CN117098789A - Maleimide resin mixture, curable resin composition, prepreg, and cured product thereof - Google Patents

Maleimide resin mixture, curable resin composition, prepreg, and cured product thereof Download PDF

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Publication number
CN117098789A
CN117098789A CN202280026458.7A CN202280026458A CN117098789A CN 117098789 A CN117098789 A CN 117098789A CN 202280026458 A CN202280026458 A CN 202280026458A CN 117098789 A CN117098789 A CN 117098789A
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Prior art keywords
acid
diamine
maleimide resin
bis
derived
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土方大地
桥本昌典
关允谕
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • 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
    • C08G73/12—Unsaturated 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The maleimide resin mixture of the present invention comprises a maleimide resin (A) represented by the following formula (1) and a maleimide resin (B) obtained by reacting a diamine (B) with maleic anhydride.

Description

Maleimide resin mixture, curable resin composition, prepreg, and cured product thereof
Technical Field
The present invention relates to a maleimide resin mixture, a curable resin composition, a prepreg, and a cured product thereof, and is suitable for use in light-weight high-strength materials such as semiconductor packages, printed wiring boards, electrical electronic components such as build-up (build-up) laminates, carbon fiber reinforced plastics, glass fiber reinforced plastics, and 3D printing applications.
Background
In recent years, as the field of use of laminated boards for mounting electrical and electronic components has been expanding, characteristics have been demanded to be widely increased. Conventionally, although semiconductor chips (chips) are mainly mounted on metal lead frames, many semiconductor chips (chips) having high processing capability such as CPUs are mounted on laminated boards made of polymer materials. As the speed of devices such as CPUs increases, it is considered important to solve the problems of signal delay and transmission loss, and laminated boards made of polymer materials are required to have a low dielectric constant and a low dielectric tangent.
In addition, from the viewpoint of development of communication technology, in recent years, 5G operation of devices has been increasing, and it is expected that communication devices using millimeter waves and quasi-millimeter waves of 10GHz or more, particularly 28GHz or more, are being increased explosively, and substrate materials corresponding to high frequencies are being demanded in base stations, antennas and communication devices. Among these substrate materials and the like, in order not to reduce the transfer speed, a high degree of dielectric characteristics (in particular, dielectric tangent) has been regarded as important, and materials that can be stably used in these fields have been demanded.
In addition, because of the popularization of portable electronic devices such as mobile phones, precision electronic devices are required to be used and carried in outdoor environments or around the human body, and thus durability against external environments (particularly, damp-heat environments) is required in substrate materials. Further, in the automotive field, there is a case where precision electronic devices are arranged in the vicinity of the engine, and heat resistance and moisture resistance are demanded at a higher level.
A wiring board using BT resin which is a resin of bisphenol a type cyanate ester compound and bismaleimide compound disclosed in patent document 1 and is used in combination has been widely used as a high-performance wiring board in the past because of excellent heat resistance, chemical resistance, dielectric characteristics, and the like, but improvement is required to cope with the higher performance as described above.
Among them, maleimide resins, which have been commercially available, have significantly improved heat resistance and exhibit excellent dielectric characteristics in a high-frequency range, compared to epoxy resins and the like, which have been conventionally used for the above-mentioned applications. However, maleimide resins having high heat resistance have disadvantages of low moisture resistance, rigidity, vulnerability, and low adhesion to copper foil.
On the other hand, maleimide resins such as patent documents 2 and 3 have been developed, but it has been difficult to achieve the sufficient effect.
In addition, although a composition comprising a maleimide resin and a phenol resin containing an acryl group as in patent document 4 has been proposed, there is a problem that a phenolic hydroxyl group which does not participate in the reaction remains at the time of the hardening reaction, and thus the dielectric characteristics are insufficient and the water absorption rate is high.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] Japanese patent publication No. 54-3040
[ patent document 2] Japanese patent laid-open No. 03-100016
[ patent document 3] Japanese patent No. 5030297
[ patent document 4] Japanese patent laid-open No. 04-359911
[ patent document 5] Japanese patent publication No. 04-75222
[ patent document 6] Japanese patent publication No. 06-37465.
Disclosure of Invention
[ problem to be solved by the invention ]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a maleimide resin mixture, a curable resin composition, and a cured product thereof, which exhibit excellent heat resistance, mechanical properties, and dielectric properties after moisture absorption.
[ means for solving the problems ]
The present inventors have made intensive studies to solve the above problems, and as a result, they have completed the present invention. That is, the present invention relates to the following [1] to [11].
[1]
A maleimide resin mixture comprising a maleimide resin (A) represented by the following formula (1) and a maleimide resin (B) obtained by reacting a diamine (B) with maleic anhydride;
( In the formula (1), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
[2]
The maleimide resin mixture according to the above item [1], wherein the aforementioned component (b) is obtained by reacting a diamine (b-1) having 4 to 60 carbon atoms with a tetracarboxylic dianhydride (b-2).
[3]
The maleimide resin mixture according to the above [2], wherein the aforementioned component (b-1) is a diamine (b-1 a) derived from a dimer acid.
[4]
The maleimide resin mixture according to the above item [2] or [3], wherein the component (b-2) is represented by the following formula (4).
[5]
The maleimide resin mixture according to any of the above items [1] to [4], wherein the aforementioned component (A) is represented by the following formula (2),
( In the formula (2), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
[6]
The maleimide resin mixture according to any of the preceding items [1] to [5], wherein the aforementioned component (B) is represented by the following formula (3).
(in the formula (3), R 1 Represents a 2-valent hydrocarbon group (c) derived from a dimer acid, R 2 Represents a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from the dimer acid, R 3 Represents any one selected from the group consisting of a 2-valent hydrocarbon group (c) derived from a dimer acid and a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from a dimer acid, R 4 R is R 5 Each independently represents 1 or more organic groups selected from a 4-valent organic group having 4 to 40 carbon atoms and having a single-ring alicyclic structure or a condensed polycyclic alicyclic structure, a 4-valent organic group having 8 to 40 carbon atoms and having both an alicyclic structure and an aromatic ring, wherein the organic groups having a single-ring alicyclic structure are linked directly or via a crosslinked structure. m is an integer of 1 to 30, n is an integer of 0 to 30, R 4 R is R 5 May be the same or different. )
[7]
The maleimide resin mixture according to any of the preceding items [1] to [6], wherein the weight ratio of the aforementioned component (A) to the aforementioned component (B) is 99/1 to 60/40.
[8]
A curable resin composition comprising the maleimide resin mixture according to any of the preceding items [1] to [7 ].
[9]
The maleimide resin mixture according to the above item [8], further comprising a hardening accelerator.
[10]
A prepreg comprising a fibrous substrate having a sheet-like structure and the maleimide resin mixture according to any one of the above items [1] to [7], or the curable resin composition according to the above item [8] or [9 ].
[11]
A cured product obtained by curing the maleimide resin mixture according to any one of the above items [1] to [7], the curable resin composition according to the above item [8] or [9], or the prepreg according to the above item [10 ].
[ Effect of the invention ]
The maleimide resin mixture and the cured product of the curable resin composition of the present invention are excellent in heat resistance, mechanical properties and dielectric properties after moisture absorption.
Drawings
FIG. 1 GPC chart of Synthesis example 1.
FIG. 2 GPC chart of synthetic example 2.
Detailed Description
The maleimide resin mixture of the present invention contains a maleimide resin (hereinafter, also referred to as component (a)) represented by the following formula (1) and a maleimide resin (B) (hereinafter, also referred to as component (B)), wherein the maleimide resin (B) is obtained by reacting a diamine (B) with maleic anhydride.
( In the formula (1), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
In the above formula (1), m is usually 0 to 3, more preferably 0 to 2, still more preferably 0.R is usually a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but is more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom. When m is more than 3 or R is an alkyl group having 6 or more carbon atoms, there is a concern that the electrical characteristics may be lowered due to molecular vibration when the alkyl group is exposed to high frequency.
In the above formula (1), the value of n can be calculated from the value of the number average molecular weight obtained by measurement of the gel permeation chromatography (GPC, detector: RI) of maleimide resin or from the respective area ratio of the separated peaks.
In the above formula (1), when n=1, the solubility in a solvent is low, and when n is 5 or more, the fluidity at the time of molding is poor, and the characteristics as a cured product cannot be sufficiently exhibited.
The component (a) is preferably one having a molecular weight distribution, and in the formula (1), the content obtained by GPC analysis (RI) of n=1 body is preferably 98 area% or less, more preferably 20 to 90 area%, still more preferably 30 to 80 area%, particularly preferably 40 to 80 area%. When the content of n=1 bodies is 98 area% or less, heat resistance becomes good. In addition, crystallinity is lowered, and solvent solubility is improved. On the other hand, when the lower limit of n=1 is 20 area% or more, the viscosity of the resin solution is lowered and the impregnation property is improved. In addition, since the solvent can be removed at a low temperature when the polymer is taken out as a solid, self-polymerization is difficult to occur, and the workability becomes easy.
