TW202305038A - Maleimide resin mixture, curable resin composition, prepreg and cured article thererof - Google Patents

Abstract

A maleimide resin mixture of this invention contains a maleimide resin (B) obtained by reacting a maleimide resin (A) represented by the following formula (1), a diamine (b), and a maleic acid anhydride. (In the formula (1), plurality of R each 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 is 1 < n < 5.).

Description

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

The present invention relates to a maleimide resin mixture, a curable resin composition, a prepreg, and a cured product thereof, which can be suitably used for semiconductor packaging materials, printed wiring boards, build-up laminates, etc. Lightweight and high-strength materials such as electrical and electronic components, carbon fiber reinforced plastics, and glass fiber reinforced plastics, and 3D printing applications.

In recent years, with the expansion of the field of use of laminated boards equipped with electrical and electronic components, the required characteristics have been extensive and advanced. In the past, although semiconductor chips were mounted on metal leadframes, semiconductor chips with high processing capabilities such as CPUs were mostly mounted on laminates made of polymer materials. With the high-speed progress of CPU and other components, as the clock frequency becomes higher, the problem of signal transmission delay or transmission loss has been regarded as very important. Laminates made of polymer materials have been required to have low dielectric constant or low Dielectric tangent.

Also, from the perspective of advanced communication technology, the operation of 5G devices has increased in recent years. Not only the Sub6 frequency band, but also quasi-millimeter waves above 10GHz, especially above 28GHz, are expected to be used. Millimeter wave communication devices will increase explosively, and substrate materials corresponding to high frequencies will become necessary in base stations, antennas, and communication devices. In such substrate materials and the like, in order not to lower the transfer speed, high dielectric properties (especially, dielectric tangent) have been regarded as important, and materials that can be stably used in these fields have been demanded.

Furthermore, due to the popularization of portable electronic devices such as mobile phones, precision electronic devices can be used/carried in the outdoor environment or around the human body, so the substrate material is resistant to the external environment (especially, the humidity and heat environment) durability becomes necessary. Further, in the field of automobiles, electronicization is rapidly progressing, and precision electronic devices are sometimes placed near the engine, and heat/humidity resistance is required at a higher level.

A wiring board using BT resin, which is a bisphenol A-type cyanate compound and a bismaleimide compound disclosed in Patent Document 1, has excellent heat resistance, chemical resistance, and dielectric properties. , has been widely used as a high-performance wiring board, but in order to correspond to higher performance as mentioned above, it must be improved.

Among them, compared with the epoxy resins used in the above-mentioned applications in the past, the heat resistance of the maleimide resin series available in the market is greatly improved, and it exhibits excellent dielectric properties in the high-frequency region. characteristic. However, the maleimide resin with high heat resistance has the disadvantages of being fragile and having low adhesion to copper foil due to its low moisture resistance and rigidity.

On the other hand, although maleimide resins such as Patent Documents 2 and 3 have also been developed, they are still insufficient.

Also, although a composition comprising maleimide resin and propylene group-containing phenolic resin such as Patent Document 4 has been proposed, phenolic hydroxyl groups that do not participate in the reaction remain during the hardening reaction, so the dielectric properties In addition to being insufficient, there is still the problem of high water absorption.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Patent Publication No. 54-30440

[Patent Document 2] Japanese Patent Application Laid-Open No. 03-100016

[Patent Document 3] Japanese Patent No. 5030297

[Patent Document 4] Japanese Patent Application Laid-Open No. 04-359911

[Patent Document 5] Japanese Patent Publication No. 04-75222

[Patent Document 6] Japanese Patent Publication No. 06-37465

The present invention is made in view of such circumstances, and an object thereof is to provide a maleimide resin mixture, a curable resin composition, and a cured product thereof that exhibit excellent heat resistance, mechanical properties, and dielectric properties after moisture absorption .

The inventors of the present invention have finally completed the present invention as a result of diligent research in order to solve the above-mentioned problems. That is, the present invention relates to the following [1] to [11].

[1]

A kind of maleimide resin mixture, is to comprise maleimide resin (B), and this maleimide resin (B) is to make maleimide resin (A) shown in following formula (1) ), diamine (b), and maleic anhydride reaction obtained;

(In the formula (1), the plural R systems independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 5. m represents an integer from 0 to 3. n represents the number of repetitions, and its average value is 1<n <5.)

[2]

The maleimide resin mixture as described in item [1] above, wherein the aforementioned component (b) is made by reacting diamine (b-1) having 4 to 60 carbon atoms with tetracarboxylic dianhydride (b-2) earner.

[3]

The maleimide resin mixture as described in [2] above, wherein the component (b-1) is a diamine (b-1a) derived from a dimer acid.

[4]

The maleimide resin mixture as described in [2] or [3] above, wherein the component (b-2) is represented by the following formula (4).

[5]

The maleimide resin mixture according to any one of the preceding items [1] to [4], wherein the aforementioned component (A) is represented by the following formula (2):

(In the formula (2), the plural R systems independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 5. m represents an integer from 0 to 3. n represents the number of repetitions, and its average value is 1<n <5.)

[6]

The maleimide resin mixture according to any one of [1] to [5] above, wherein the component (B) is represented by the following formula (3).

(In the formula (3), ^R1 represents the divalent hydrocarbon group (c) derived from the dimer acid, and ^R2 represents a divalent organic group other than the divalent hydrocarbon group (c) derived from the dimer acid (d), R ^represents a divalent organic group (d) selected from a divalent hydrocarbon group (c) derived from a dimer acid and a divalent organic group (c) derived from a dimer acid. In any one of the groups formed, R ⁴ and R ⁵ each independently represent a tetravalent organic group with a carbon number of 4 to 40 having a monocyclic or condensed polycyclic alicyclic structure, a monocyclic The organic group of the alicyclic structure is a tetravalent organic group with 8 to 40 carbon atoms linked directly or via a cross-linking structure, and a semi-alicyclic organic group having both an alicyclic structure and an aromatic ring. One or more organic groups among tetravalent organic groups of 8 to 40. m is an integer of 1 to 30, n is an integer of 0 to 30, and R ⁴ and R ⁵ may be the same or different. )

[7]

The maleimide resin mixture according to any one of [1] to [6] above, 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 described in any one of [1] to [7].

[9]

The maleimide resin mixture as described in [8] above further contains a hardening accelerator.

