Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring

Definitions

• the present invention relates to a thermosetting resin composition, a cured product thereof, a method for producing a structure using the thermosetting resin composition, and a structure containing the cured product.
• the encapsulant which is a plastic material, is also required to have high heat resistance.
• transfer molding the material is heated and softened in the plunger, and the heated and softened material is pushed into the heated mold cavity through the flow path in the mold such as a gate, sprue, and runner, and inside the mold cavity. It is a method of curing with. Since the material is injected into the cavity in a highly fluid state, it can be molded at low pressure. Transfer molding is characterized in that it is less likely to damage the insert than other molding methods that require high pressure. Transfer molding is known as a typical molding method in sealing molding of power semiconductors and ICs because it can be miniaturized and microfabricated and has high productivity.
• thermosetting resin compositions containing a large amount of polyfunctional epoxy resin, bismaleimide, triazine skeleton, benzoxazine skeleton, and silsesquioki Thermosetting resin compositions and the like containing a highly heat-resistant structure such as a sun skeleton have been proposed.
• Patent Document 1 Japanese Unexamined Patent Publication No. 11-14277 describes (A) a phenol resin containing 30 to 100 parts by mass of a novolak-structured phenol resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule. (B) An epoxy resin containing 30 to 100 parts by mass of a novolak-structured epoxy resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule, (C) an inorganic filler, and (D) a curing accelerator. Describes an epoxy resin composition for encapsulating a semiconductor, which is characterized by being an essential component.
• Patent Document 2 Japanese Unexamined Patent Publication No. 5-43630 describes an aromatic bismaleimide containing N, N'-(alkyl-substituted diphenylmethane) bismaleimide and polyallylphenol from condensed polyphenol of salicylaldehyde and phenol. Describes the resin composition.
• Patent Document 3 Japanese Unexamined Patent Publication No. 5-6869 describes (A) a maleimide compound having two or more maleimide groups in one molecule, (B) an allylated phenol resin having a specific repeating unit, and (C). A semiconductor device in which a semiconductor element is sealed using a resin composition containing a curing catalyst is described.
• Patent Document 4 Japanese Unexamined Patent Publication No. 6-93047 describes a curable resin composition in which a maleimide compound, an alkenylphenol compound having a specific structure, and an epoxy group-containing organic silane compound are blended in a specific ratio.
• Japanese Unexamined Patent Publication No. 11-14277 Japanese Unexamined Patent Publication No. 5-43630 Japanese Unexamined Patent Publication No. 5-6869 Japanese Unexamined Patent Publication No. 6-93047
• the heat resistance of the molded product is improved by using the bismaleimide resin as compared with the epoxy-phenolic thermosetting resin material which has been conventionally used (Patent Documents 2 to 4).
• the conventional encapsulant using bismaleimide resin has a drawback that the adhesion to other members, particularly metal materials, is very low as compared with the epoxy-phenolic thermosetting resin material.
• the electronic device contains metal parts such as a conductor and copper that is responsible for cooling, and if peeling occurs between the metal and the sealing material, there is a problem in terms of internal protection. Therefore, it is an issue to improve the adhesion between the metal and the sealing material.
• thermosetting resin composition having excellent adhesion to a metal and adhesiveness without impairing moldability is described.
• thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure according to the formula (1), and a radical initiator (D).
• R 1 and R 2 are hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, carboxy groups, or amino groups, and at least one of R 1 and R 2 is an amino group.
• R 3 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group
• R 4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there.
• the compound (C) is 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5-.
• the above aspect 1 comprises at least one selected from bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole.
• the thermocurable resin composition according to the above. [3] The thermosetting resin composition according to the above aspect 2, wherein the compound (C) contains at least one selected from 5-aminoindazole and 6-aminoindazole. [4]
• the contents of the compound (C) are 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A) and the polymaleimide compound (B).
• the thermosetting resin composition according to any one of.