The component (A) has excellent solvent solubility and can improve dielectric characteristics in a cured product thereof by increasing the proportion of an asymmetric structure having different orientations with respect to maleimide groups. The orientation ratio in the n=1 body of the above formula (1) can be determined from HPLC analysis (225 nm), and the ortho-para-position is more preferably 30 area% or more and less than 60 area%, still more preferably 35 area% or more and less than 55 area%, and particularly preferably 40 area% or more and less than 55 area% of the total n=1 body.
The softening point of the component (A) is more preferably 50℃to 150 ℃, still more preferably 80℃to 120 ℃, still more preferably 90℃to 120 ℃, particularly preferably 95℃to 120 ℃. Further, the melt viscosity at 150℃is preferably 0.05 to 100 Pa.s, more preferably 0.1 to 40 Pa.s.
The compound represented by the above formula (1) is more preferable when represented by the following formula (2). In the formula (1), the crystallinity is lowered when the substitution position of the propyl group for the benzene ring to which the maleimide group is not bonded is compared with the para position.
( In the formula (2), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
The preferable range of R, m in the above formula (2) is the same as that of the above formula (1).
The following description is directed to a method for producing the component (a), but is not limited to the present method.
[ method for producing aromatic amine resin ]
The component (a) may use an aromatic amine resin represented by the following formula (5) as a precursor.
( In the formula (5), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
The preferable range of R, m in the above formula (5) is the same as that of the above formula (1).
The method for producing the aromatic amine resin represented by the formula (5) is not particularly limited, and for example, in patent document 5, an n=1 body in the formula (5) is obtained as a main component by reacting aniline with m-diisopropenylbenzene or m-di (α -hydroxyisopropyl) benzene in the presence of an acidic catalyst at 180 to 250 ℃. The n=1 isomer contains 3 isomers of a compound having the same symmetrical structure for the aniline 2 molecule of 1, 3-bis (p-aminoisopropyl) benzene, 1, 3-bis (o-aminoisopropyl) benzene, or a compound having different asymmetrical structures for the aniline 2 molecule of 1- (o-aminoisopropyl) -3- (p-aminoisopropyl) benzene. In addition, n=2 to 5 forms are also produced as subcomponents, but these were purified by crystallization in patent document 5 to obtain 1, 3-bis (p-aminoisopropyl) benzene with a purity of 98%. In patent document 6, N' - (1, 3-phenylene-bis- (2, 2-propylene) -bis-p-phenylene) bismaleimide is synthesized by maleinizing 1, 3-bis (p-aminocumyl) benzene to obtain a crystalline product, but this is required to be heated in order to dissolve in a solvent, and if left at room temperature after heating, the crystallization is completely precipitated over several hours. Therefore, when the resin composition is adjusted, there is a possibility that crystals may be precipitated, and the higher the concentration of N, N' - (1, 3-phenylene-bis- (2, 2-propylene) -bis-p-phenylene) bismaleimide is, the higher the possibility of crystallization is. In order to produce a printed wiring board or a composite material, although a glass cloth or carbon fiber is impregnated into a varnish to adhere the resin, the impregnation work is impossible if crystals are precipitated, and on the other hand, if the temperature is raised to maintain a dissolved state, the reaction of the composition is too fast, and the usable time of the varnish becomes short.
Examples of the acidic catalyst used in the synthesis of the aromatic amine resin represented by the above formula (5) include acidic catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferrous chloride, aluminum chloride, p-toluenesulfonic acid and methanesulfonic acid. In the present invention, a protonic acid such as hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, etc. is preferable. These may be used singly or in combination. The amount of the catalyst to be used is preferably 1 to 12% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 7% by weight, based on 100% by weight of the aniline to be used, and if more than 12% by weight, the desired asymmetric compound is small, and the compound having a symmetrical structure is preferably completed. On the other hand, if the content is less than 1%, the reaction may not be completed, as well as the progress of the reaction may be slow.
The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or may be carried out without a solvent. For example, when the catalyst contains water after adding an acidic catalyst to a mixed solution of aniline and a solvent, it is preferable to remove water from the system by azeotropic distillation. After that, diisopropenylbenzene or bis (α -hydroxyisopropyl) benzene is added, and thereafter, the temperature is raised while removing the solvent from the system, and the reaction is carried out at 140 to 190 ℃, preferably 160 to 190 ℃ for 5 to 50 hours, more preferably 5 to 30 hours. When the reaction temperature is too high, the asymmetric structure is bonded after formation, and the symmetric structure is preferentially completed, so that the solvent solubility and electrical properties as the purposes cannot be exerted. When bis (α -hydroxyisopropyl) benzene is used, water is by-produced, and therefore, the bis (α -hydroxyisopropyl) benzene is removed from the system while azeotroping with the solvent when the temperature is raised. After the reaction, the acidic catalyst was neutralized with an aqueous alkali solution, and then a water-insoluble organic solvent was added to the oil layer to repeat the water washing until the wastewater became neutral, followed by removal of the solvent and the excess aniline derivative under reduced pressure and heating. When activated clay or ion exchange resin is used, the reaction mixture is filtered to remove the catalyst after the reaction is terminated.
In addition, since phenylamine is produced by two-fold production depending on the reaction temperature or the kind of the catalyst, it is preferable to remove it if necessary. The diphenyl amine derivative is removed at a high temperature and under a high vacuum or by means such as steam distillation to 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less.
The compound represented by the formula (5) is more preferably a compound represented by the following formula (5-a).
( In the formula (5-a), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is a repetition number, and the average value of n is more than 1 and less than 5. )
A preferable range of R, m in the above formula (5-a) is the same as that of the above formula (1).
[ method for producing maleimide resin ]
The component (a) is obtained by an addition or dehydration condensation reaction of the aromatic amine resin represented by the formula (5) obtained in the above step with maleic acid or maleic anhydride (hereinafter also referred to as "maleic anhydride") in the presence of a solvent and a catalyst.
The solvent used in the reaction is preferably a water-insoluble solvent because the water produced in the reaction must be removed from the system. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl isobutyl ketone and cyclopentanone, and the like are exemplified, but the present invention is not limited thereto, and 2 or more kinds may be used in combination.
In addition, aprotic polar solvents may be used in addition to the aforementioned water-insoluble solvents. Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazoline dione, and N-methyl-2-pyrrolidone (Methyl pyrrolidone), and 2 or more kinds thereof may be used in combination. When an aprotic polar solvent is used, it is preferable to use a water-insoluble solvent having a boiling point higher than that of the solvent used in combination.
The catalyst acidic catalyst used in the reaction is not particularly limited, but examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, and the like. The amount of the acid catalyst used is usually 0.1 to 10% by weight, more preferably 1 to 5% by weight, relative to the aromatic amine resin.
For example, an aromatic amine resin represented by the above formula (5) is dissolved in toluene and N-methyl-2-pyrrolidone (Methyl pyrrolidone), maleic anhydride is added thereto to produce amic acid, and then p-toluenesulfonic acid is added thereto, and the reaction is carried out while removing the produced water from the system under reflux conditions.
Alternatively, maleic acid is dissolved in toluene, and an N-methyl-2-pyrrolidone (Methyl pyrrolidone) solution of the aromatic amine resin represented by the above formula (5) is added with stirring to produce an amic acid, after which p-toluenesulfonic acid is added thereto, and the reaction is carried out while removing the produced water from the system under reflux conditions.
Alternatively, maleic anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and while dropping a solution of N-methyl-2-pyrrolidone (Methyl pyrrolidone) of the aromatic amine resin represented by the above formula (5) in a stirred/refluxed state, water azeotroped in the middle is removed to the outside of the system, and toluene is returned to the system and reacted (the above is the first-stage reaction).
In any of the methods, maleic anhydride is generally used in an amount of 1.0 to 3.0 equivalents, more preferably 1.2 to 2.0 equivalents, relative to the amine groups of the aromatic amine resin represented by the above formula (5).
In order to reduce the number of non-ring-closed amic acids, water is added to the reaction solution after the above-mentioned maleinization reaction, and the reaction solution is separated into a resin solution layer and an aqueous layer, and the excess maleic acid or maleic anhydride, aprotic polar solvent, catalyst, etc. are dissolved in the aqueous layer side, so that this is separated and removed, and the same operation is repeated to completely remove the excess maleic acid or maleic anhydride, aprotic polar solvent, catalyst, etc. The catalyst is added again to the maleimide resin solution from which the excess maleic acid or maleic anhydride, aprotic polar solvent, and catalyst have been removed, and the dehydration ring-closure reaction of the residual amic acid under the heating reflux condition is performed again, whereby a maleimide resin solution having a low acid value (the above is the second-stage reaction) can be obtained.