[10]

A prepreg comprising the maleimide resin mixture described in any one of the preceding items [1] to [7], or the curable resin composition described in the preceding item [8] or [9] held on a sheet Shaped fiber substrate.

[11]

A cured product, which is the maleimide resin mixture described in any one of the preceding items [1] to [7], the curable resin composition described in the preceding item [8] or [9], or the preceding item [10 ] Obtained by the hardening of the prepreg.

The cured product of the maleimide resin mixture and curable resin composition of the present invention is excellent in heat resistance, mechanical properties, and dielectric properties after moisture absorption.

FIG. 1 is a GPC chart of Synthesis Example 1.

FIG. 2 is a GPC chart of Synthesis Example 2.

The maleimide resin mixture of the present invention contains maleimide resin (B) (hereinafter also referred to as component (B).), and the maleimide resin (B) has the following formula The thing obtained by reacting the maleimide resin shown in (1) (Hereinafter, also called component (A).), diamine (b), and maleic anhydride.

(In the formula (1), the plural R systems independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 5. m represents an integer from 0 to 3. n represents the number of repetitions, and its average value is 1<n <5.)

In the aforementioned formula (1), m is usually 0 to 3, preferably 0 to 2, and more preferably 0. R is usually a hydrogen atom, or an alkyl group having 1 to 5 carbons, preferably a hydrogen atom, methyl or ethyl, and even more preferably a hydrogen atom. When m is greater than 3 or when R is an alkyl group having 6 or more carbon atoms, the electrical characteristics may be lowered because the alkyl group is exposed to molecular vibration at high frequencies.

In the aforementioned formula (1), the value of n is the value of the number average molecular weight that can be obtained from the measurement of gel permeation chromatography (GPC, detector: RI) of maleimide resin, or from the The individual area ratios of the separated peaks were calculated.

In the aforementioned formula (1), when n=1, the solubility to solvents is low, and when n is 5 or more, the fluidity during molding is deteriorated, and the characteristics as a cured product cannot be fully exhibited.

Ingredient (A) preferably has a molecular weight distribution. In the above-mentioned formula (1), the content obtained by GPC analysis (RI) of n=1 body is preferably below 98 area%, more preferably 20 to 90% by area, more preferably 30 to 80% by area, especially preferably 40 to 80% by area. When the content of the n=1 body is 98 area % or less, the heat resistance becomes good. Moreover, crystallinity will fall, and solvent solubility will become favorable. On the other hand, if the lower limit of the n=1 body is 20 area % or more, the viscosity of the resin solution will decrease and the impregnation property will become better. In addition, when taken out as a solid, the solvent can be removed at low temperature, so self-polymerization is less likely to occur, and handling becomes easier.

Component (A) improves the solvent solubility by increasing the ratio of the asymmetric structure having a different orientation to the maleimide group, and improves the dielectric properties in its cured product. The orientation ratio system in the n=1 body of the aforementioned formula (1) can be obtained from HPLC analysis (225nm), and the ortho-para system is more than 30 area% and less than 60 area% % is better, more than 35 area % and less than 55 area % is even more preferable, and more than 40 area % and less than 55 area % is especially preferred.

The softening point of component (A) is preferably from 50°C to 150°C, more preferably from 80°C to 120°C, more preferably from 90°C to 120°C, especially preferably from 95°C to 120°C. Also, the melt viscosity at 150°C is 0.05 to 100 Pa‧s, preferably 0.1 to 40 Pa‧s.

When the compound represented by said formula (1) is represented by following formula (2), it is more preferable. In the formula (1), the substitution position of the propyl group of the phenyl ring to which the maleimide group is not bonded is because the crystallinity is lowered compared to the para position.

(In the formula (2), the plural R systems independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 5. m represents an integer from 0 to 3. n represents the number of repetitions, and its average value is 1<n <5.)

The preferred ranges of R and m in the aforementioned formula (2) are the same as those of the aforementioned formula (1).

Hereinafter, although the manufacturing method about the component (A) is demonstrated, it is not limited to this manufacturing method.

[Manufacturing method of aromatic amine resin]

Component (A) can use the aromatic amine resin represented by following formula (5) as a precursor.

(In the formula (5), the R systems that exist in plural are independently representing a hydrogen atom or an alkyl group with 1 to 5 carbons. M is an integer representing 0 to 3. N is the number of repetitions, and its average value is 1<n <5.)

The preferred ranges of R and m in the aforementioned formula (5) are the same as those of the aforementioned formula (1).

The preparation method of the aromatic amine resin shown in the aforementioned formula (5) is not particularly limited. ) benzene is reacted at 180 to 250° C. in the presence of an acidic catalyst to obtain the n=1 body in the aforementioned formula (5) as a main component. In the n=1 body, it contains the orientation of 2 molecules of aniline to 1,3-bis(p-aminocumyl)benzene and 1,3-bis(o-aminocumyl)benzene Compounds with the same symmetrical structure, or for aniline 2 such as 1-(o-aminocumyl)-3-(p-aminocumyl)benzene The molecular orientation is three isomers of compounds with different asymmetric structures. Furthermore, n=2 to 5 bodies are also generated as side components, but in Patent Document 5, these are purified by crystallization to obtain 1,3-bis(p-aminocumyl) with a purity of 98%. )benzene. Also, in Patent Document 6, N,N'-(1,3-phenylene-di-( 2,2-propylene)-bis-p-phenylene)bismaleimide to obtain a crystalline product, but in order to dissolve this in the solvent, it must be heated, if it is placed at room temperature after heating , after several hours the crystallization will be completely precipitated. Therefore, when adjusting the resin composition, crystals may also precipitate, and N,N'-(1,3-phenylene-di-(2,2-propylene)-di-p-phenylene)bis The higher the concentration of maleimide, the higher the possibility of crystallization. In order to make printed wiring boards or composite materials, glass cloth or carbon fiber is impregnated with varnish to attach resin, but if the crystals are precipitated, it is impossible to carry out the impregnation operation. On the other hand, in order to maintain the dissolved state, if the temperature is increased, the composition If the reaction is too fast, the usable time of the varnish will be shortened.