• thermosetting resin composition according to any one of the above aspects 1 to 4, wherein the amount of the polyalkenylphenol compound (A) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymaleimide compound (B). .. [6]
• the polyalkenylphenol compound (A) is represented by the formula (2) -1 :.
• equation (2) -2 In formulas (2) -1 and (2) -2, R 5 independently has a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms, respectively.
• R 6 Represents an alkoxy group of 5, and R 6 is an independent formula (3):
• R 7 , R 8 , R 9 , R 10 and R 11 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and carbon atoms, respectively. It is a cycloalkyl group of number 5 to 10 or an aryl group having 6 to 12 carbon atoms, where * in the formula (3) represents a bond with a carbon atom constituting an aromatic ring, and R 5 and R 6 are.
• thermosetting resin composition each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• the thermosetting resin composition according to any one of the above aspects 1 to 5.
• thermosetting resin composition When the average number of structural units shown in formula (2) -1 per molecule is p and the average number of structural units shown in formula (2) -2 per molecule is q, p is 1.1 to The thermosetting resin according to the above aspect 6, wherein 35 is a real number, p + q is a real number of 1.1 to 35, and q is a real number having a value of the formula: p / (p + q) of 0.4 to 1. Composition. [8] The thermosetting resin composition according to any one of the above aspects 1 to 7, wherein the polymaleimide compound (B) is an aromatic bismaleimide compound. [9] The thermosetting resin composition according to any one of the above aspects 1 to 8, wherein the radical initiator (D) is an organic peroxide.
• the thermosetting resin composition according to the above aspect 10 wherein the filler (E) is at least one selected from the group consisting of silica, alumina, magnesium oxide and solid rubber particles.
• the content of the filler (E) is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D).
• the thermosetting resin composition according to the above aspect 10 or 11 which is 200 to 1900 parts by mass.
• a method for producing a structure wherein the thermosetting resin composition according to any one of the above aspects 1 to 12 is molded by molding.
• thermosetting resin composition having excellent adhesion and adhesiveness to a metal without impairing moldability.
• the thermosetting resin composition of the present disclosure can be cured in an appropriate time and gives excellent productivity.
• a highly reliable cured product can be formed by using the thermosetting resin composition of the present disclosure.
• thermosetting resin composition of one embodiment contains a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure represented by the formula (1), and a radical initiator (D). Including.
• the polyalkenylphenol compound (A) is a compound having at least two phenol skeletons in the molecule and having a 2-alkenyl group bonded to a part or all of the aromatic ring forming the phenol skeleton in the molecule. ..
• a group having a structure represented by the formula (3) is preferable.
• R 7 , R 8 , R 9 , R 10 and R 11 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, or carbons, respectively. It is an aryl group having 6 to 12 atoms. * In the formula (3) represents a bond with a carbon atom constituting an aromatic ring.
• alkyl group having 1 to 5 carbon atoms constituting R 7 , R 8 , R 9 , R 10 and R 11 in the formula (3) include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like.
• Specific examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group and the like.
• the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group and the like. It is preferable that the 2-alkenyl group represented by the formula (3) is an allyl group, that is, R 7 , R 8 , R 9 , R 10 and R 11 are all hydrogen atoms.
• a 2-alkenyl group is contained in preferably 40 to 100%, more preferably 60 to 100%, still more preferably 80 to 100% of the total aromatic rings forming the phenol skeleton. It is combined.
• Known basic skeletons of the polyalkenylphenol compound (A) include phenol novolac resin, cresol novolac resin, triphenylmethane-type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin.
• the skeleton of phenolic resin can be mentioned.
• the polyalkenylphenol compound (A) having the following formula (2) -1 and optionally the structural unit represented by the formula (2) -2 can be preferably used.
• the structural units represented by the formulas (2) -1 and (2) -2 are preferable phenol skeleton units constituting the polyalkenylphenol compound (A), and the binding order of these phenol skeleton units is not particularly limited.