The period of the re-dehydration ring-closure reaction is usually 1 to 5 hours, more preferably 1 to 3 hours, and the aprotic polar solvent described above may be added as needed. After the reaction is terminated, cooling is performed, and water washing is repeated until the water becomes neutral. After that, the water is removed by azeotropic dehydration under reduced pressure by heating, or the solvent is distilled off, or another solvent may be added to adjust the solvent to a resin solution of a desired concentration, or the solvent may be completely distilled off to take out the resin as a solid component.
Next, the component (B) will be described.
The component (B) can be obtained by reacting a diamine (B) with maleic anhydride.
The component (b) may be a linear or branched aliphatic diamine, an aliphatic ether diamine, a cyclic aliphatic diamine, an aromatic diamine, or the like. The diamine may be used in 1 kind or 2 kinds or more.
Examples of the linear or branched aliphatic diamine include 1, 4-butane diamine, 1, 6-hexane diamine, 1, 8-octane diamine, 1, 9-nonane diamine, 1, 10-decane diamine, 1, 11-undecane diamine, 1, 12-dodecane diamine, 1, 14-tetradecane diamine, 1, 16-hexadecane diamine, 1, 18-octadecane diamine, 1, 20-eicosane diamine, 2-methyl-1, 8-octane diamine, 2-methyl-1, 9-nonane diamine, and 2, 7-dimethyl-1, 8-octane diamine. Further, from the viewpoint of obtaining a cured product having a lower modulus of elasticity in tension, the carbon number of the diamine is more preferably 6 to 60, and the diamine derived from the dimer acid is more preferably used.
Examples of the aliphatic ether diamine include 2,2 '-oxybis (ethylamine), 3' -oxybis (propylamine), and 1, 2-bis (2-aminoethoxy) ethane.
Examples of the cyclic aliphatic diamine include 1, 3-bis (aminomethyl) cyclohexane, 1, 4-diaminocyclohexane, methylcyclohexane diamine, isophorone diamine, and the like.
Examples of the aromatic diamine include 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (aminomethyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-diaminobenzene, 1, 3-diaminobenzene, 2, 4-diaminotoluene, and 4,4' -diaminodiphenyl methane; 4,4' -diaminodiphenyl sulfone; 3,3' -diaminodiphenyl sulfone; 4, 4-diaminobenzophenone; 4, 4-diaminodiphenyl sulfide; 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
The component (b) is more preferably a diamine (b-1) having 4 to 60 carbon atoms, which is obtained by reacting a tetracarboxylic dianhydride (b-2), and the component (b-1) is particularly preferably a diamine (b-1 a) derived from a dimer acid. In this case, the component (B) is obtained by reacting a diamine (B-1 a) derived from a dimer acid, a tetracarboxylic dianhydride (B-2), and maleic anhydride, and the component (B) has a 2-valent hydrocarbon group (c) derived from a dimer acid and a cyclic imide bond.
The above-mentioned 2-valent hydrocarbon group (c) derived from dimer acid means a 2-valent residue obtained by removing 2 carboxyl groups from a dicarboxylic acid contained in dimer acid. In the present invention, such a dimer acid-derived 2-valent hydrocarbon group (c) may be incorporated into a maleimide resin by reacting a diamine (b-1 a) obtained by substituting an amine group with 2 carboxyl groups of a dicarboxylic acid contained in a dimer acid with a tetracarboxylic dianhydride (b-2) and maleic anhydride described later to form an imide bond.
In the present invention, the dimer acid is preferably a dicarboxylic acid having 20 to 60 carbon atoms. Specific examples of the dimer acid include a dimer of unsaturated bonds of unsaturated carboxylic acids such as linoleic acid, oleic acid and linolenic acid, and a product obtained by subjecting the resulting product to distillation and purification. The dimer acid of the above specific example mainly contains dicarboxylic acids having 36 carbon atoms, and usually contains a limit of about 5 mass% of tricarboxylic acids having 54 carbon atoms and a limit of about 5 mass% of monocarboxylic acids. The diamine (b-1 a) derived from the dimer acid (hereinafter, referred to as dimer acid-derived diamine (b-1 a) as the case may be) of the present invention is usually a mixture obtained by substituting 2 carboxyl groups of each dicarboxylic acid contained in the dimer acid with amine groups. In the present invention, such a dimer acid-derived diamine (b-1 a) may be exemplified by a diamine containing [3, 4-bis (1-aminoheptyl) 6-hexyl-5- (1-octenyl) ] cyclohexane or the like, or a diamine obtained by further hydrogenating such a diamine to saturate unsaturated bonds.
The dimer acid-derived 2-valent hydrocarbon group (c) of the present invention introduced into the maleimide resin using such dimer acid-derived diamine (b-1 a) is more preferably a residue in which 2 amine groups are removed from the dimer acid-derived diamine (b-1 a). In addition, when the dimer acid-derived diamine (B-1 a) is used to obtain the maleimide resin (B) according to the present invention, 1 kind of the dimer acid-derived diamine (B-1 a) may be used alone or 2 or more kinds of diamines differing in composition may be used in combination. In addition, as the diamine (b-1 a) derived from the dimer acid, for example, commercially available products such as "PRIAMINE1074" (manufactured by CRODA JAPAN Co., ltd.) can be used.
In the present invention, the tetracarboxylic dianhydride (b-2) has an alicyclic structure adjacent to an anhydride group, and when a maleimide resin is formed after the reaction, the imide ring adjacent site is a tetracarboxylic dianhydride having a structure which has an alicyclic structure. If the adjacent part of the imide ring has an alicyclic structure, the other part may contain an aromatic ring in its structure.
In the present invention, the component (B) is more preferably represented by the following formula (3). In the following formula (3), R 4 R is R 5 The structure derived from tetracarboxylic dianhydride (b-2).
(in the formula (3), R 1 Represents a 2-valent hydrocarbon group (c) derived from a dimer acid, R 2 Represents a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from the dimer acid, R 3 Represents any one selected from the group consisting of a 2-valent hydrocarbon group (c) derived from a dimer acid and a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from a dimer acid, R 4 R is R 5 Each independently represents 1 or more organic groups selected from 4-40 (more preferably 6-40) carbon atoms having a alicyclic structure selected from a monocyclic or condensed polycyclic structure, 8-40 carbon atoms having an alicyclic structure and an alicyclic structure which are linked directly or via a crosslinked structure. m is an integer of 1 to 30, n is an integer of 0 to 30, R 4 R is R 5 The two may be the same or different. )
In the present invention, the tetracarboxylic dianhydride (b-2) is more preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (6). The tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (6) has an alicyclic structure adjacent to the anhydride group.
(in formula (6), cy comprises a 4-valent organic group having 4 to 40 carbon atoms of a hydrocarbon ring, which may also comprise an aromatic ring.)
The tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the above formula (6) is specifically represented by the following formula (6-a).
(in the formula (6-a), R 6 A 4-valent organic group having 4 to 40 carbon atoms which contains a hydrocarbon ring, and the organic group may also contain an aromatic ring. )
In the present invention, the tetracarboxylic dianhydride (b-2) is more preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formulas (7-1) to (7-11). The tetracarboxylic dianhydrides (b-2) represented by the formulas (7-1) to (7-11) have a structure comprising: the 4-valent organic group having 4 to 40 carbon atoms (more preferably 6 to 40 carbon atoms) and having a monocyclic or condensed polycyclic alicyclic structure, the organic group having a monocyclic alicyclic structure, being a 4-valent organic group having 8 to 40 carbon atoms and being bonded to each other directly or via a crosslinked structure, or the 4-valent organic group having 8 to 40 carbon atoms and having a semi-alicyclic structure, both of which are alicyclic structures and aromatic rings.
(in the formula (7-4), X 1 A direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a 2-valent organic group of 1 to 3 carbon atoms. In the formula (7-6), X 2 Direct bond, oxygen atom, sulfur atom, sulfonyl group, 2-valent organic group of 1 to 3 carbon atoms, or arylene group. )
The tetracarboxylic dianhydrides (b-2) having an alicyclic structure represented by the above formulas (7-1) to (7-11) can be specifically represented by the following formulas (7-1 a) to (7-11 a).
(in the formula (7-4 a), X 1 A direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a 2-valent organic group of 1 to 3 carbon atoms. In formula (7-6 a), X 2 Direct bond, oxygen atom, sulfur atom, sulfonyl groupA 2-valent organic group having 1 to 3 carbon atoms, or an arylene group. )
The tetracarboxylic dianhydride (b-2) used in the present invention has a 4-valent organic group having 4 to 40 carbon atoms (more preferably 6 to 40 carbon atoms) in a single-or condensed polycyclic alicyclic structure, a 4-valent organic group having 8 to 40 carbon atoms in which the organic groups having a single-ring alicyclic structure are bonded to each other directly or through a crosslinked structure, or a 4-valent organic group having 8 to 40 carbon atoms in a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. Specific examples of the tetracarboxylic dianhydride (b-2) having an alicyclic structure include 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA), 1, 2-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (H-PMDA), and 1,1' -dicyclohexyl-3, 3',4' -tetracarboxylic acid-3, 4:3',4' -dianhydride (H-BPDA), 4- (2, 5-bisoxo-tetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, 5- (2, 5-bisoxo-tetrahydrofuran-3-cyclohexene-1, 2-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 3,5, 6-tricarboxyl-2-noretnaneacetic acid dianhydride, or compounds in which the alicyclic tetracarboxylic dianhydride of each of these or the aromatic ring of these is substituted with an alkyl group or a halogen atom, such as 1, 3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-bisoxo-3-furanyl) naphthalene [1,2-c ] furan-1, 3-dione, or compounds in which the hydrogen atom of each of the alicyclic tetracarboxylic dianhydrides of these or the aromatic ring of these is substituted with a halogen atom.