When synthesizing the aromatic amine resin represented by the aforementioned formula (5), the acidic catalyst used may include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferrous chloride, aluminum chloride, p-toluenesulfonic acid , methanesulfonic acid and other acidic catalysts. In the present invention, protonic acids such as hydrochloric acid, p-toluenesulfonic acid, and methanesulfonic acid are preferred. These systems may be used alone or in combination of two or more. Relative to 100% by weight of the aniline used, the amount of the catalyst used is preferably 1 to 12% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 7% by weight, if more than 12% by weight, There are few compounds with asymmetric structure as the target, and compounds with symmetrical structure will be completed first. On the other hand, if it is less than 1%, not only the progress of the reaction will be slowed down, but sometimes the reaction cannot be completed, so it is not good.

The reaction can be carried out using organic solvents such as toluene and xylene as needed, or without a solvent. For example, after adding an acidic catalyst to a mixed solution of aniline and a solvent, When the catalyst contains water, it is preferable to remove water from the system by azeotroping. After that, diisopropenylbenzene or bis(α-hydroxyisopropyl)benzene is added, and thereafter, the temperature is raised while removing the solvent from the system at 140 to 190° C., preferably 160 to 190° C. The reaction is for 5 to 50 hours, preferably for 5 to 30 hours. When the reaction temperature is too high, the asymmetric structure will be bonded after formation, and the symmetric structure will be completed preferentially, and the intended solvent solubility and electrical properties cannot be exerted. When bis(α-hydroxyisopropyl)benzene is used, water is a by-product, so when the temperature rises, it is removed from the system while azeotroping with the solvent. After the reaction is terminated, neutralize the acidic catalyst with an aqueous alkali solution, add a non-water-soluble organic solvent to the oil layer and repeatedly wash with water until the wastewater becomes neutral, then remove the solvent and excess aniline derivatives under heating and reduced pressure. When activated clay or ion exchange resin is used, after the reaction is terminated, the reaction liquid is filtered to remove the catalyst.

Moreover, since phenylamine is produced as a by-product depending on the reaction temperature or the type of catalyst, it is preferable to remove it as needed. Under high temperature/high vacuum, or by means of steam distillation, etc., the diphenylamine derivatives are removed until less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.2% by weight.

Furthermore, the compound represented by the aforementioned formula (5) is more preferably a structure represented by the following formula (5-a).

(In the formula (5-a), the plural Rs are independently representing a hydrogen atom or an alkyl group with 1 to 5 carbons. m is an integer representing 0 to 3. n is the number of repetitions, and its average value is 1 <n<5.)

The preferred ranges of R and m in the aforementioned formula (5-a) are the same as those of the aforementioned formula (1).

[Manufacturing method of maleimide resin]

Component (A) is the aromatic amine resin represented by the aforementioned formula (5) obtained by the above steps, and maleic acid or maleic anhydride (hereinafter also referred to as "maleic anhydride") in a solvent, It can be obtained by addition or dehydration condensation reaction in the presence of a catalyst.

The solvent used in the reaction must remove water generated during the reaction from the system, so it is preferable to use a non-water-soluble solvent. Examples include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, and ester solvents such as ethyl acetate and butyl acetate. , methyl isobutyl ketone, cyclopentanone, and other ketone-based solvents, etc., are not limited thereto, and two or more of them may be used in combination.

In addition, an aprotic polar solvent may also be used in combination in addition to the aforementioned water-insoluble solvent. For example, dimethylsulfide, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2 -Pyrrolidone and the like may be used in combination of two or more. When an aprotic polar solvent is used, it is preferable to use one having a higher boiling point than the water-insoluble solvent used together.

Also, the catalyst used in the reaction is an acidic catalyst and 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, preferably 1 to 5% by weight, relative to the aromatic amine resin.

For example, dissolve the aromatic amine resin represented by the aforementioned formula (5) in toluene and N-methyl-2-pyrrolidone, add maleic anhydride here to generate amic acid, and then add p- Toluenesulfonic acid was reacted while removing the generated water from the system under reflux conditions.

Alternatively, dissolve maleic acid in toluene, add the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the aforementioned formula (5) under stirring to generate amic acid, and then add For p-toluenesulfonic acid, the reaction was carried out while removing the generated water from the system under reflux conditions.

Alternatively, dissolve maleic anhydride in toluene, add p-toluenesulfonic acid, and in a stirring/reflux state, drop N-methyl-2-pyrrolidine of the aromatic amine resin represented by the aforementioned formula (5) For the ketone solution, the water that comes out of the azeotrope in the middle is removed to the outside of the system, and the toluene is returned to the system and reacted (the above is the first stage of the reaction).

In either method, maleic anhydride is usually used in an amount of 1.0 to 3.0 times, preferably in an amount of 1.2 to 2.0 times, relative to the amine groups of the aromatic amine resin represented by the aforementioned formula (5).

In order to reduce the unclosed amide acid, add water to the reaction solution after the above-mentioned maleimidization reaction, and separate it into a resin solution layer and a water layer. Excess maleic acid or maleic anhydride, aprotic Polar solvents, catalysts, etc. are dissolved in the water layer side, so they are removed by liquid separation. Then, repeat the same operation to completely remove excess maleic acid or maleic anhydride, aprotic polar solvents, and catalysts. . After removing excess maleic acid or maleic anhydride, aprotic polar solvent, and the maleimide resin solution of the organic layer of the catalyst, the catalyst is added again to carry out the remaining amic acid under heating and reflux conditions again. The dehydration ring-closing reaction, thereby, can obtain the maleimide resin solution (above, be the second stage reaction) that acid value is low.

The time for the re-dehydration and ring-closing reaction is usually 1 to 5 hours, preferably 1 to 3 hours, and the aforementioned aprotic polar solvent can be added as needed. After the reaction was terminated, cooling was performed, and washing with water was repeated until the washing water became neutral. After that, azeotropic dehydration under reduced pressure After water is removed, the solvent can be distilled off, or another solvent can be added to adjust the desired concentration of the resin solution, or the solvent can be completely distilled off to take out the resin as a solid component.

Next, component (B) is demonstrated.

Component (B) can be obtained by making diamine (b) and maleic anhydride react.

Component (b) includes linear or branched aliphatic diamine, aliphatic ether diamine, or cyclic aliphatic diamine, or aromatic diamine. Only 1 type may be used for a diamine system, and 2 or more types may be used.