• R 5 is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, respectively, and is represented by the formula (2).
• R 6 is a 2-alkoxy group independently represented by the formula (3).
• R 5 and R 6 may be the same or different for each phenol skeleton unit.
• Equation (2) -1 and the formula (2) each Q is at -2 independently formula -CR 12 R 13 - in the alkylene group represented, a cycloalkylene group having 5 to 10 carbon atoms, divalent having an aromatic ring , A divalent organic group having an alicyclic condensed ring, or a divalent organic group in combination thereof.
• R 12 and R 13 are independently hydrogen atoms and alkyl having 1 to 5 carbon atoms, respectively.
• p is preferably 1.
• a real number of 1 to 35, p + q is a real number of 1.1 to 35, and q satisfies a real number in which the value of the formula: p / (p + q) is 0.4 to 1.
• alkyl group having 1 to 5 carbon atoms constituting R 5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and n. -Pentyl group and the like can be mentioned.
• alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group and the like. Can be mentioned.
• cycloalkyl groups having 5 to 10 carbon atoms include cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, cycloheptyl groups and the like, and have carbon atoms.
• aryl groups 6 to 12 include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group and the like.
• cycloalkylene group having 5 to 10 carbon atoms constituting Q include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group and the like.
• divalent organic group having an aromatic ring include a phenylene group, a tolylen group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4-methylenediphenyl group and the like.
• the number of carbon atoms of the divalent organic group having an aromatic ring can be 6 to 20 or 6 to 14.
• divalent organic group having an alicyclic condensed ring examples include a dicyclopentadienylene group and the like.
• the number of carbon atoms of the divalent organic group having an alicyclic condensed ring can be 7 to 20 or 7 to 10.
• Q is a dicyclopentadienylene group, a phenylene group, a methylphenylene group, a xylylene group, or a biphenylene group in terms of high mechanical strength of the cured product. Since the viscosity of the polyalkenylphenol compound (A) is low and it is advantageous for mixing with the polymaleimide compound (B), it is preferable that Q is ⁇ CH 2 ⁇ .
• P is preferably a real number of 1.1 to 35, more preferably a real number of 2 to 30, and even more preferably a real number of 3 to 10.
• the thermal decomposition start temperature when the cured product of the thermosetting resin composition is placed in a high temperature environment is appropriate, and when p is 35 or less, the viscosity of the thermosetting resin composition Is in a suitable range depending on the processing at the time of molding.
• P + q is preferably a real number of 1.1 to 35, more preferably a real number of 2 to 30, and even more preferably a real number of 3 to 10.
• p + q is 1.1 or more, the thermal decomposition start temperature when the cured product of the thermosetting resin composition is placed in a high temperature environment is appropriate, and when it is 35 or less, the viscosity of the thermosetting resin composition Is in a suitable range depending on the processing at the time of molding.
• q is preferably a real number having a value of the formula: p / (p + q) of 0.4 to 1, and more preferably a real number having a value of the formula: p / (p + q) of 0.6 to 1. More preferably, it is a real number in which the value of the formula: p / (p + q) is 0.8 to 1. Equation: When the value of p / (p + q) is 1, q is 0. That is, in this embodiment, the polyalkenylphenol compound (A) does not contain the structural unit represented by the formula (2) -2.
• the polyalkenylphenol compound (A) can consist of the structural units represented by the formula (2) -1.
• q is a value satisfying the above conditions, the degree of curing of the thermosetting resin composition can be made sufficient depending on the application.
• the preferred number average molecular weight Mn of the polyalkenylphenol compound (A) is 300 to 5000, more preferably 400 to 4000, and even more preferably 500 to 3000.
• the thermal decomposition start temperature is appropriate when the cured product of the thermosetting resin composition is placed in a high temperature environment, and when it is 5000 or less, the viscosity of the thermosetting resin composition. Is in a suitable range depending on the processing at the time of molding.