In the present invention, the tetracarboxylic dianhydride (b-2) is more preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (8).
In the present invention, the tetracarboxylic dianhydride (b-2) is more preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (4).
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In the present invention, tetracarboxylic dianhydride (b-2) is a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (9).
In the present invention, tetracarboxylic dianhydride (b-2) is a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (10).
In the present invention, in addition to the tetracarboxylic dianhydride (b-2) having an alicyclic structure, an acid dianhydride having no alicyclic structure or an acid dianhydride containing an aromatic ring adjacent to an anhydride group may be added. The lower limit of the tetracarboxylic dianhydride (b-2) is more preferably 40 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more, based on the total amount of the acid dianhydride. The upper limit may be 100 mol% or less. When the content of the tetracarboxylic dianhydride (b-2) in the total amount of the acid dianhydrides is less than 40 mol%, there is a concern that the aromatic ring structure is increased and the dielectric characteristics are lowered.
The acid dianhydride adjacent to the anhydride group and containing an aromatic ring other than the tetracarboxylic dianhydride (b-2) is specifically exemplified by pyromellitic dianhydride, 4' -oxydiphthalic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2', aromatic tetracarboxylic acid dianhydrides such as 3,3' -benzophenone tetracarboxylic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, 1,2,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 2,3,5, 6-pyridine tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, or aromatic cyclic alkyl substituted aromatic acid dianhydrides such as bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride or these compounds, and aromatic acid anhydrides having an amide group. These may be used in combination with 2 or more kinds of alicyclic structures having 4 to 40 carbon atoms or acid dianhydrides having semi-alicyclic structures.
The component (b-1) is not limited to the dimer acid-derived diamine (b-1 a), but may be a maleimide resin obtained by reacting a diamine (b-1 b) other than the dimer acid-derived diamine (b-1 a), the tetracarboxylic dianhydride (b-2), and the maleic anhydride, or may be a maleimide resin obtained by reacting a diamine (b-1 a) derived from the dimer acid, a diamine (b-1 b) other than the dimer acid-derived diamine (b-1 a), the tetracarboxylic dianhydride (b-2), and the maleic anhydride. The desired physical properties such as further lowering of the tensile modulus of elasticity of the cured product obtained can be controlled by copolymerizing diamines (b-1 b) other than the dimer acid-derived diamines (b-1 a).
The diamine (b-1 b) other than the dimer acid-derived diamine (b-1 a) (hereinafter, simply referred to as diamine (b-1 b) as the case may be) refers to a diamine other than the diamine contained in the dimer acid-derived diamine (b-1 a) in the present invention. Such a diamine (b-1 b) is not particularly limited, and examples thereof include aliphatic diamines such as 1, 6-hexamethylenediamine; alicyclic diamines such as 1, 4-diaminocyclohexane and 1, 3-bis (aminomethyl) cyclohexane; aromatic diamines such as 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (aminomethyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-diaminobenzene, 1, 3-diaminobenzene, 2, 4-diaminotoluene, and 4,4' -diaminodiphenylmethane; 4,4' -diaminodiphenyl sulfone; 3,3' -diaminodiphenyl sulfone; 4,4' -diaminobenzophenone; 4,4' -diaminodiphenyl sulfide; 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane. Among these, aliphatic diamines having 6 to 12 carbon atoms such as 1, 6-hexamethylenediamine are more preferable from the viewpoint of obtaining cured products having a lower tensile modulus; diamine-based cyclohexane such as 1, 4-diaminocyclohexane; aromatic diamines having an aliphatic structure having 1 to 4 carbon atoms in an aromatic skeleton such as 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane. In addition, when these diamines (B-1B) are used to obtain the maleimide resin (B) according to the present invention, 1 kind of these diamines (B-1B) may be used alone or 2 or more kinds may be used in combination.
The method of reacting the dimer acid-derived diamine (b-1 a), the tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the maleic anhydride, or the method of reacting the dimer acid-derived diamine (b-1 a), the diamine (b-1 b), the tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the maleic anhydride is not particularly limited, and any suitable publicly known method can be employed. For example, first, the diamine (b-1 a) derived from a dimer acid, the tetracarboxylic dianhydride (b-2), and the diamine (b-1 b) as required are stirred in a solvent such as toluene, xylene, tetrahydronaphthalene, N-dimethylacetamide, N-methyl-2-pyrrolidone (Methyl pyrrolidone), or a solvent such as a mixed solvent of these at room temperature (about 23 ℃) for 30 to 60 minutes to synthesize a polyamic acid, and then maleic anhydride is added to the obtained polyamic acid and stirred at room temperature (about 23 ℃) for 30 to 60 minutes to synthesize a polyamic acid to which maleic acid is added at both ends. The desired maleimide resin can be obtained by adding a solvent such as toluene to the polyamic acid, which is azeotroped with water, and refluxing the resultant polyamide acid at a temperature of 100 to 160℃for 3 to 6 hours while removing the water produced by imidization. In such a method, a catalyst such as pyridine or methanesulfonic acid may be further added.
The raw materials to be mixed in the above reaction are preferably mixed (total mole number of all diamines contained in the dimer acid-derived diamine (b-1 a) and the diamine (b-1 b)): (the total mole number of the tetracarboxylic dianhydride (b-2) having an alicyclic structure+1/2 of the mole number of the maleic anhydride) is 1:1. in the case of using the diamine (b-1 b) in combination, it is preferable that the ratio of the number of moles of the diamine (b-1 b)/(the number of moles of all diamines contained in the diamine (b-1 a) derived from the dimer acid) is 1 or less, more preferably 0.4 or less, from the viewpoint of exhibiting flexibility derived from the dimer acid and obtaining a cured product having a lower modulus of elasticity. In the case of using the diamine (b-1 b) in combination, the polymerization mode of the amic acid unit composed of the diamine (b-1 a) derived from dimer acid and the tetracarboxylic dianhydride (b-2) having an alicyclic structure and the amic acid unit composed of the diamine (b-1 b) and the tetracarboxylic dianhydride (b-2) having an alicyclic structure may be random polymerization or block polymerization.
The component (B) thus obtained is more preferably represented by the following formula (3).
(in the formula (3), R 1 Represents a 2-valent hydrocarbon group (c) derived from a dimer acid, R 2 Represents a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from the dimer acid, R 3 Represents any one selected from the group consisting of a 2-valent hydrocarbon group (c) derived from a dimer acid and a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from a dimer acid, R 4 R is R 5 Each independently represents 1 or more organic groups selected from a 4-valent organic group having 4 to 40 carbon atoms and having a single-ring alicyclic structure or a condensed polycyclic alicyclic structure, a 4-valent organic group having 8 to 40 carbon atoms and having both an alicyclic structure and an aromatic ring, wherein the organic groups having a single-ring alicyclic structure are linked directly or via a crosslinked structure. m1 to 30, n0 to 30, R 4 R is R 5 May be the same or different. )
The 2-valent hydrocarbon group (c) derived from the dimer acid in the above formula (3) is as described above. In the present invention, the term "2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from a dimer acid" in the formula (2) means a 2-valent residue obtained by removing 2 amine groups from the diamine (b-1 b). However, in the same compound, the above-mentioned 2-valent hydrocarbon group (c) derived from the dimer acid is different from the above-mentioned 2-valent organic group (d). The 4-valent organic group in the formula (2) means a 4-valent residue obtained by removing 2 groups represented by-CO-O-CO-from the tetracarboxylic dianhydride.
In the foregoing formula (3), m contains the number of the foregoing repeating unit of the 2-valent hydrocarbon group (c) derived from the dimer acid (hereinafter, referred to as a structure derived from the dimer acid, as the case may be), and represents an integer of 1 to 30. When the value of m exceeds the upper limit, the solubility in a solvent tends to be low, and in particular, the solubility in a developer during development described later tends to be low. In addition, from the viewpoint that solubility in a developing solution is suitable at the time of developing, a value of 3 to 10 is particularly preferable as m.
In the above formula (3), n is a number including a repeating unit of the above 2-valent organic group (d) (hereinafter, referred to as a structure of an organic diamine, as the case may be), and represents an integer of 0 to 30. When the value of n exceeds the upper limit, the resulting cured product tends to be hard and brittle, and the flexibility thereof is deteriorated. In addition, from the viewpoint of the tendency to obtain a cured product having a low elastic modulus, the value of n is particularly preferably 0 to 10.