Examples of the linear or branched aliphatic diamine include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1,9-nonanediamine. , 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 2, 7-Dimethyl-1,8-octanediamine, etc. Also, from the viewpoint of obtaining a cured product with a lower tensile modulus, the carbon number of the diamine is preferably from 6 to 60, and the diamine derived from dimer acid is more preferred.

Examples of the aforementioned aliphatic ether diamine include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), 1,2-bis(2-aminoethoxy base) ethane, etc.

Examples of the cyclic aliphatic diamine include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diamino Cyclohexane, methylcyclohexanediamine, isophoronediamine, etc.

Examples of the aforementioned 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, 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylmethane; 3,3'-diaminodiphenylmethane; 4,4-diamine benzophenone; 4,4-diaminodiphenyl sulfide; 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

The aforementioned component (b) is more preferably obtained by reacting diamine (b-1) with 4 to 60 carbon atoms and tetracarboxylic dianhydride (b-2), and component (b-1) is particularly preferably The case of diamine (b-1a) derived from dimer acid. In this case, component (B) can be obtained by reacting diamine (b-1a) derived from dimer acid, tetracarboxylic dianhydride (b-2) and maleic anhydride, and component (B) ) has a divalent hydrocarbon group (c) derived from a dimer acid bonded to a cyclic imide.

The divalent hydrocarbon group (c) derived from the dimer acid refers to a divalent residue obtained by removing two carboxyl groups from the dicarboxylic acid contained in the dimer acid. In the present invention, such a divalent hydrocarbon group (c) derived from a dimer acid may be obtained by substituting two carboxyl groups contained in a dicarboxylic acid contained in a dimer acid with an amino group. Diamine (b-1a) reacts with tetracarboxylic dianhydride (b-2) and maleic anhydride described later to form an imide bond, thereby introducing it into the maleimide resin.

In the present invention, the aforementioned dimer acid is preferably a dicarboxylic acid with 20 to 60 carbon atoms. Specific examples of the aforementioned dimer acid include those obtained by dimerizing unsaturated bonds of unsaturated carboxylic acids such as linolenic acid, oleic acid, and linolenic acid, followed by distillation and purification. The dimer acid related to the above-mentioned specific examples mainly contains dicarboxylic acids with 36 carbon atoms, and usually contains about 5% by mass of tricarboxylic acids with 54 carbon atoms as a limit, and contains about 5% by mass of monocarboxylic acids. as a limit. The diamine (b-1a) derived from a dimer acid (hereinafter referred to as the diamine (b-1a) derived from a dimer acid as the case may be) related to the present invention is derived from the above two The diamine obtained by substituting two carboxyl groups of each dicarboxylic acid contained in the polymer acid into an amine group is usually a mixture. In the present invention, such diamines (b-1a) derived from dimer acids include, for example, [3,4-bis(1-aminoheptanyl] base) diamines such as 6-hexyl-5-(1-octenyl)]cyclohexane, or diamines obtained by hydrogenating such diamines to saturate unsaturated bonds.

The dimer acid-derived divalent hydrocarbon group (c) related to the present invention introduced into the maleimide resin using such dimer acid-derived diamine (b-1a) is preferably The residue of two amine groups is removed from the dimer acid-derived diamine (b-1a). Also, when the maleimide resin (B) related to the present invention is obtained by using the aforementioned dimer acid-derived diamine (b-1a), the aforementioned dimer acid-derived diamine (b-1a) 1a) may be used individually by 1 type, and may use it combining 2 or more types from which a composition differs. In addition, commercial items, such as "PRIAMINE1074" (made by CRODA JAPAN Co., Ltd.), can be used about diamine (b-1a) derived from such a dimer acid, for example.

In the present invention, the so-called tetracarboxylic dianhydride (b-2) has an alicyclic structure adjacent to the anhydride group. When forming a maleimide resin after the reaction, the adjacent part of the imide ring has a Tetracarboxylic dianhydride with a ring structure. If the adjacent portion of the imide ring has an alicyclic structure, others may contain an aromatic ring in the structure.

In the present invention, the component (B) is preferably represented by the following formula (3). In the following formula (3), R ⁴ and R ⁵ are derived from the structure of tetracarboxylic dianhydride (b-2).

(In the formula (3), ^R1 represents the divalent hydrocarbon group (c) derived from the dimer acid, and ^R2 represents a divalent organic group other than the divalent hydrocarbon group (c) derived from the dimer acid (d), R ^represents a divalent organic group (d) selected from a divalent hydrocarbon group (c) derived from a dimer acid and a divalent organic group (c) derived from a dimer acid Any one of the group consisting of, R ⁴ and R ⁵ each independently represent a carbon number of 4 to 40 (preferably carbon number 6 to 40) having an alicyclic structure selected from a monocyclic or condensed polycyclic ring The 4-valent organic group, the organic group with a monocyclic alicyclic structure is a 4-valent organic group with a carbon number of 8 to 40 connected to each other directly or through a cross-linking structure, and a 4-valent organic group with an alicyclic structure and an aromatic ring. One or more organic groups among the tetravalent organic groups with a semi-alicyclic structure of 8 to 40 carbon atoms. m is an integer from 1 to 30, n is an integer from 0 to 30, R ⁴ and R ⁵ are respectively may be the same or different.)

In the present invention, the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (6). The tetracarboxylic dianhydride (b-2) which has an alicyclic structure represented by following formula (6) has an alicyclic structure adjacent to an anhydride group.

(In the formula (6), Cy is a tetravalent organic group with 4 to 40 carbon atoms including a hydrocarbon ring, and the organic group may also include an aromatic ring.)

The tetracarboxylic dianhydride (b-2) which has an alicyclic structure represented by said formula (6) can be specifically represented by following formula (6-a).

(In formula (6-a), R ⁶ is a tetravalent organic group with 4 to 40 carbon atoms containing a hydrocarbon ring, and the organic group may also contain an aromatic ring.)

In the present invention, the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formulas (7-1) to (7-11) . The tetracarboxylic dianhydride (b-2) represented by formulas (7-1) to (7-11) has a structure comprising the following: alicyclic structure having a monocyclic or condensed polycyclic structure with carbon numbers from 4 to A tetravalent organic group with 40 (preferably 6 to 40 carbons), and an organic group with a monocyclic alicyclic structure are tetravalent organic groups with 8 to 40 carbons linked directly or via a crosslinking structure. An organic group, or a tetravalent organic group having 8 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring.