• the polyalkenylphenol compound (A) can be obtained by converting a part of the hydroxyl groups of the raw material phenol resin into alkenyl ether and then rearranging the 2-alkenyl group by the Claisen rearrangement reaction.
• the raw material phenol resin a known phenol resin having a structural unit represented by the following formula (2) -2 can be preferably used.
• raw material phenol resin of the polyalkenylphenol compound (A) include phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, phenol-dicyclopentadiene copolymer resin and the like. Can be mentioned.
• the 2-alkenyl etherification reaction of the raw material phenol resin includes (i) a known method for reacting a halogenated 2-alkenyl compound such as allyl chloride, methallyl chloride, and allyl bromide with a phenol compound, and (ii) allyl acetate.
• a halogenated 2-alkenyl compound such as allyl chloride, methallyl chloride, and allyl bromide with a phenol compound
• allyl acetate Two known methods of reacting such a carboxylic acid 2-alkenyl compound with a phenol compound can be exemplified.
• the method described in JP-A-2-91113 can be used.
• the method described in JP-A-2011-26253 can be used as a method for reacting the carboxylic acid 2-alkenyl compound with the phenol resin.
• the amount of the halogenated 2-alkenyl compound or the carboxylic acid 2-alkenyl compound used with respect to the phenolic hydroxyl group is preferably 0.4 to 5.0 equivalents, more preferably 0.6 to 4.0 equivalents.
• the 2-alkenyl etherification reaction is carried out by mixing the 2-alkenyl compound with the raw material phenol resin and reacting for 4 to 40 hours. In the 2-alkenyl etherification reaction, a solvent in which the raw material phenol resin dissolves can be used.
• the reaction can also be carried out without a solvent using a carboxylic acid 2-alkenyl compound capable of dissolving the raw material phenol resin.
• the 2-alkenyl etherification rate of the raw material phenol resin is determined by using a larger amount of the halogenated 2-alkenyl compound or the carboxylic acid 2-alkenyl compound than the above amount and adjusting the reaction time to be shorter than the above reaction time. It can also be controlled by suppressing the reaction rate (conversion rate) of the 2-alkenyl compound to a low level.
• the target polyalkenylphenol compound (A) can be obtained by subjecting the polyalkenyl ether compound produced by the method according to (i) or (ii) above to a Claisen rearrangement reaction.
• the Claisen rearrangement reaction can be carried out by heating the polyalkenyl ether compound to a temperature of 100 to 250 ° C. and reacting it for 1 to 20 hours.
• the Claisen rearrangement reaction may be carried out using a solvent having a high boiling point, or may be carried out without a solvent.
• Inorganic salts such as sodium thiosulfate and sodium carbonate can also be added to promote the rearrangement reaction. Details are disclosed in, for example, Japanese Patent Application Laid-Open No. 2-911113.
• the polymaleimide compound (B) is a compound having two or more maleimide groups represented by the formula (4).
• * represents an aromatic ring or a bond with an organic group containing a straight chain, a branched chain or a cyclic aliphatic hydrocarbon group.
• polymaleimide compound (B) examples include bismaleimide such as bis (4-maleimidephenyl) methane, trismaleimide such as tris (4-maleimidephenyl) methane, and tetraxmaleimide such as bis (3,4-dimaleimidephenyl) methane. And polymaleimide such as poly (4-maleimide styrene).
• polymaleimide compound examples include an aromatic polymaleimide compound and an aliphatic polymaleimide compound, and the aromatic polymaleimide compound is preferable in that the obtained cured product has particularly excellent flame retardancy.
• An aromatic polymaleimide compound is a compound having two or more maleimide groups represented by the formula (4), and these maleimide groups are bonded to the same or different aromatic rings.
• Specific examples of the aromatic ring include a monocyclic ring such as benzene, a condensed ring such as naphthalene and anthracene, and the like.