In the formula (3), when m is 2 or more, R 1 R is R 4 The repeating units may be the same or different from each other. In the formula (3), when n is 2 or more, R 2 R is R 5 The repeating units may be the same or different from each other. In the maleimide resin represented by the formula (3), the dimer acid-derived structure may be random or block-derived structure.
When the maleimide resin (B) of the present invention is obtained from the dimer acid-derived diamine (B-1 a), the maleic anhydride, the tetracarboxylic dianhydride (B-2) and the organic diamine (f) as required, the n and m can be represented by the mixed molar ratio of all the diamines contained in the dimer acid-derived diamine (B-1 a), the diamine (B-1B), the maleic anhydride and the tetracarboxylic dianhydride (B-2) when the reaction rate is 100%. That is, (m+n): (m+n+2) is defined as (total mole number of all diamines contained in diamine (b-1 a) and diamine (b-1 b) derived from dimer acid): (total mole number of maleic anhydride and tetracarboxylic dianhydride (b-2)), m: n is defined as (the number of moles of all diamines contained in diamine (b-1 a) derived from dimer acid): (mole number of diamine (b-1 b)) represents 2: (m+n) in (moles of maleic anhydride): (mole number of tetracarboxylic dianhydride (b-2)).
In addition, in the component (B), the sum (m+n) of m and n is more preferably 2 to 30 from the viewpoint of the tendency to obtain a cured product having a lower elastic modulus. In addition, from the viewpoint of flexibility derived from dimer acid and a tendency to obtain a cured product having a lower elastic modulus, the ratio of m to n (n/m) is preferably 1 or less, more preferably 0.4 or less.
The curable resin composition of the present invention may be used alone as component (B), or may be used in combination of at least 2 kinds.
The weight ratio of the component (A) to the component (B) in the curable resin composition of the present invention is preferably 99/1 to 60/40, more preferably 97/3 to 60/40, still more preferably 95/5 to 70/30. When the weight ratio of the component (B) is 1 or more, the water absorption property becomes good. On the other hand, when the weight ratio of the component (B) is 40 or less, the heat resistance becomes good.
Any publicly known resin material may be used in addition to the components (a) and (B) of the curable resin composition of the present invention. Specifically, phenol resins, epoxy resins, amine resins, resins containing active olefins, isocyanate resins, polyamide resins, polyimide resins, cyanate resins, acrylic resins, methallyl resins, active ester resins, and the like can be used in 1 kind, or in a plurality of combinations. In addition, the maleimide resin other than the component (A) and the component (B) may be used in combination.
The phenol resin, epoxy resin, amine resin, active olefin-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, and active ester resin may be exemplified as follows, but are not limited thereto.
Phenol resin: the polyphenylene ether resin is obtained by condensation of a polymer of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, m-xylenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, phthalic aldehyde, alkyl-substituted phthalic aldehyde, hydroxy-phthalic aldehyde, naphthalene aldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), a polymer of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, nordiene, vinylnortriptylene, tetrahydroindene, divinylbenzene, diisopropenylbiphenyl, butadiene, isoprene, etc.), a polymer of phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), a polymer of phenols with substituted biphenyls (4, 4 '-bis (chloromethyl) -1,1' -biphenyl, 4 '-bis (methoxymethyl) -1,1' -biphenyl, etc.), or a polymer of substituted phenols (1, 4-bis (chloromethyl) benzene, 1, 4-bis (methoxymethyl) benzene, bisphenol, etc.), a polymer of substituted phenols with bisphenol, etc.
Epoxy resin: glycidyl ether epoxy resins obtained by glycidylating the aforementioned phenol resins, alcohols and the like, alicyclic epoxy resins represented by 4-vinyl-1-cyclohexene diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4' -epoxycyclohexane carboxylate and the like, glycidyl amine epoxy resins represented by tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidyl-p-aminophenol and the like, and glycidyl ester epoxy resins.
Amine resin: diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, naphthalene diamine, aniline novolac, o-ethylaniline novolac, aniline resins obtained by the reaction of aniline and xylene chloride, aniline and substituted biphenyls (4, 4 '-bis (chloromethyl) -1,1' -biphenyls and 4,4 '-bis (methoxymethyl) -1,1' -biphenyls, etc.), or substituted phenyls (1, 4-bis (chloromethyl) benzene, 1, 4-bis (methoxymethyl) benzene and 1, 4-bis (hydroxymethyl) benzene, etc.), as described in Japanese patent No. 6429862.
Resins containing active olefins: the polycondensates of the aforementioned phenol resins with halogen compounds containing active olefins (methyl styrene chloride, allyl chloride, methallyl chloride, acryl chloride, allyl chloride, etc.), the polycondensates of phenols containing active olefins (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, clove oil, isoeugenol, etc.), with halogen compounds (4, 4' -bis (methoxymethyl) -1,1' -biphenyl, 1, 4-bis (chloromethyl) benzene, 4' -difluorobenzophenone, 4' -dichlorobenzophenone, 4' -dibromobenzophenone, cyanuric chloride, etc.), the polycondensates of epoxy resins or alcohols with substituted or unsubstituted acrylic esters (acrylic esters, methacrylic esters, etc.), maleimide resins (4, 4' -diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2' -bis [ 4- (4-maleimidophenoxy) phenyl ] propane, 3' -dimethyl-5 ' -diphenyl maleimide, 4' -diphenyl maleimide, 3,4' -bis (4-maleimido) maleimide, 3,4' -diphenyl maleimide, 3-bis (4, 4' -diphenyl maleimide, 4-bisphenol-4, 3-diphenyl maleimide, 4-bisphenol-4-phenylmaleimide, 3, 4-diphenyl-maleimide, 4-bisphenol-3, 4-bisphenol-phenylmaleimide, etc.).
Isocyanate resin: aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norzhen diisocyanate, and lysine diisocyanate; polyisocyanates such as biuret of one or more types of isocyanate monomers or isocyanate obtained by trimerizing the above-mentioned diisocyanate compound; polyisocyanates obtained by urethanization of the above isocyanate compounds with polyol compounds.
Polyamide resin: aliphatic diamines selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactams (epsilon-caprolactam, omega-undecanolactam, omega-laurolactam), diamines (ethylenediamine, trimethylene diamine, tetramethylenediamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1, 5-diaminopentane, 2-methyl-1, 8-diaminooctane, etc.); an alicyclic diamine such as cyclohexane diamine, bis- (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, an alicyclic dicarboxylic acid such as xylene diamine, and the like), and an aliphatic dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and the like, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methyl-terephthalic acid, 5-methyl-isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and the like, an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid, and the like, and a dialkyl ester and dichloride of these dicarboxylic acids), and the like.
Polyimide resin: the diamine and tetracarboxylic dianhydride (4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 5- (2, 5-bisoxo-tetrahydro-3-furanyl) -3-methyl-cyclohexene-1, 2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, 3',4,4 '-benzophenone tetracarboxylic dianhydride, 2',3 '-benzophenone tetracarboxylic dianhydride, 3',4,4 '-biphenyltetracarboxylic dianhydride, 3',4 '-diphenylsulfone tetracarboxylic dianhydride, 2',3,3 '-biphenyltetracarboxylic dianhydride, methylene-4, 4' -diphthalic dianhydride, 1-ethylene-4, 4 '-diphthalic dianhydride, 2' -propylene-4, 4 '-diphthalic dianhydride, 1, 2-ethylene-4, 4' -diphthalic dianhydride, 1, 3-trimethylene-4, 4 '-diphthalic dianhydride, 1, 4-tetramethylene-4, 4' -diphthalic dianhydride, 1, 5-pentamethylene-4, 4 '-diphthalic dianhydride, 4' -oxydiphthalic dianhydride, sulfur-4, 4 '-diphthalic dianhydride, sulfonyl-4, 4' -diphthalic dianhydride 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis [2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, 1, 4-bis [2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, bis [3- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, bis [4- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, 2-bis [3- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, bis (3, 4-dicarboxyphenoxy) dimethylsilane dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) -1, 3-tetramethyldisiloxane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, 1,2,7, 8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3, 4-butane tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, 3 '; 4,4' -dicyclohexyltetracarboxylic dianhydride, carbonyl-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, methylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 2-ethyleneyl-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1-ethyleneyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 2-propylene-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, oxo-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, thioxo-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, sulfonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, rel- [1S,5R ] -3, 3-bicyclo [3, 6-oxo-3 '- (2, 3-bicyclo [ 3-2-spiro-3, 6-spiro-2-dione) 2-spiro-3, 6-dione 5' -dione), 4- (2, 5-dihydroxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, polyethylene glycol-bis- (3, 4-dicarboxylic anhydride phenyl) ether, 4 '-biphenylbis (trimellitic acid monoester anhydride), 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride).