(In formula (7-4), _X1 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a divalent organic group with 1 to 3 carbons. In formula (7-6), _X2 is a direct bond knot, oxygen atom, sulfur atom, sulfonyl group, divalent organic group with 1 to 3 carbons or aryl group.)

The tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the above formulas (7-1) to (7-11) can be specifically expressed as the following formulas (7-1a) to (7- 11a).

(In formula (7-4a), _X1 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a divalent organic group with 1 to 3 carbons. In formula (7-6a), _X2 is a direct bond bond, oxygen atom, sulfur atom, sulfonyl group, divalent organic group with 1 to 3 carbons or aryl group.)

The tetracarboxylic dianhydride (b-2) used in the present invention is a tetravalent organic group with a carbon number of 4 to 40 (preferably a carbon number of 6 to 40) having a monocyclic or condensed polycyclic alicyclic structure The organic group having a monocyclic alicyclic structure is a tetravalent organic group having 8 to 40 carbon atoms connected to each other directly or through a crosslinking structure, or having both an alicyclic structure and an aromatic ring A tetravalent organic group with 8 to 40 carbon atoms having a semialicyclic structure. The tetracarboxylic dianhydride (b-2) having an alicyclic structure specifically includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride (H-PMDA), 1,1'-bicyclohexane-3,3', 4,4'-tetracarboxylic acid-3,4: 3',4'-dianhydride (H-BPDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3, 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2 .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-nor Various types of acetic dianhydride Alicyclic tetracarboxylic dianhydride or compounds whose aromatic rings are substituted with alkyl or halogen atoms, such as 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5 - Various semi-alicyclic tetracarboxylic dianhydrides of dioxo-3-furyl)naphthalene[1,2-c]furan-1,3-dione or the hydrogen atoms of these aromatic rings are alkane Compounds substituted with groups or halogen atoms.

In the present invention, tetracarboxylic dianhydride (b-2) is preferably tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (8).

In the present invention, the tetracarboxylic dianhydride (b-2) is preferably a tetracarboxylic dianhydride (b-2) having an alicyclic structure represented by the following formula (4).

In this invention, tetracarboxylic dianhydride (b-2) is tetracarboxylic dianhydride (b-2) which has an alicyclic structure represented by following formula (9).

In this invention, tetracarboxylic dianhydride (b-2) is tetracarboxylic dianhydride (b-2) which has an alicyclic structure represented by following formula (10).

In the present invention, in addition to the tetracarboxylic dianhydride (b-2) having an alicyclic structure, an acid dianhydride without an alicyclic structure or an acid dianhydride containing an aromatic ring adjacent to an anhydride group may be added. . In the total amount of acid dianhydride, the lower limit of tetracarboxylic dianhydride (b-2) is preferably at least 40 mole %, more preferably at least 80 mole %, and more than 90 mole % is particularly good. 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 dianhydride is less than 40 mol %, the aromatic ring structure may increase and the dielectric properties may decrease.

The acid dianhydrides adjacent to the anhydride group and containing an aromatic ring other than the aforementioned tetracarboxylic dianhydride (b-2) include pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyl base tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2 -Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) Ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl) ) methane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, Aromatic tetracarboxylic dianhydride such as 3,4,9,10-perylenetetracarboxylic dianhydride, or bis(3,4-dicarboxyphenyl)pyridine dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or compounds in which the aromatic rings of these compounds are substituted with alkyl or halogen atoms, and compounds with amide groups Aromatic acid dianhydrides such as acid dianhydrides. These can be used in combination of 2 or more types with the alicyclic structure which has 4-40 carbon atoms, or the acid dianhydride containing a semi-alicyclic structure.

The aforementioned component (b-1) is not limited to the aforementioned dimer acid-derived diamine (b-1a), but may be a diamine other than the aforementioned dimer acid-derived diamine (b-1a). (b-1b), the above-mentioned tetracarboxylic dianhydride (b-2), the maleimide resin obtained by reacting the above-mentioned maleic anhydride, and the above-mentioned diamine derived from dimer acid may also be used. (b-1a), diamine (b-1b) other than diamine (b-1a) derived from dimer acid, tetracarboxylic dianhydride (b-2), reaction with maleic anhydride The obtained maleimide resin. By copolymerizing diamines (b-1b) other than the diamine (b-1a) derived from the dimer acid, it is possible to control further reduction in the modulus of tensile elasticity of the obtained hardened product. The required physical properties.

The diamine (b-1b) other than the diamine (b-1a) derived from the dimer acid (hereinafter referred to simply as diamine (b-1b) depending on the situation) refers to the aforementioned source in the present invention. Diamines other than the diamines contained in the diamine (b-1a) derived from the dimer acid. Such diamines (b-1b) are not particularly limited, for example, aliphatic diamines such as 1,6-hexamethylenediamine; 1,4-diaminocyclohexane, 1,3-bis Alicyclic diamines such as (aminomethyl)cyclohexane; 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, 4,4'-diaminodiphenylmethane and other aromatic diamines; 4, 4'-Diaminodiphenylsulfide; 3,3'-Diaminodiphenylsulfone; 4,4'-Diaminobenzophenone; 4,4'-Diaminodiphenylsulfide ; 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 a cured product with a lower tensile modulus of elasticity; 1, Diaminocyclohexanes such as 4-diaminocyclohexane; having 1 to 4 carbons in an aromatic skeleton such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane Aromatic diamines of aliphatic structure. Also, use this When obtaining the maleimide resin (B) related to the present invention from diamines (b-1b), one of these diamines (b-1b) may be used alone or two or more of them may be combined And use.

A method of reacting the aforementioned diamine (b-1a) derived from dimer acid, the aforementioned tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the aforementioned maleic anhydride, or making the aforementioned diamine derived from di The diamine (b-1a) of the polymeric acid, the aforementioned diamine (b-1b), the aforementioned tetracarboxylic dianhydride (b-2) having an alicyclic structure, and the method of reacting the aforementioned maleic anhydride are not particularly specific. For restrictions, a suitable known method can be used. For example, first, the aforementioned diamine (b-1a) derived from dimer acid, the aforementioned tetracarboxylic dianhydride (b-2), and the aforementioned diamine (b-1b) as needed are mixed in toluene, xylene , tetrahydronaphthalene, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other solvents or their mixed solvents, stirred at room temperature (about 23 ° C) for 30 to 60 Minutes to synthesize polyamic acid, then add maleic anhydride to the obtained polyamic acid and stir at room temperature (about 23°C) for 30 to 60 minutes to synthesize polyamic acid added at both ends Polyamide. Add a solvent such as toluene that azeotropes with water to the polyamic acid, and reflux at a temperature of 100 to 160°C for 3 to 6 hours while removing the water generated with imidization, and the desired polyamic acid can be obtained. imide resin. In addition, in such a method, a catalyst such as pyridine or methanesulfonic acid may be further added.