• the polymaleimide compound (B) is preferably an aromatic bismaleimide compound and an aliphatic bismaleimide compound, and more preferably an aromatic bismaleimide compound because it mixes well in the thermosetting resin composition. ..
• aromatic bismaleimide compound examples include bis (4-maleimidephenyl) methane, bis (3-maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, and bis (3,5-dimethyl-).
• 4-maleimidephenyl) methane bis (3-ethyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, bis (3-propyl-4-maleimidephenyl) methane, bis ( 3,5-Dipropyl-4-maleimidephenyl) methane, bis (3-butyl-4-maleimidephenyl) methane, bis (3,5-dibutyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimide) -5-Methylphenyl) methane, 2,2-bis (4-maleimidephenyl) propane, 2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, bis (4-maleimidephenyl) ether, bis (3-Maleimidephenyl) ether, bis (4-maleimidephenyl) ketone, bis (3-maleimidephenyl)
• aliphatic bismaleimide compound examples include bis (4-maleimidecyclohexyl) methane and bis (3-maleimidecyclohexyl) methane. Of these, bis (4-maleimidephenyl) methane and 2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane are preferable. Examples of commercially available products include the BMI (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) series.
• the blending amount of the polyalkenylphenol compound (A) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and 20 to 20 to 150 parts by mass. It is more preferably 130 parts by mass.
• the compounding amount is 5 parts by mass or more, the fluidity at the time of molding is better.
• the compounding amount is 200 parts by mass or less, the heat resistance of the cured product is better.
• Compound (C) is represented by the formula (1).
• R 1 and R 2 are hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, carboxy groups, or amino groups, and at least one of R 1 and R 2 is an amino group.
• R 3 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group
• R 4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is a compound represented by).
• one of R 1 and R 2 is preferably a hydrogen atom
• both R 3 and R 4 are preferably hydrogen atoms.
• halogen atom constituting R 1 or R 2 include a chlorine atom, a bromine atom, an iodine atom and the like.
• alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
• R 1 or R 2 other than the amino group a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a hydroxyl group and a carboxy group are preferable, and a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group and a carboxy group are more preferable.
• Hydrogen atom is more preferable.
• alkyl group having 1 to 3 carbon atoms constituting R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
• alkenyl group having 2 to 3 carbon atoms include a vinyl group and an allyl group.
• R 3 a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an allyl group, and a cyano group are preferable, a hydrogen atom, a methyl group, an ethyl group, and a cyano group are more preferable, and a hydrogen atom is further preferable.
• alkyl group having 1 to 3 carbon atoms constituting R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
• R 4 a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is further preferable.
• Examples of the compound (C) include 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, and 6-amino-5.
• Examples thereof include -bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole.
• 6-aminoindazole and 5-aminoindazole are preferable because they are excellent in adjusting the gel time and having an affinity for the metal surface, particularly copper. By controlling the gel time within an appropriate range, it is considered that the wetting of the thermosetting resin composition with respect to the substrate can be improved.
• the curing rate of compound (C) can be adjusted in the curing reaction by radical polymerization. Without being bound by any theory, it is believed that the aniline moiety of compound (C) temporarily traps and stabilizes radicals, thereby adjusting the curing rate of the thermosetting resin composition.
• the radical polymerization rate is generally adjusted by the amount of the radical polymerization initiator. If the radical polymerization reaction rate of the composition is too fast, the initial curing of, for example, 0 to 30 seconds after the start of molding and curing proceeds in a state where sufficient wetting with respect to the base material cannot be ensured, and the distance between the cured product and the base material is increased. Sufficient adhesion is not obtained.
• the amount of the radical polymerization initiator is reduced in order to slow down the radical polymerization, not only the initial curing but also the reaction rate in the middle stage of curing, for example, 30 seconds to 180 seconds after the start of molding curing, becomes slow, which is sufficient for removing the molded product from the mold. It takes longer to reach the desired hardness and productivity is reduced.