Cyanate resin: specific examples of the cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide include dicyanoxybenzene, tricyanoxybenzene, dicyanoxynaphthalene, dicyanoxybiphenyl, 2 '-bis (4-cyanooxyphenyl) propane, bis (4-cyanooxyphenyl) methane, bis (3, 5-dimethyl-4-cyanooxyphenyl) methane, 2' -bis (3, 5-dimethyl-4-cyanooxyphenyl) propane, 2 '-bis (4-cyanooxyphenyl) ethane, 2' -bis (4-cyanooxyphenyl) hexafluoropropane, bis (4-cyanooxyphenyl) sulfone, bis (4-cyanooxyphenyl) sulfide, phenol novolac cyanooxy, and a phenol/dicyclopentadiene co-condensate, but are not limited thereto.
In addition, JP-A2005-264154 describes that a cyanate ester compound obtained by the synthesis method is particularly preferable as a cyanate ester compound because of its low hygroscopicity, flame resistance and excellent dielectric characteristics.
The cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetone, and dibutyltin maleate, in order to trimerize a cyanate group to form a sym-triazine ring, if necessary. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, more preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the curable resin composition.
Active ester resin: if necessary, a compound having 1 or more active ester groups in 1 molecule may be used as a hardener for curable resins such as epoxy resins. As the active ester hardener, a compound having 2 or more reactive ester groups in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc., is preferable. The active ester hardener is more preferably obtained by condensation reaction of at least one compound selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds with at least one compound selected from the group consisting of hydroxyl compounds and thiol compounds. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxyl compound is more preferable, and an active ester hardener obtained from a carboxylic acid compound and at least one compound of a phenol compound and a naphthol compound is more preferable.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, iconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of the phenol compound or naphthol compound include hydroquinone, m-xylylene phenol, bisphenol a, bisphenol F, bisphenol S, phenol naphthalene, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin (phloroglucinol), dicyclopentadiene type diphenol compound, phenol novolac, and the like. The "dicyclopentadiene type diphenol compound" herein means a diphenol compound obtained by condensing phenol 2 molecules in dicyclopentadiene 1 molecules.
More preferable specific examples of the active ester hardener include active ester compounds containing dicyclopentadiene type diphenol structure, active ester compounds containing naphthalene structure, active ester compounds containing acetyl compounds of phenol novolac, and active ester compounds containing benzoyl compounds of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" means a 2-valent structural unit composed of phenylene-dicyclopentylene-phenylene.
Examples of commercially available products of the active ester hardener include "EXA9451", "EXA9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXA-8000L-65TM", "EXA-8150-65T" (manufactured by DIC corporation); examples of the active ester compound having a naphthalene structure include "EXA9416-70AK" (manufactured by DIC Co., ltd.); examples of the active ester compound containing an acetyl compound of a phenol novolac include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound containing a benzoyl compound of a phenol novolac include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester hardener belonging to the acetyl compound of the phenol novolac include "DC808" (manufactured by mitsubishi chemical company); as the phosphorus atom-containing active ester hardener, "EXA-9050L-62M" manufactured by DIC company; etc.
The curable resin composition of the present invention may further be used in combination with a curing accelerator (curing catalyst) to improve the curability. Specific examples of the hardening accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, tertiary amines such as 2- (dimethylaminomethyl) phenol and 1, 8-diaza-bicyclo (5, 4, 0) undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, cetyltrimethylammonium salt, quaternary ammonium salts such as cetyltrimethylammonium hydroxide, triphenylbenzyl phosphonium salt, triphenylethyl phosphonium salt, quaternary phosphonium salts such as tetrabutylphosphonium salt (the relative ion halogen of quaternary salt, organic acid ion, hydroxide ion, etc.), transition metal compounds (transition metal salts) such as zinc compounds such as zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate, zinc phosphate (zinc octylphosphate, zinc stearyl phosphate, etc.), and the like, but are not particularly limited thereto. The amount of the hardening accelerator to be blended is 0.01 to 5.0 parts by weight based on 100 parts by weight of the curable resin composition.
The curable resin composition of the present invention may optionally contain a curing accelerator as a radical polymerization initiator. Examples of the radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, diisopropylbenzene peroxide, alkyl peroxyesters such as 1, 3-bis- (tert-butylperoxyisopropyl) -benzene, tert-butylperoxybenzoate, peroxyketals such as 1, 1-di-tert-butylcyclohexane, α -cumyl peroxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxytrimethylacetate, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, alkyl peroxyesters such as tert-amyl peroxy-3, 5-trimethylhexanoate, tert-butyl peroxy-3, 5-trimethylhexanoate, tert-amyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxyisopropyl carbonate, 1, 6-bis (tert-butylperoxy) trimethylacetate, bis (tert-butylperoxy) 2-ethylhexanoate, bis (4 ' -butylperoxy) azo-2-n-lauroyl peroxide, 4' -bis (4-butylperoxy) and azo-4, 4' -bis (3, 62 ' -peroxy) and azo-2 ' -bis (3, 62 ' -peroxy) peroxy compounds, and azo-2-n-bis (4-peroxy compounds, 4' -peroxy compounds, and the azo-peroxy compounds are known to be preferred. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, alkyl peroxyacid esters, peroxycarbonates, and the like are more preferable, and dialkyl peroxides are even more preferable. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the dielectric characteristics of the cured product may be deteriorated.
In addition, the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame resistance imparting component. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of the phosphorus-containing compound include phosphates such as trimethyl phosphate, triethyl phosphate, trimethyl phenyl phosphate, trixylenyl phosphate (Trixylyleneyl phosphate), toluene diphenyl phosphate (Cresyldiphenyl phosphate), cresyl-2, 6-xylyl phosphate (Cresyl-2, 6-dixylenyl phosphate), 1, 3-phenylene bis (xylyl phosphate), 1, 4-phenylene bis (xylyl phosphate), and 4,4' -biphenyl (xylyl phosphate); phosphanes such as 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 10 (2, 5-dihydroxyphenyl) -10H-9-oxo-10-phosphaphenanthrene-10-oxide; the phosphorus-containing epoxy compound or red phosphorus obtained by reacting the epoxy resin with active hydrogen of the above-mentioned phosphane is more preferably a phosphate, phosphane or phosphorus-containing epoxy compound, and 1, 3-phenylenedi (xylyl phosphate), 1, 4-phenylenedi (xylyl phosphate), 4' -biphenyl (xylyl phosphate) or phosphorus-containing epoxy compound is particularly preferred. The content of the phosphorus-containing compound is more preferably in the range of 0.1 to 0.6 (weight ratio) per resin component in the curable resin composition. When the flame resistance is not more than 0.1, the hygroscopicity of the cured product may be adversely affected by the dielectric properties of the cured product or more than 0.6.
In addition, a light stabilizer may be added to the curable resin composition of the present invention as needed. Light stabilizers amine-blocking light stabilizers are particularly suitable for HALS and the like. The HALS is not particularly limited, but typical examples thereof include dibutylamine/1, 3, 5-triazine/N, poly condensate of N' - [ bis (2, 6-tetramethyl-4-piperidinyl-1, 6-hexamethylenediamine and N- (2, 6-tetramethyl-4-piperidinyl) butylamine ], poly condensate of dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2, 6-tetramethylpiperidine succinate, poly [ (6- (1, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2, 6-tetramethyl-4-piperidinyl) imino } hexamethylene { (2, 6-tetramethyl-4-piperidinyl) imino } ], poly (6- (1, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl }) bis (1, 2, 6-pentamethyl-4-piperidinyl) [ 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl } methyl ] butylmalonate, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, bis (1-octyloxy-2, 6-tetramethyl-4-piperidinyl) sebacate, 2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-N-butylmalonate bis (1, 2, 6-pentamethyl-4-piperidinyl), and the like, HALS may be used only in 1, more than 2 kinds may be used in combination.
The curable resin composition of the present invention may be formulated with a binder resin as needed. The binder resin includes, but is not limited to, butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NAR-phenol resin, epoxy-NAR resin, polyamide resin, polyimide resin, silicone resin, and the like. The amount of the binder resin to be blended is preferably in a range of not impairing the flame resistance and heat resistance of the cured product, more preferably in a range of 0.05 to 50 parts by mass, still more preferably in a range of 0.05 to 20 parts by mass, as required, relative to 100 parts by mass of the resin component.
Further, if necessary, a powder such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, iron oxide asbestos, glass powder, or an inorganic filler in which these are formed into a spherical shape or a crushed shape may be added to the curable resin composition of the present invention. In addition, in particular, when a curable resin composition for semiconductor packaging is obtained, the amount of the inorganic filler used is usually in the range of 80 to 92 mass%, more preferably 83 to 90 mass% in the curable resin composition.
In addition, publicly known additives may be formulated as needed in the curable resin composition of the present invention. Specific examples of the additive that can be used include colorants such as polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and fillers of silane coupling agents, release agents, carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be blended is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the resin component.