The mixing ratio of the raw materials in the aforementioned reaction is preferably such that (the total moles of all diamines and diamines (b-1b) contained in the diamine (b-1a) derived from the dimer acid): (with The total number of moles of tetracarboxylic dianhydride (b-2) of alicyclic structure + 1/2 of the number of moles of maleic anhydride) becomes 1:1. Also, when the aforementioned diamine (b-1b) is used in combination, it is preferable to use (diamine (b-1b) from the viewpoint of the tendency to develop flexibility derived from the dimer acid and obtain a cured product with a lower modulus of elasticity. The number of moles of -1b)/(the number of moles of all diamines contained in the dimer acid-derived diamine (b-1a)) is 1 or less, more preferably 0.4 or less. Also, when the aforementioned diamine (b-1b) is used in combination, diamine (b-1a) derived from dimer acid and Amino acid unit composed of tetracarboxylic dianhydride (b-2) having alicyclic structure, diamine (b-1b) and tetracarboxylic dianhydride (b-2) having alicyclic structure The polymerization form of the amide acid unit can be random polymerization or block polymerization.

The component (B) obtained in this way is preferably represented by the following formula (3).

(In formula (3), R ¹ represents a divalent hydrocarbon group (c) derived from a dimer acid, and R ² represents a divalent organic group other than a divalent hydrocarbon group (c) derived from a dimer acid. In the group (d), R ^represents a divalent organic group (d) selected from a divalent hydrocarbon group (c) derived from a dimer acid and a divalent hydrocarbon group (c) derived from a dimer acid In any one of the groups formed, R ⁴ and R ⁵ are each independently representing a tetravalent organic group with a carbon number of 4 to 40 having a monocyclic or condensed polycyclic alicyclic structure, a monocyclic The organic group of the alicyclic structure in the formula is a tetravalent organic group with a carbon number of 8 to 40 connected to each other directly or via a crosslinking structure, and a carbon having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. One or more organic groups among the tetravalent organic groups with the number 8 to 40. m is an integer from 1 to 30, n is an integer from 0 to 30, and R ⁴ and R ⁵ can be the same or different .)

The divalent hydrocarbon group (c) derived from the dimer acid in the aforementioned formula (3) is as described above. Also, in the present invention, the divalent organic group (d) other than the divalent hydrocarbon group (c) derived from the dimer acid in the aforementioned formula (2) refers to the divalent organic group (d) removed from the aforementioned diamine (b-1b). A divalent residue of 2 amine groups. However, in the same compound, the aforementioned divalent hydrocarbon group (c) derived from the dimer acid and the aforementioned divalent organic group (d) are Are not the same. In addition, the said tetravalent organic group in said formula (2) means the tetravalent residue which removed the group represented by two -CO-O-CO- from the said tetracarboxylic dianhydride.

In the aforementioned formula (3), m is the number of repeating units (hereinafter referred to as the structure derived from the dimer acid as appropriate) including the aforementioned divalent hydrocarbon group (c) derived from the dimer acid, and Represents an integer from 1 to 30. When the value of m exceeds the aforementioned upper limit, the solubility to solvents decreases, and in particular, the solubility to a developing solution at the time of development described later tends to decrease. In addition, from the viewpoint of suitable solubility in a developing solution during development, the value of m is particularly preferably 3 to 10.

In the aforementioned formula (3), n is the number of repeating units (hereinafter referred to as structures derived from organic diamine as appropriate) including the aforementioned divalent organic group (d), and represents an integer of 0 to 30. When the value of n exceeds the aforementioned upper limit, the flexibility of the obtained cured product tends to be poor, and it tends to be a hard and brittle resin. Also, from the viewpoint of the tendency to obtain a cured product with a low modulus of elasticity, the value of n is particularly preferably 0 to 10.

Furthermore, when m in the aforementioned formula (3) is 2 or more, R ¹ and R ⁴ may be the same or different between the respective repeating units. Also, when n in the aforementioned formula (3) is 2 or more, R ² and R ⁵ may be the same or different between the respective repeating units. Furthermore, in the maleimide resin represented by the aforementioned formula (3), the structure derived from the dimer acid and the structure derived from the organic diamine may be random or block.

In addition, the present invention can be obtained from the aforementioned dimer acid-derived diamine (b-1a), the aforementioned maleic anhydride, the aforementioned tetracarboxylic dianhydride (b-2) and, if necessary, the aforementioned organic diamine (f). In the case of the maleimide resin (B), when the reaction rate is 100%, the aforementioned n and m can be determined by all the diamines contained in the aforementioned dimer acid-derived diamine (b-1a), It represents by the mixing molar ratio of the said diamine (b-1b), the said maleic anhydride, and the said tetracarboxylic dianhydride (b-2). That is, (m+n): (m+n+2) is given by (from The diamine (b-1a) of the dimer acid and the total molar number of all diamines contained in the diamine (b-1b)): (Total of maleic anhydride and tetracarboxylic dianhydride (b-2) Mole number) expressed, m: n is (the mole number of all diamines contained in the diamine (b-1a) derived from dimer acid): (the mole number of diamine (b-1b) ), 2: (m+n) is represented by (the number of moles of maleic anhydride): (the number of moles of tetracarboxylic dianhydride (b-2)).

Furthermore, in component (B), the sum of m and n (m+n) is preferably 2 to 30 from the viewpoint of the tendency to obtain a cured product with a lower elastic modulus. Also, from the viewpoint of the tendency to obtain a cured product with a lower elastic modulus due to the appearance of flexibility derived from the dimer acid, the ratio of m to n (n/m) is preferably 1 or less. , preferably less than 0.4.

In the curable resin composition of the present invention, the component (B) may be used alone or in combination of two or more.