• the compound (C) it is possible to prevent a decrease in productivity due to a delay in the curing rate while sufficiently ensuring wetting with respect to the base material.
• the pyrazole ring has higher chemical stability than the imidazole ring, which has a similar heterocyclic structure, and has a very high polymerization activity on the polymaleimide compound (B), which is catalyzed by the imidazole ring and causes a polymerization reaction. Low. This point is also excellent in terms of adjusting the curing speed.
• compound (C) has a high affinity for metals, and the amino group, which is at least one of R 1 and R 2 , is an ethylenically unsaturated bond contained in the maleimide group of the polymaleimide compound (B).
• compound (C) is covalently fixed in the molded product.
• the compound (C) can act as a coupling agent between the resin and the metal surface, and can develop a strong adhesive force between the cured product and the metal base material.
• the content of the compound (C) can be appropriately determined depending on the intended use, but is 0.05 parts by mass to 0.05 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A) and the polymaleimide compound (B). It is preferably 5 parts by mass, more preferably 0.2 parts by mass to 3 parts by mass, and further preferably 0.3 parts by mass to 2.5 parts by mass. If it is 0.05 part by mass or more, the adhesion to copper is better, and if it is 5 parts by mass or less, the function of adjusting the curing speed can be fully exhibited and the quick curing property can be maintained. Thereby, the appearance of the molded product and the moldability of the thermosetting resin composition can be improved.
• thermosetting resin composition can be promoted by blending the radical initiator (D) with the thermosetting resin composition.
• the radical initiator (D) is preferably a thermal radical initiator.
• the thermal radical initiator include organic peroxides.
• the organic peroxide is preferably an organic peroxide having a 10-hour half-life temperature of 100 to 170 ° C., specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-).
• the preferable amount of the radical initiator (D) to be used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C). , More preferably 0.05 to 7.5 parts by mass, and even more preferably 0.1 to 5 parts by mass.
• the amount of the radical initiator (D) used is 0.01 parts by mass or more, the curing reaction proceeds sufficiently, and when it is 10 parts by mass or less, the storage stability of the thermosetting resin composition is better.
• the thermosetting resin composition may further contain a filler (E).
• the type of the filler (E) is not particularly limited, and examples thereof include solid rubber particles such as solid silicone rubber particles, organic fillers such as silicone powder, and inorganic fillers such as silica, alumina, magnesium oxide, and boron nitride. It can be appropriately selected depending on the intended use.
• the filler (E) is preferably at least one selected from the group consisting of silica, alumina, magnesium oxide, and solid rubber particles.
• thermosetting resin composition when used for semiconductor encapsulation, it is preferable to add an insulating inorganic filler in order to obtain a cured product having a low coefficient of thermal expansion.
• the inorganic filler is not particularly limited, and known materials can be used. Specific examples of the inorganic filler include silica such as amorphous silica and crystalline silica, and particles such as alumina, boron nitride, aluminum nitride, and silicon nitride. From the viewpoint of reducing the viscosity, spherical amorphous silica is desirable.
• the inorganic filler may be surface-treated with a silane coupling agent or the like, but may not be surface-treated.
• the average particle size of the filler (E) is preferably 0.1 to 30 ⁇ m, and more preferably the maximum particle size is 100 ⁇ m or less, particularly 75 ⁇ m or less. When the average particle size is in this range, the viscosity of the thermosetting resin composition is appropriate at the time of use, and the injectability into a narrow pitch wiring portion or a narrow gap portion is also appropriate.
• the average particle size referred to here is a volume cumulative particle size D 50 measured by a laser diffraction / scattering type particle size distribution measuring device.
• the content of the filler (E) in the thermosetting resin composition can be appropriately determined according to the application.
• the content of the filler (E) in the thermosetting resin composition is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D).
• it is preferably 200 to 1900 parts by mass, more preferably 300 to 1000 parts by mass, and further preferably 300 to 600 parts by mass.