The curable resin composition of the present invention is obtained by uniformly mixing the above components in a predetermined ratio, and is usually prepared by curing at 130 to 180 ℃ for 30 to 500 seconds, and is then post-cured at 150 to 200 ℃ for 2 to 15 hours to perform a sufficient curing reaction, whereby the cured product of the present invention can be obtained. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and the solvent may be removed and then cured.
The curable resin composition of the present invention thus obtained has heat resistance, mechanical properties, and good dielectric properties even after water absorption. Therefore, the curable resin composition of the present invention can be used in a wide range of fields where moisture resistance, heat resistance, low dielectric constant, and low dielectric tangent are required. Specifically, the material can be used as all materials for electric/electronic components such as insulating materials, laminated boards (printed wiring boards, AGA substrates, build-up substrates, etc.), packaging materials, resists, and the like. In addition, the molding material and the composite material can be used in the fields of coating materials, adhesives, 3D printing and the like. In particular, in a semiconductor package, reflow resistance is facilitated.
The semiconductor device has a package with the curable resin composition of the present invention. Examples of the semiconductor device include a dual in-line package (DIP, dual Inline Package), a quad flat package (QFP, quad Flat Package), a Ball Grid Array (BGA), a chip (chip) size package (CSP, chip Size Package), a small package (SOP, small Outline Package), a thin small outline package (TSOP, thin Small Outline Package), a thin quad flat package (TQFP, thin Quad Flat Package), and the like.
The method for preparing the curable resin composition of the present invention is not particularly limited, but as described above, the components may be dispersed or dissolved in a solvent or the like, and mixed uniformly, and the solvent may be distilled off as needed to prepare the curable resin composition, or the curable resin composition may be converted into a prepolymer. For example, the prepolymer is formed by heating the component (A) and the component (B) in the presence or absence of a catalyst, in the presence or absence of a solvent. Similarly, in addition to the component (a) and the component (B), a curing agent such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives may be added to carry out the prepolymer. The components are mixed or prepolymer-formed in the absence of a solvent, and an extruder, kneader, roll or the like is used, and a reaction vessel with a stirring device is used in the presence of a solvent.
The curable resin composition is uniformly formed by mixing the curable resin composition in such a manner that the curable resin composition is uniformly mixed without using a solvent or the like, and is kneaded at a temperature in the range of 50 to 100 ℃ by using a kneader, a roll, a planetary mixer or the like. The obtained curable resin composition may be molded into a cylindrical ingot shape, a granular powder shape, or a powdery molded body by a molding machine such as a tablet press after pulverization, or a sheet shape having a thickness of 0.05mm to 10mm by melting the composition on a surface support. The obtained molded article is non-sticky at 0 to 20 ℃ and hardly has reduced fluidity and hardening properties even when stored at-25 to 0 ℃ for 1 week or more.
The molded article thus obtained can be molded into a cured product by a transfer molding machine or a compression molding machine.
The curable resin composition of the present invention may be formed into a varnish-like composition (hereinafter, also referred to as varnish) by adding an organic solvent thereto. The curable resin composition of the present invention can be formed into a cured product of the curable resin composition of the present invention by hot extrusion molding a prepreg obtained by dissolving the curable resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone (Methyl pyrrolidone) or the like as necessary to form a varnish, impregnating the varnish with a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like, and heat-drying the resultant. The solvent used in this case is usually used in an amount of 10 to 70% by weight, more preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present invention and the solvent. If the amount of the solvent is less than this range, the varnish viscosity becomes high and workability becomes poor, and if the amount of the solvent is large, voids are generated in the cured product. In addition, in the case of a liquid composition, a resin cured product containing carbon fibers can be obtained directly by, for example, an RTM method.
The curable resin composition of the present invention may be used as a modifier for a film composition. Specifically, it is possible to use a case of improving the flexibility in the A-stage or the like. The curable resin composition of the present invention is formed into the curable resin composition varnish, applied to a release film, and subjected to a-stage after the solvent is removed under heating, thereby obtaining a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
The curable resin composition of the present invention can be impregnated with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers by melting by heating to reduce the viscosity, thereby obtaining a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and fibers of inorganic substances other than glass, poly-p-phenylene terephthalamide (Kevlar (registered trademark), manufactured by Dupont corporation), wholly aromatic polyamide, and polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not limited thereto. The shape of the base material is not particularly limited, but examples thereof include woven fabrics, nonwoven fabrics, rovings, strand mats, and the like. As a method of knitting a woven fabric, plain weave, basket weave, twill weave, and the like are known, and from these disclosures, they can be appropriately selected and used according to the intended use or performance. In addition, a glass woven fabric obtained by subjecting a woven fabric to a fiber opening treatment or a surface treatment with a silane coupling agent or the like is suitably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. The varnish may be impregnated into the reinforcing fiber and dried by heating to obtain a prepreg.
The laminated board of the present embodiment includes 1 or more prepregs. The laminate sheet is not particularly limited as long as it has 1 or more sheets of prepreg, and may have any other layers. The method for producing the laminated sheet is not particularly limited, and may be generally applied by publicly known methods. For example, in forming a metal foil-clad laminate, a multi-stage extruder, a multi-stage vacuum extruder, a continuous molding machine, an autoclave molding machine, or the like may be used, and the prepregs may be laminated to each other and heated and pressure-molded to obtain a laminate. In this case, the heating temperature is not particularly limited, but is more preferably 65 to 300℃and still more preferably 120 to 270 ℃. The pressure at which the lamination is performed is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate, and the quality is unstable, and if the pressure is too low, the adhesion between the bubbles and the lamination is deteriorated, so that it is more preferable to use 2.0 to 5.0MPa, and still more preferable to use 2.5 to 4.0 MPa. The laminated board of the present embodiment is preferably used as a metal foil-clad laminated board described later by including a layer made of metal foil.
The prepreg is cut into a desired shape, and laminated with copper foil or the like as needed, and then the laminate is heated and cured by applying pressure thereto by an extrusion molding method, an autoclave molding method, a sheet winding molding method, or the like, whereby an electrical/electronic laminate (printed wiring board) or a carbon fiber reinforced material can be obtained.
The cured product of the present invention can be used for various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition of the present invention exhibits excellent heat resistance and dielectric characteristics, and is therefore suitable for use as a semiconductor element package, a liquid crystal display element package, an organic EL element package, a printed wiring board, a flexible electronic component such as a build-up laminate, or a composite material for a lightweight high-strength structural material such as a carbon fiber reinforced plastic or a glass fiber reinforced plastic.
Examples (example)
The present invention will be specifically described below with reference to examples and comparative examples. In the present description, "parts" and "%" refer to "parts by weight" and "% by weight", respectively. The softening point and melt viscosity were measured as follows.
GPC (gel permeation chromatography) analysis
The manufacturer: waters
And (3) pipe column: SHODEXGPCKF-601 (2 book), KF-602, KF-602.5, KF-603 flow rate: 0.5ml/min.
Column temperature: 40 DEG C
Solvent was used: THF (tetrahydrofuran)
A detector: RI (differential refraction detector)
HPLC (high-speed liquid chromatography) analysis
And (3) pipe column: inertsilODS-2
Flow rate: 1.0ml/min.
Column temperature: 40 DEG C
Solvent was used: acetonitrile/water
A detector: LED array (225 nm)
Amine equivalent weight
The obtained value was used as an amine equivalent according to JIS K-7236, appendix A (correction method for glycidyl amine).
DMA analysis
The manufacturer: TA Instrument
The device comprises: DMAQ800
Measurement mode: stretching
Heating rate: 2 ℃/min.
Measuring temperature range: 25 ℃ to 350 DEG C
Measuring frequency: 10Hz
The temperature at which the tan delta value becomes maximum is taken as Tg.
Mechanical strength
The manufacturer: shijin production station
The device comprises: autograph AGS-X
Stretching speed: 0.5mm/min
The test piece was clamped so that the length of the test piece became 5cm, and the tensile measurement was performed at the test speed described above in the direction of 180 °.
Water absorption test
Immersed in water for 24 hours, taken out, and the weight of the mixture was measured and calculated after being left at 25℃for 24 hours under 30% conditions.
Dielectric constant test, dielectric tangent test
The manufacturer: AET shares Limited
The device comprises: 10GHz cavity resonator
The test piece having a width of 2.5mm and a length of 5cm was dried at 120℃for 2 hours by a dryer and then measured. The test piece was immersed in water for 24 hours, taken out, left at 25℃for 24 hours in a 30% environment, and then measured again.
