit is preferably the structural unit (B3).
• the method for producing the polyimide resin of the present invention by reacting a compound (tetracarboxylic acid component) that provides the above-mentioned structural unit A with a compound (diamine component) that provides the above-mentioned structural unit B,
• the method is a method for obtaining polyimide resin.
• a polyimide resin can be obtained directly from the tetracarboxylic acid component and the diamine component.
• the polyimide resin is produced by reacting a tetracarboxylic acid component containing a compound that provides the above-mentioned structural unit (A1) with a diamine component that contains a compound that provides the above-mentioned structural unit (B1). can do.
• Examples of the compound that provides the structural unit (A1) include the compound represented by formula (a1), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit.
• Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by formula (a1) and an alkyl ester of the tetracarboxylic acid. Among these, tetracarboxylic dianhydride represented by formula (a1) is preferred.
• examples of the compound that provides the structural unit (A2) include, but are not limited to, compounds represented by formula (a2). It may be a derivative thereof within the range given. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by formula (a2) and an alkyl ester of the tetracarboxylic acid. Among these, tetracarboxylic dianhydride represented by formula (a2) is preferred.
• the molar ratio [(A1)/(A2)] of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) in the tetracarboxylic acid component is preferably 70/30 to 100/0, and more Preferably 80/20 to 100/0, more preferably 85/15 to 100/0, even more preferably 85/15 to 99/1, even more preferably 85/15 to 97/3 and even more preferably 85/15 to 95/5.
• the tetracarboxylic acid component does not contain the compound that provides the structural unit (A2). By setting this molar ratio, the elastic modulus can be lowered, and both a low glass transition temperature and heat resistance can be achieved.
• the ratio of the compound providing the structural unit (A1) in the tetracarboxylic acid component is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably from the viewpoint of heat resistance and solvent solubility. 70 mol% or more, even more preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more. , and preferably 100 mol% or less.
• the tetracarboxylic acid component may consist only of the compound that provides the structural unit (A1).
• the ratio of the compound providing the structural unit (A2) in the tetracarboxylic acid component is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, and still more preferably 0 to 15 mol%, Even more preferably it is 1 to 15 mol%, even more preferably 3 to 15 mol%, even more preferably 5 to 15 mol%.
• the total ratio of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) in the tetracarboxylic acid component is more preferably 90 mol% or more, and preferably 100 mol% or less.
• the tetracarboxylic acid component may consist only of a compound that provides the structural unit (A1) and a compound that provides the structural unit (A2).
• the tetracarboxylic acid component may contain a tetracarboxylic dianhydride other than the compound providing the structural unit (A1) and the compound providing the structural unit (A2).
• tetracarboxylic dianhydrides include, but are not particularly limited to, aromatic tetracarboxylic dianhydrides other than the compound represented by formula (a1), alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides. Examples include tetracarboxylic dianhydride.
• the tetracarboxylic dianhydride optionally included in the tetracarboxylic acid component may be one type or two or more types.
• Examples of the compound that provides the structural unit (B1) include the compound represented by formula (b1), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit.
• Examples of the derivative include diisocyanates corresponding to the compound (diamine) represented by formula (b1). Among these, the compound represented by formula (b1) (ie, diamine) is preferred.
• the diamine component may contain a structural unit other than the compound that provides the structural unit (B1), but preferably further contains a compound that provides the structural unit (B2) derived from the compound represented by formula (b2).
• examples of the compound that provides the structural unit (B2) include, but are not limited to, compounds represented by formula (b2). It may be a derivative thereof within the range given. Examples of the derivative include diisocyanates corresponding to the compound (diamine) represented by formula (b2). Among these, the compound represented by formula (b2) (ie, diamine) is preferred.
• the molar ratio [(B1)/(B2)] of the compound providing the structural unit (B1) and the compound providing the structural unit (B2) in the diamine component is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, more preferably 40/60 to 80/20, even more preferably 40/60 to 60/40, from the viewpoint of reducing the elastic modulus and improving laser releasability. be.
• the diamine component does not contain the compound that provides the structural unit (B2).
• the ratio of the compound providing the structural unit (B1) in the diamine component is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more from the viewpoint of heat resistance, colorlessness, and strength. It is mol% or more, still more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less.