• thermosetting resin composition As other additives, a defoaming agent, a coloring agent, a phosphor, a denaturing agent, a leveling agent, a light diffusing agent, a flame retardant, an adhesion imparting agent, a mold release agent, a coupling agent, etc. are blended in the thermosetting resin composition. It is also possible to do.
• various waxes such as ester waxes such as carnauba wax and montanic acid ester wax, amide-based waxes such as lauric acid amide, stearic acid amide, and N-stearyl erucate amide, polyethylene, and polyethylene oxide are appropriately selected. can do.
• examples of the coupling agent include vinyl triethoxysilane, vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N-phenyl-3.
• -A silane coupling agent such as aminopropyltrimethoxysilane can be mentioned.
• the coupling agent may be used alone or in combination of two or more.
• the blending amount of the coupling agent in the thermosetting resin composition is preferably 0.1 to 5% by mass. When the blending amount is 0.1% by mass or more, the effect of the coupling agent is sufficiently exhibited, and when it is 5% by mass or less, the melt viscosity, the hygroscopicity and the strength of the cured product are more good.
• thermosetting resin composition The method for preparing the thermosetting resin composition is as long as the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), the radical initiator (D), and other optional components can be uniformly mixed and dispersed. There is no particular limitation.
• the method of first melting and mixing the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C), and then adding the radical initiator (D) and any additive is to make each material uniform. It is preferable because it is easy to mix.
• each component is not particularly limited.
• Reaction vessel pot mill, two-roll mill, three-roll mill, rotary mixer, twin-screw mixer, dispenser, single-screw or twin-screw (same direction or different direction) extruder, kneader, etc. It can be mixed by putting it in a mixer and stirring or kneading it.
• a rotary mixer is preferable because the stirring conditions can be easily changed, and industrially, a twin-screw mixer is preferable from the viewpoint of productivity.
• Each mixer can be used by appropriately changing the stirring conditions.
• the method is not particularly limited as long as the resin is not melted by the heat generated in the work process, but it is convenient to use an agate mortar if the amount is small.
• a commercially available crusher it is preferable that the amount of heat generated during crushing is small in order to suppress the melting of the mixture.
• the particle size of the powder is preferably 1 mm or less.
• thermosetting resin composition can be melted by heating.
• a structure can be produced by molding the melted thermosetting resin composition into an arbitrary preferable shape, curing it if necessary, and removing the mold.
• molding molding particularly transfer molding and compression molding are preferable.
• preferable conditions for transfer molding for example, in the case of a mold having a size of 10 mm ⁇ 75 mm ⁇ 3 mm, the temperature of the top plate and the mold is 170 to 190 ° C., the holding pressure is 50 to 150 kg / cm 2 , and the holding time is set. It can be 1.5 to 10 minutes.
• the temperature of the top plate and the mold is 170 to 190 ° C.
• the molding pressure is 5 to 20 MPa
• the pressurizing time is 1. It can be 5 to 10 minutes.
• the thermosetting resin composition can be cured by heating.
• the curing temperature is preferably 130 to 300 ° C, more preferably 150 to 230 ° C, and even more preferably 150 to 200 ° C.
• the curing temperature is 130 ° C. or higher, the thermosetting resin composition before curing can be sufficiently melted and easily filled in the mold, and the mold can be easily removed after curing.
• the curing temperature is 300 ° C. or lower, thermal deterioration or volatilization of the material can be avoided.
• the heating time can be appropriately changed depending on the thermosetting resin composition and the curing temperature, but 0.1 to 24 hours is preferable from the viewpoint of productivity. This heating may be performed in a plurality of times.
• the final curing temperature is preferably 250 ° C. or lower, preferably 230 ° C. or lower, without curing at an excessively high temperature, for example, by raising the temperature as the curing progresses. Is more preferable.
• thermosetting resin composition can be used, for example, in applications such as semiconductor encapsulants, prepregs, interlayer insulating resins, solder resists, and die attaches.