Synthesis example 1: synthesis of aromatic amine resin (A-1)
A flask equipped with a thermometer, a cooling tube, a DEAN-STARK azeotropic distillation trap and a stirrer was charged with 192 parts of aniline, 112 parts of toluene and 100 parts of 1, 3-bis (2-hydroxy-2-propyl) benzene, and 21.5 parts of 35% hydrochloric acid was dropped over 10 minutes. The temperature in the system was raised to 160℃and the reaction was carried out at the same temperature for 17 hours while distilling off water and toluene. After this, after cooling to 80 ℃, 124 parts of toluene was added, and 30 parts of 30% aqueous sodium hydroxide solution was dropped over 10 minutes. After this, the mixture was stirred at the same temperature for 2 minutes and allowed to stand for 30 minutes. The separated lower aqueous layer was removed, and the reaction mixture was washed with water repeatedly until the washing solution became neutral. Then, 158 parts of the aromatic amine resin (A-1) represented by the above formula (2) was obtained by distilling off excess aniline and toluene from the oil layer under reduced pressure and heating by a rotary evaporator. The amine equivalent of the aromatic amine resin (A-1) was 186.1g/eq and the softening point was 58.8 ℃. By GPC analysis (RI), n=1 bodies were 62.5 area%. GPC chart is shown in FIG. 1.
Synthesis example 2: synthesis of maleimide resin (M-1)
A flask equipped with a thermometer, a cooling tube, a DEAN-STARK azeotropic distillation trap, and a stirrer was charged with 73.5 parts of maleic anhydride, 126 parts of toluene, 1.86 parts of methanesulfonic acid, and 12.6 parts of N-methyl-2-pyrrolidone (Methyl pyrrolidone) to form a heated reflux state. Next, 93 parts of the aromatic amine resin (a-1) was dissolved in 55.8 parts of toluene to prepare a resin solution, which was then dropped over 4 hours while maintaining the reflux state. In this case, the condensed water azeotroped under reflux conditions and toluene were cooled and separated in a DEAN-STARK azeotropic distillation trap, and toluene belonging to the organic layer was returned to the system, and the water was discharged from the system. After the completion of the dropping of the resin solution, the reaction was carried out for 10 hours while maintaining the reflux state and performing the dehydration operation.
After the completion of the reaction, the water washing was repeated 4 times to remove methane sulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure at 70 ℃. Then, 0.93 part of methanesulfonic acid was added thereto, and the reaction was carried out in a heated reflux state for 4 hours. After the reaction was terminated, the water washing was repeated 4 times until the water washing became neutral, water was removed from the system by azeotropic distillation of toluene and water under a heating and pressure reduction at 70 ℃ or lower, toluene was distilled off under a heating and pressure reduction until the resin concentration became about 70 to 80%, and toluene was added to prepare a resin concentration of 60%. Thus, a maleimide solution (V-1) containing a maleimide resin (M-1) was obtained. By GPC analysis (RI), the obtained maleimide resin (M-1) had 57.4 area% of n=1 bodies, 21.3 area% of n=2 bodies and 21.3 area% or more of n=3 bodies. The orientation ratio (ortho-ortho/para-para/ortho-para) in the n=1-mer was 32.0%/25.4%/42.6% from HPLC analysis (225 nm). In addition, the softening point was 115.5℃and the viscosity was 6.0 Pa.s. GPC charts are shown in FIG. 2.
Synthesis example 3: synthesis of maleimide resin (B-1)
110g of toluene and 36g of N-methylpyrrolidone (Methyl pyrrolidone) were charged into a 500ml round-bottomed flask equipped with a stirring bar coated with Teflon (registered trademark). Next, 85.6g (0.16 mol) of PRIAMINE 1074 (manufactured by CRODA JAPAN Co., ltd.) was added, and then 15.4g (0.16 mol) of anhydrous methanesulfonic acid was slowly added to form a salt. Stirring was carried out for about 10 minutes and mixed, and then 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (24.5 g, 0.08 mol) was slowly added to the stirred mixture. A DEAN-STARK trap was installed in the flask with a condenser. The mixture was heated at reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water produced from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature and 18.8g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for 8 hours to obtain a desired amount of produced water. After cooling to room temperature, 200ml of toluene was further added to the flask. Next, the diluted organic layer was washed with water (100 ml. Times.3) to remove salts or unreacted starting materials. After this, the solvent was removed under vacuum to obtain 108g (yield 90%, mw=3,600) of an amber waxy maleimide resin (B-1).
Examples 1 to 5 and comparative examples 1 to 8
Various maleimide resins and thermoplastic resins (SEPTON 2104) were weighed in the proportions shown in table 1, and acetone was added so as to form 50 wt% of the resin solid content, followed by mixing to prepare a varnish. In addition, 2-ethyl-4-methylimidazole (2E 4MZ, manufactured by Sichuang chemical industry Co., ltd.) as a hardening accelerator was dissolved in a varnish. The varnish in which the hardening accelerator was dissolved was heated at 60℃for 30 minutes and at 150℃for 1 hour by a vacuum dryer to prepare a curable resin composition. The resulting curable resin composition was sandwiched between copper foils, and a pressure of 1MPa was applied under vacuum and cured at 220℃for 2 hours. The hardenability was confirmed at this time, and physical properties were evaluated. The results of various measurements on the cured products obtained are shown in table 1.
M-1 (component (A)) and the solvent obtained in Synthesis example 2 was distilled off under reduced pressure by heating
B-1 (component (B)) obtained in Synthesis example 3
MIR-3000 (MIR-3000-70 MT (manufactured by Nippon chemical Co., ltd.) was distilled off under reduced pressure by heating)
SEPTON 2104 (thermoplastic resin, manufactured by KURARAY Co., ltd.)
2E4MZ (hardening accelerator, manufactured by four-country chemical industry Co., ltd.)
TABLE 1
The results of examples 1 to 5 were that the heat resistance, mechanical properties, water absorption and dielectric properties were all good. In addition, examples 1 to 4 had Tg of 200℃or higher, and heat resistance was more excellent. On the other hand, the dielectric properties after water absorption were not preferable as the results of comparative example 1, the heat resistance was not preferable as the results of comparative examples 2 to 4, the dielectric properties were not preferable as the results of comparative examples 5 to 7, the heat resistance and the elastic modulus were not preferable as the results of comparative example 8, and all the properties could not be satisfied.
The present application has been described in detail with reference to specific examples, but it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
In addition, the present application is incorporated by reference in its entirety according to Japanese patent application No. (Japanese patent application No. 2021-056834) filed on 3/30 of 2021. In addition, the entire contents to be cited herein are incorporated in their entirety.

Claims (11)

1. A maleimide resin mixture comprising a maleimide resin (A) represented by the following formula (1) and a maleimide resin (B) obtained by reacting a diamine (B) with maleic anhydride;
In the formula (1), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents an integer of 0 to 3, and n is a repetition number, and the average value thereof is 1 < n < 5.
2. The maleimide resin mixture according to claim 1, wherein the aforementioned component (b) is obtained by reacting a diamine (b-1) having 4 to 60 carbon atoms with a tetracarboxylic dianhydride (b-2).
3. The maleimide resin mixture according to claim 2, wherein the aforementioned component (b-1) is a diamine (b-1 a) derived from a dimer acid.
4. A maleimide resin mixture according to claim 2 or 3, wherein the aforementioned component (b-2) is represented by the following formula (4),
5. the maleimide resin mixture according to any of claims 1 to 4, wherein the aforementioned component (A) is represented by the following formula (2),
in the formula (2), R which is present in many cases independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents an integer of 0 to 3, and n is a repetition number, and the average value thereof is 1 < n < 5.
6. The maleimide resin mixture according to any of claims 1 to 5, wherein the aforementioned component (B) is represented by the following formula (3),
in the formula (3), R 1 Represents a 2-valent hydrocarbon group (c) derived from a dimer acid, R 2 Represents a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from the dimer acid, R 3 Represents any one selected from the group consisting of a 2-valent hydrocarbon group (c) derived from a dimer acid and a 2-valent organic group (d) other than the 2-valent hydrocarbon group (c) derived from a dimer acid, R 4 R is R 5 Each independently represents 1 or more organic groups selected from a 4-valent organic group having 4 to 40 carbon atoms and having a single-ring alicyclic structure or a condensed polycyclic alicyclic structure, a 4-valent organic group having 8 to 40 carbon atoms and having both an alicyclic structure and an aromatic ring, wherein the organic groups having a single-ring alicyclic structure are linked directly or via a crosslinked structure; m is an integer of 1 to 30, n is an integer of 0 to 30, R 4 R is R 5 May be the same or different.
7. The maleimide resin mixture according to any of claims 1 to 6, wherein the weight ratio of the aforementioned component (a) to the aforementioned component (B) is 99/1 to 60/40.
8. A curable resin composition comprising the maleimide resin mixture according to any one of claims 1 to 7.
9. The maleimide resin mixture according to claim 8, further comprising a hardening accelerator.
10. A prepreg comprising a fibrous substrate having a sheet-like structure and the maleimide resin mixture according to any one of claims 1 to 7 or the curable resin composition according to claim 8 or 9.
11. A cured product obtained by curing the maleimide resin mixture according to any one of claims 1 to 7, the curable resin composition according to claim 8 or 9, or the prepreg according to claim 10.
CN202280026458.7A 2021-03-30 2022-03-25 Maleimide resin mixture, curable resin composition, prepreg, and cured product thereof Pending CN117098789A (en)

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