• the diamine component may consist only of the compound that provides the structural unit (B1).
• the ratio of the compound providing the structural unit (B2) in the diamine component is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 20 to 60 mol%, and even more Preferably it is 40 to 60 mol%.
• the total ratio of the compound providing the structural unit (B1) and the compound providing the structural unit (B2) in the diamine component is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. It is mol% or more, and preferably 100 mol% or less.
• the diamine component may consist only of a compound that provides the structural unit (B1) and a compound that provides the structural unit (B2).
• the diamine component may contain diamines other than the compound providing the structural unit (B1) and the compound providing the structural unit (B2).
• Diamines that provide such structural units include, but are not particularly limited to, aromatic diamines excluding compounds represented by formula (b1) and excluding compounds represented by formula (b2), alicyclic diamines, and Examples include aliphatic diamines.
• the diamines other than the structural unit (B1) and the structural unit (B2) optionally included in the diamine component may be one type or two or more types.
• the compounds that provide the structural unit (B3) are preferred.
• the tetracarboxylic acid component contains a compound that provides the structural unit (B3)
• examples of the compound that provides the structural unit (B3) include, but are not limited to, compounds represented by formula (b3). It may be a derivative thereof within the range given. Examples of the derivative include diisocyanates corresponding to the compound (diamine) represented by formula (b3). Among these, the compound represented by formula (b3) (ie, diamine) is preferred.
• the sum of the compound giving the structural unit (B1) and the compound giving the structural unit (B2) in the diamine component and the molar ratio of the compound giving the structural unit (B3) [((B1)+(B2))/(B3) ] is preferably 70/30 to 100/0, more preferably 80/20 to 100/0, even more preferably 85/15 to 100/0, even more preferably 85/15 to 99 /1, even more preferably 85/15 to 97/3, even more preferably 85/15 to 95/5.
• the diamine component is the compound that provides the structural unit (B3). Does not include.
• the ratio of the compound providing the structural unit (B3) in the diamine component is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, and still more preferably 0 to 15 mol%.
• the ratio of the compound that provides the structural unit (B3) in the diamine component is preferably 1 to 30 mol%, more preferably 3 to 20 mol%.
• the content is more preferably 5 to 15 mol%.
• the total ratio of the compound providing the structural unit (B1), the compound providing the structural unit (B2), and the compound providing the structural unit (B3) in the diamine component is preferably 50 mol% or more, more preferably 70 mol % or more, more preferably 90 mol% or more, and preferably 100 mol% or less.
• the diamine component may consist only of a compound that provides the structural unit (B1), a compound that provides the structural unit (B2), and a compound that provides the structural unit (B3).
• the charging ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component per 1 mol of the tetracarboxylic acid component.
• a terminal capping agent may be used in the production of the polyimide resin.
• the terminal capping agent monoamines or dicarboxylic acids are preferable.
• the amount of the terminal capping agent to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
• Examples of monoamine terminal capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Examples include ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like, with benzylamine and aniline being preferred.
• dicarboxylic acid terminal capping agent dicarboxylic acids are preferred, and a portion thereof may be ring-closed.
• phthalic acid for example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2 -dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc., with phthalic acid and phthalic anhydride being preferred.
• the specific reaction method is as follows: (1) A tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, stirred at 0 to 80°C for 0.5 to 30 hours, and then heated to imidize. Method of conducting the reaction, (2) After charging the diamine component and the reaction solvent into a reactor and dissolving them, charging the tetracarboxylic acid component and stirring at room temperature of 0 to 80 ° C.
• Examples include a method in which the imidization reaction is carried out by raising the temperature thereafter, and (3) a method in which the tetracarboxylic acid component, the diamine component, and the reaction solvent are charged into a reactor and the temperature is immediately raised to carry out the imidization reaction.
• the organic solvent (reaction solvent) used in the production of polyimide resin may be any organic solvent as long as it does not inhibit the imidization reaction and can dissolve the polyimide resin produced. Examples include aprotic solvents, phenolic solvents, ether solvents, carbonate solvents, and the like.
• aprotic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, 3-methoxy-N,N- Amide solvents such as dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide, lactone solvents such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, etc.