• a structure of 30 mm ⁇ 30 mm ⁇ 5 mmt in which the molding time was lengthened by 30 s, 60 s and 15 s at 180 ° C. was prepared by a compression mold, respectively, and the structure obtained by using a type D durometer compliant with JIS K 7215 (1986). Body hardness was measured at 180 ° C. The time (seconds) required for the hardness to exceed 85 is defined as the curing time.
• the adhesiveness to metal is evaluated from the viewpoint of shear adhesive force.
• As the adherend base material a base material of oxygen-free copper (C1020) having a size of 18 mm ⁇ 14 mm ⁇ 1.6 mmt is used.
• the adherend is immersed in acetone for 5 minutes, immersed in 5% by mass sulfuric acid for 5 minutes, washed twice or more with ion-exchanged water, and dried at 50 ° C. for 10 minutes before use.
• a thermosetting resin composition is formed on the surface of the adherend base material into a conical tower shape (a circle having a ground contact portion of 3 mm ⁇ , a height of 3 mm, and an upper portion of 1.5 mm ⁇ ) using a transfer molding machine.
• the molding conditions are a mold temperature of 180 ° C., a holding pressure of 100 kg / cm 2 , and a holding time of 3 minutes.
• a lead frame is used in which the material is rolled oxygen-free copper (C1020), the outer dimensions are 52 mm in width, 38 mm in length, and 0.5 mm in thickness, and the bed is 18 mm in length and width in the center.
• the pretreatment of the lead frame is performed under the same conditions as the pretreatment of the adherend base material in the shear adhesion test.
• a thermosetting resin composition is used to seal the bed around the center of the lead frame with outer dimensions of 30 mm in length, 30 mm in width, and 3 mm in thickness. Sealing was performed by molding a thermosetting resin composition using a transfer molding machine under the conditions of a mold temperature of 180 ° C., a holding pressure of 100 kg / cm 2, and a holding time of 3 minutes.
• test piece after the reflow test is analyzed in the same manner as in the post-molding adhesion test, and the obtained value is determined as the post-reflow adhesion.
• For the production method refer to Example 1 of JP-A-2016-28129.
• BMI-4000 (2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, Daiwa Kasei Kogyo Co., Ltd.)
• BMI-1100H bis (4-maleimidephenyl) methane, Daiwa Kasei Kogyo Co., Ltd.
• thermosetting resin composition 35 parts by mass of BRG-APO as the polyalkenylphenol compound (A), 65 parts by mass of BMI-4000 as the polymaleimide compound (B), 1.5 parts by mass of Park Mill D as the radical initiator (D), filler ( 400 parts by mass of MSR5100 treated with KBM-603 as E) and 0.35 parts by mass of 5-aminoindazole as compound (C) were mixed and melt-kneaded (2 rolls manufactured by Toyo Seiki Seisakusho Co., Ltd.). At 110 ° C. for 10 minutes) at a diameter of 8 inches).
• thermosetting resin composition was obtained.
• a powdery thermosetting resin composition was compacted into a tablet shape by a tableting machine (manufactured by Fuji Yakuhin Machinery Co., Ltd.).
• a tableting machine manufactured by Fuji Yakuhin Machinery Co., Ltd.
• thermosetting resin composition was produced and evaluated in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 1.
• Examples 1 to 6 the structure could be easily removed from the mold, and the moldability was good.
• the shear adhesive force, the adhesion rate after molding, and the adhesion rate after reflow were high, and the adhesion to the metal and the adhesiveness were excellent.
• the gel times of Examples 1 to 6 were in an appropriate range.
• the curing times of Examples 1 to 6 were in an appropriate range, and the productivity was also excellent.
• Comparative Examples 1 to 5 the shear adhesive force and the adhesion after molding, particularly the adhesion after reflow, were low, and the adhesiveness and adhesion to the metal, particularly the adhesion after the reflow test, were poor.

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