The weight ratio of component (A) to 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, and even more preferably 95/5 to 70/30. When the weight ratio of the component (B) is 1 or more, water absorption characteristics become favorable. On the other hand, when the weight ratio of a component (B) is 40 or less, heat resistance will become favorable.

Any known resin materials may be used in addition to the curable resin composition of the present invention (A) and (B). Specifically, phenol resin, epoxy resin, amine resin, active olefin-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, acrylic resin, methallyl resin , active ester resin, etc., one kind may be used, and plural may be used together. Moreover, maleimide resin other than component (A) and component (B) may be used together.

Phenolic resins, epoxy resins, amine resins, reactive olefin-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate resins, and active ester resins can be used as examples below, but are not subject to These are limited.

Phenol resin: by phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, hydroquinone, m-xylenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxybenzene Naphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furan formaldehyde, etc.) Polycondensates, phenols and various diene compounds (dicyclopentadiene, terpenes, vinyl cyclohexene, norbutadiene, vinyl norbutene, tetrahydroindenene, divinylbenzene, di Vinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl phenylene, benzophenone, etc.), polycondensates of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis (methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.) obtained by polycondensation of phenolic resins, polycondensates of bisphenols and various aldehydes, and polyphenylene ether.

Epoxy resin: Glycidyl ether-based epoxy resin, 4-vinyl-1-cyclohexene diepoxide or 3,4-ring Alicyclic epoxy resin represented by oxycyclohexylmethyl-3,4'-epoxycyclohexane carboxyl, tetraglycidyldiaminodiphenylmethane (TGDDM) or triglycidyl Glycidylamine-based epoxy resins and glycidyl ester-based epoxy resins represented by p-aminophenol.

Amine resin: obtained by the reaction of diaminodiphenylmethane, diaminodiphenylmethane, isophoronediamine, naphthalenediamine, aniline novolac, o-ethylaniline novolak, aniline and chlorinated xylene Aniline resins, anilines and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxy methyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1, 4-bis(hydroxymethyl)benzene, etc.).

Resins containing active olefins: Polymerization of the aforementioned phenolic resins and halogen-based compounds containing active olefins (chlorinated methyl styrene, allyl chloride, methallyl chloride, acryl chloride, allyl chloride, etc.) Condensates, phenols containing active olefins (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, clove oil, iso- clove oil, etc.) and halogen compounds (4 ,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4' - Polycondensates of dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy resins or alcohols and substituted or unsubstituted acrylates (acrylates , methacrylate, etc.), maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene Bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl -4,4'-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide Amine, 4,4'-diphenylbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene).

Isocyanate resin: p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, naphthalene diisocyanate and other aromatic diisocyanates; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate Diisocyanates of aliphatic or alicyclic structure such as isocyanate, norbutene diisocyanate, and lysine diisocyanate; biurets of one or more types of isocyanate monomers, or trimerization of the above-mentioned diisocyanate compounds Polyisocyanates such as isocyanates; polyisocyanates obtained by the urethane reaction of the above-mentioned isocyanate compounds and polyol compounds.

Polyamide resin: selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactam ( ε-caprolactam, ω-undecylactam, ω-laurolactam) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine , Hexamethylenediamine, Heptamethylenediamine, Octamethylenediamine, Nonamethylenediamine, Decanediamine, Undecanediamine, Dodecanediamine, Tridecanediamine Amine, Tetradecanediamine, Pentadecanediamine, Hexadecanediamine, Heptadecanediamine, Octadecanediamine, Nonadecanediamine, Eicosanediamine, 2-Methyl-1 , 5-diaminopentane, 2-methyl-1,8-diaminooctane and other aliphatic diamines; cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3 -Alicyclic diamines such as methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine, etc.) and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, hexamethylene Aliphatic dicarboxylic acids such as dioic acid, pimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2- Aromatic dicarboxylic acids such as methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid A polymer of one or more kinds of mixtures of dicarboxylic acids; dialkyl esters of these dicarboxylic acids, and dichlorides) as a main raw material.

Polyimide resin: the aforementioned diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furan base)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4' -Benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-Diphenyltetracarboxylic dianhydride, 2,2',3,3'-Biphenyltetracarboxylic dianhydride, Methylene-4,4'-diphthalein Acid dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-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, 4,4'-oxo Diphthalic 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)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2 -(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis [3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-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)-1,1,3,3-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, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4 '-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2- Ethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxygen-4,4'-bis(cyclohexane-1, 2-dicarboxylic acid) dianhydride, sulfur-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1, 2-dicarboxylic acid dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxo Bicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxytetrahydrofuran- 3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-bis Polycondensate of phenylbis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl) fluorine dianhydride).

Cyanate resin: a cyanate compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanoxybenzene, tricyanoxybenzene, dicyanoxynaphthalene, dicyanoxybis Phenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl) Methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'- Bis(4-cyanoxyphenyl)hexafluoropropane, bis(4-cyanoxyphenyl)sulfide, bis(4-cyanoxyphenyl)sulfide, phenol novolac cyanoxy, phenol/bicyclic The hydroxyl group of the pentadiene cocondensate is converted into a cyanate group, etc., but it is not limited thereto.

Furthermore, the cyanate ester compound whose synthesis method is described in JP-A-2005-264154 is particularly preferable as a cyanate ester compound because of its low hygroscopicity, flame resistance, and excellent dielectric properties.

The cyanate resin may also contain zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, and octyl in order to trimerize the cyanate group to form a sym-triazine ring. Zinc acid, tin octylate, lead acetylacetone, dibutyltin maleate and other catalysts. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably in a range of 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total curable resin composition.

Active ester resin: A compound having one or more active ester groups in one molecule can be used as a hardener for hardening resins such as epoxy resins as needed. As an active ester-based hardener, it is preferably a compound having two or more highly reactive ester groups such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds in one molecule. . The active ester-based hardener is preferably obtained by condensation reaction of at least any one of a carboxylic acid compound and a thiocarboxylic acid compound with at least one of a hydroxyl compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, active compounds derived from carboxylic acid compounds and hydroxyl compounds are preferred. The ester-based hardener is more preferably an active ester-based hardener obtained from a compound of a carboxylic acid compound and at least any one of a phenolic compound and a naphthol compound.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol naphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol Hydroxylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene Phenolic compounds, phenolic novolaks, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound in which 2 molecules of phenol are condensed in 1 molecule of dicyclopentadiene.