• GBL ⁇ -butyrolactone
• ⁇ -valerolactone diethylene glycol dimethyl ether
• triethylene glycol triethylene glycol
• triethylene glycol dimethyl ether etc.
• Glycol solvents examples include phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, acetone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.
• Examples include ketone solvents, amine solvents such as picoline and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
• phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -xylenol, 3,5-xylenol, etc.
• ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
• carbonate-based solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
• aprotic solvents are preferred, amide solvents and lactone solvents are more preferred, and lactone solvents are more preferred.
• the above reaction solvents may be used alone or in combination of two or more.
• imidization catalysts include base catalysts and acid catalysts.
• the base catalyst include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole,
• organic base catalysts such as N,N-dimethylaniline and N,N-diethylaniline
• inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
• examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned.
• the above imidization catalysts may be used alone or in combination of two or more.
• it is preferable to use a base catalyst more preferably to use an organic base catalyst, and even more preferably to use at least one selected from the group consisting of triethylamine and triethylenediamine.
• the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C from the viewpoint of reaction rate and suppression of gelation and the like. Further, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• the polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
• the organic solvent is not particularly limited as long as it dissolves the polyimide resin, but it is preferable to use the compounds described above as a reaction solvent used in the production of the polyimide resin alone or in a mixture of two or more.
• the polyimide varnish of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or it may be a polyimide solution obtained by further adding a solvent to dilute the polyimide solution. good.
• the polyimide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyimide resin of the present invention.
• the viscosity of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
• the viscosity of the polyimide varnish is a value measured at 25°C using an E-type viscometer.
• the polyimide varnish of the present invention may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, etc.
• the method for producing the polyimide varnish of the present invention is not particularly limited, and known methods can be applied.
• the temporary fixing material composition of the present invention contains the polyimide resin. Therefore, the polyimide varnish can also be used as a temporary fixing material composition.
• the temporary fixing material composition of the present invention is preferably one in which the polyimide resin of the present invention is dissolved in an organic solvent. That is, the temporary fixing material composition of the present invention preferably contains the polyimide resin of the present invention and an organic solvent, and it is more preferable that the polyimide resin is dissolved in the organic solvent.
• the organic solvent is not particularly limited as long as it dissolves the polyimide resin, but it is preferable to use the compounds described above as a reaction solvent used in the production of the polyimide resin alone or in a mixture of two or more.
• the temporary fixing material composition of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or it may be a polyimide solution obtained by further adding a solvent to dilute the polyimide solution. There may be.
• the polyimide resin of the present invention Since the polyimide resin of the present invention has solvent solubility, it can be made into a highly concentrated temporary fixing material composition that is stable at room temperature.
• the temporary fixing material composition of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyimide resin of the present invention.
• the viscosity of the temporary fixing material composition is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
• the viscosity of the temporary fixing material composition is a value measured at 25° C. using an E-type viscometer.
• the temporary fixing material composition of the present invention may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, and leveling agents within the range that does not impair the required properties of the polyimide resin and the temporary fixing material. , an antifoaming agent, a fluorescent whitening agent, a crosslinking agent, a polymerization initiator, a photosensitizer, and other various additives.
• the polyimide film of the present invention contains the polyimide resin. Therefore, the polyimide film of the present invention has a low elastic modulus, is compatible with a low glass transition temperature and heat resistance, has excellent solvent solubility, and has a low light transmittance at a wavelength of 355 nm.
• the light transmittance at a wavelength of 355 nm when the thickness is 30 ⁇ m is preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.2% or less, and even more Preferably it is 0.1% or less.
• the glass transition temperature is preferably 210°C or lower, more preferably 180°C or lower, even more preferably 160°C or lower.
• the 5% weight loss temperature is preferably 450°C or higher, more preferably 480°C or higher, and still more preferably 500°C or higher.
• the weight loss rate when held at 350° C. for 60 minutes is preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.4% or less.
• the tensile modulus when the thickness is 30 ⁇ m is preferably 3.0 GPa or less, more preferably 2.6 GPa or less, and still more preferably 2.3 GPa or less.
• the above-mentioned physical property values in the present invention can be specifically measured by the method described in the Examples.
• the polyimide film of the present invention contains the polyimide resin described above, has a low elastic modulus, has both a low glass transition temperature and heat resistance, has excellent solvent solubility, and has a low light transmittance at a wavelength of 355 nm. Therefore, the polyimide film of the present invention can be suitably used as a temporary fixing material by forming the polyimide film of the present invention on a semiconductor electronic circuit forming substrate by the above method.
• the thickness of the polyimide film of the present invention is not particularly limited, but when used as a temporary fixing material, it is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 8 to 80 ⁇ m. , more preferably 10 to 80 ⁇ m.
• the thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.
• the thickness can be easily controlled by adjusting the solid content concentration and viscosity of the temporary fixing material composition.
• the method for producing the polyimide film of the present invention there is no particular restriction on the method for producing the polyimide film of the present invention, and known methods can be used.
• a method may be mentioned in which the varnish of the present invention is applied onto a support and heated.
• a method may be used in which the varnish is applied onto a smooth support such as a glass plate, metal plate, or plastic, and then organic solvents such as reaction solvents and diluting solvents contained in the varnish are removed by heating.
• a polyimide varnish containing the polyimide resin of the present invention is suitably used as a raw material for a temporary fixing material.
• a semiconductor electronic circuit forming substrate is used as the support.
• the coating method examples include known coating methods such as spin coating, slit coating, and blade coating. Among these, spin coating is preferable from the viewpoint of improving film uniformity and workability.
• the method of removing the organic solvent contained in the varnish by heating is to evaporate the organic solvent at a temperature of 150°C or lower to make it tack-free, and then heat the varnish to a temperature higher than the boiling point of the organic solvent used (although not particularly limited). It is preferable to dry at a temperature of 200 to 500°C. Moreover, it is preferable to dry under an air atmosphere or a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure, or increased pressure.
• the method for peeling off the polyimide film formed on the support is not particularly limited, but includes a laser lift-off method, a method using a sacrificial layer for peeling (preliminary coating of a release agent on the surface of the support), and a method using a sacrificial layer for peeling. method of adding a release agent) and a method of adding a release agent. Note that when the polyimide film of the present invention is used as a temporary fixing material, the semiconductor electronic circuit forming substrate and the supporting substrate are peeled off and the temporary fixing material is finally removed. A method of dissolving the material, and a method of peeling off by irradiating a laser from the support substrate side are used.
• Thickness of polyimide film The thickness of the polyimide film was measured using a digital gauge "SA-S110/03N" manufactured by Citizen Fine Device Co., Ltd.
• the total light transmittance and YI of the polyimide film are based on JIS K7361-1:1997, and the YI is ASTM E313-05 (D light source, 65°) for the polyimide film after peeling from the glass plate. All measurements were conducted using a simultaneous color and turbidity meter "COH7700" manufactured by Nippon Denshoku Kogyo Co., Ltd., in accordance with the above.
• the greater the total light transmittance value of the polyimide film the more excellent the transparency of the polyimide resin.
• the larger the YI value of the polyimide film the better the colorlessness of the polyimide resin.
• the light transmittance of the polyimide film at a wavelength of 355 nm was determined by the following method for the polyimide film after it was peeled off from the glass plate. Measurement was performed using an ultraviolet-visible near-infrared spectrophotometer "UV-3600Plus+MPC-603A" manufactured by Shimadzu Corporation. The smaller the value of the light transmittance at a wavelength of 355 nm, the better the LLO (laser lift-off) releasability. In Table 1, " ⁇ 0.1" indicates "less than 0.1%”.
• Tg Glass transition temperature
• 5% weight loss temperature (Td5%) A simultaneous differential thermogravimetric measurement device "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample (polyimide film) was heated from 40°C to 50°C at a heating rate of 10°C/min, held at 150°C for 30 minutes to remove moisture, and then heated to 500°C. The temperature at which the weight decreased by 5% compared to the weight after being held at 150° C. for 30 minutes was defined as the 5% weight loss temperature. The larger the weight loss temperature value (temperature) is, the better the heat resistance is. In Table 1, those with Td5% exceeding 500°C (those whose weight loss did not reach 5% even at 500°C) were designated as ">500".
• Weight reduction rate (%) A simultaneous differential thermogravimetric measurement device "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample (polyimide film) was heated from 40°C to 150°C at a heating rate of 10°C/min, held at 150°C for 30 minutes to remove moisture, and then heated to 350°C. Based on the weight when reaching 350°C, the weight loss rate after holding at 350°C for 60 minutes was defined as the weight loss rate. The smaller the weight reduction rate, the better the heat resistance.
• a low water absorption solvent can be used in the stripping process, and it is less affected by humidity and moisture during stripping, which is preferable.
• TPE-M 1,3-bis(3-aminophenoxy)benzene (compound represented by formula (b11), manufactured by Seika Co., Ltd.)
• DA5MG 4,4'-pentamethylenebisoxyaniline (compound represented by formula (b22), manufactured by Seika Co., Ltd.)
• Example 1 29.234 g (0.100 mol) of TPE-M was placed in a 500 mL 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark fitted with a cooling tube, a thermometer, and a glass end cap. ) and 136.802 g of GBL were added, the system temperature was set to 70° C. under a nitrogen atmosphere, and the mixture was stirred at a rotational speed of 200 rpm to obtain a solution.
• the obtained polyimide varnish was applied onto the silicon wafer by spin coating, held at 120 °C for 20 minutes on a hot plate, and then heated at 220 °C for 30 minutes in a hot air dryer in an air atmosphere to evaporate the solvent.
• a polyimide film was obtained. Table 1 shows the physical properties and evaluation results of the film.
• Examples 2, 3, 5 and comparative example 2 A solution containing a polyimide resin was obtained in the same manner as in Example 1, except that 6F-BPADA was changed to the tetracarboxylic acid component shown in Table 1. GBL was added to the resulting solution to make it uniform so that the solid content concentration was 20% by mass, thereby obtaining a polyimide varnish containing a polyimide resin. Subsequently, the obtained polyimide varnish was applied onto the silicon wafer by spin coating, held at 120 °C for 20 minutes on a hot plate, and then heated at 220 °C for 30 minutes in a hot air dryer in an air atmosphere to evaporate the solvent. A polyimide film was obtained. Table 1 shows the physical properties and evaluation results of the film.
• Example 4 A solution containing a polyimide resin was obtained in the same manner as in Example 1 except that TPE-M was changed to the diamine component shown in Table 1. GBL was added to the resulting solution to make it uniform so that the solid content concentration was 20% by mass, thereby obtaining a polyimide varnish containing a polyimide resin. Subsequently, the obtained polyimide varnish was applied onto the silicon wafer by spin coating, held at 120 °C for 20 minutes on a hot plate, and then heated at 220 °C for 30 minutes in a hot air dryer in an air atmosphere to evaporate the solvent. A polyimide film was obtained. Table 1 shows the physical properties and evaluation results of the film.
• Comparative example 1 A solution containing a polyimide resin was obtained in the same manner as in Example 1, except that 6F-BPADA was changed to the tetracarboxylic acid component shown in Table 1. GBL was added to the obtained solution so that the solid content concentration was 20% by mass, but it was not compatible with GBL and could not be homogenized. Therefore, NMP was added to the obtained solution to make it uniform so that the solid content concentration was 20% by mass, thereby obtaining a polyimide varnish containing a polyimide resin.
• the polyimide resin (polyimide film) of the example has a low light transmittance at a wavelength of 355 nm, a high weight loss temperature despite a low glass transition temperature, a low elastic modulus, and a GBL. It also has excellent solvent solubility for cyclohexanone. From this, the polyimide resin of the present invention has a low elastic modulus and a low glass transition temperature, and therefore has excellent low-temperature adhesive properties. Moreover, since the polyimide resin of the present invention exhibits a high weight loss temperature, it also has heat resistance in the manufacturing process of semiconductor electronic components.
• the polyimide resin of the present invention has a low light transmittance at a wavelength of 355 nm, so laser peeling is possible, and since it has excellent solvent solubility for GBL and cyclohexanone, it can be seen that solvent peeling is possible with various solvents.
• the polyimide resin of the present invention can be suitably used as a temporary fixing material, and a temporary fixing material composition containing the polyimide resin has the above-mentioned excellent properties.

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• 2023
  • 2023-09-08 CN CN202380065556.6A patent/CN119866354A/zh active Pending
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