Preferable specific examples of active ester-based hardeners include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, and active ester compounds containing acetylated phenol novolaks. 1 . Active ester compounds comprising benzoyl compounds of phenolic novolaks. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The term "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

Examples of commercially available active ester hardeners include "EXA9451", "EXA9460", "EXA9460S", "HPC-8000-65T", " HPC-8000H-65TM", "EXA-8000L-65TM", and "EXA-8150-65T" (manufactured by DIC Corporation); examples of active ester compounds containing a naphthalene structure include "EXA9416-70AK" (manufactured by DIC Corporation); Containing acetylated compounds of phenolic novolaks Examples of active ester compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds including benzoyl compounds of phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester hardeners that are acetylated compounds of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester hardeners containing phosphorus atoms include "EXA-9050L-62M" manufactured by DIC Corporation. ";wait.

The curable resin composition of the present invention can also use a curing accelerator (hardening catalyst) in combination to improve the curability. Specific examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol Or tertiary amines such as 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt , Trimethyldecylammonium salt, cetyltrimethylammonium salt, cetyltrimethylammonium hydroxide and other quaternary ammonium salts, triphenylbenzylphosphonium salt, triphenylethylphosphonium salt , tetrabutylphosphonium salt and other quaternary phosphonium salts (the relative ions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., are not specified, but especially organic acid ions and hydroxide ions ), tin octylate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate) or zinc phosphates (zinc octyl phosphate, zinc stearate transition metal compounds (transition metal salts) such as zinc compounds such as zinc phosphate, etc. The compounded amount of the curing accelerator is 0.01 to 5.0 parts by weight based on 100 parts by weight of the curable resin composition.

In the curable resin composition of the present invention, a hardening accelerator of a radical polymerization initiator may be added or used in combination as needed. Examples of radical polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, diisopropyl Phenyl peroxide, 1,3-bis-(tertiary butyl peroxyisopropyl)-benzene and other dialkyl peroxides, tertiary butyl peroxybenzoate, 1,1-di -Tertiary butyl peroxide ring Peroxyketals such as hexane, α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butylperoxytrimethyl acetate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, tertiary pentylperoxy-2-ethylhexanoate, tertiary butylperoxy-2-ethylhexanoate, tert-amylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-amylperoxybenzoate Alkyl peroxyesters, di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tertiary butylperoxyisopropyl carbonate, Peroxycarbonates such as 1,6-bis(tert-butylperoxycarbonyloxy)hexane, tert-butyl hydroperoxide, cumyl hydroperoxide, tert-butyl peroxyoctanoic acid Organic peroxides such as esters, lauryl peroxide, or azobisisobutyronitrile, 4,4'-azobis(4-cyanoxalic acid), 2,2'-azobis(2,4- known hardening accelerators of azo-based compounds such as dimethylvaleronitrile), but are not particularly limited thereto. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxycarbonates, etc. Preferably, dialkyl peroxides are more preferred. The addition amount of the radical polymerization initiator 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 properties of the cured product will deteriorate.

Furthermore, the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame resistance imparting component. Phosphorus-containing compounds may be reactive or additive. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenel phosphate, cresyldiphenyl phosphate, Cresyl-2,6-xylyl phosphate (Cresyl-2,6-dixylenyl phosphate), 1,3-phenylene bis(xylyl phosphate), 1,4- Phosphate esters such as phenylene bis(xylyl phosphate), 4,4'-biphenyl (xylyl phosphate); 9,10-dihydro-9-oxo-10-phosphaphenanthrene -10-oxides, 10(2,5-dihydroxyphenyl)-10H-9-oxo-10-phosphaphenanthrene-10-oxides and other phosphanes; make the activity of epoxy resin and the aforementioned phosphanes Phosphorus-containing epoxy compounds obtained by hydrogen reaction, red phosphorus, etc., but phosphate esters, phosphine or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(xylyl phosphate), 1,4-phenylene bis(xylyl phosphate), 4,4'-biphenyl(xylyl phosphate), or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound)/resin component in the curable resin composition from 0.1 to 0.6 (weight ratio). When it is less than 0.1, the flame resistance is insufficient, and when it is more than 0.6, there is a possibility that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, in the curable resin composition of the present invention, it does not matter if an optical stabilizer is added as needed. The light stabilizer is hindered amine light stabilizer, especially HALS etc. are suitable. HALS is not particularly limited, but representative examples include dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidine Polycondensate of 1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, dimethyl-1- (2-Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amine Base-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene {(2, 2,6,6-tetramethyl-4-piperidinyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[{3,5- Bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)decane Diacyl ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl -4-piperidinyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2, 6,6-pentamethyl-4-piperidinyl), etc. In the HALS system, only one type may be used, or two or more types may be used in combination.

Furthermore, a binder resin may also be formulated in the curable resin composition of the present invention as needed. Binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NAR-phenolic resins, epoxy-NAR resins, polyamide resins, polyamide resins, and polyamide resins. Amine-based resins, silicone-based resins, etc., but not limited thereto. The blending amount of the binder resin is preferably within the range that does not impair the flame resistance and heat resistance of the hardened product. It is preferably 0.05 to 50 parts by mass relative to 100 parts by mass of the resin component, and more preferably it can be adjusted according to needs. 0.05 to 20 parts by mass are used.

Furthermore, 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, etc. Powder, or inorganic fillers that make these into spherical or crushed shapes. Moreover, especially when obtaining a curable resin composition for semiconductor encapsulation, the usage amount of the above-mentioned inorganic filler is in the curable resin composition, usually 80 to 92% by mass, preferably 83 to 90% by mass scope.

In addition, well-known additives can be compounded in the curable resin composition of this invention as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, polysilicon Oxygen gel, silicone oil, surface treatment agent for filling materials of silane coupling agent, release agent, carbon black, phthalocyanine blue, phthalocyanine green and other colorants. The compounding quantity of these additives is preferably 1000 mass parts or less with respect to 100 mass parts of resin components, More preferably, it is the range of 700 mass parts or less.

The curable resin composition of the present invention is obtained by uniformly mixing the above-mentioned components in a predetermined ratio, usually pre-curing at 130-180°C for 30-500 seconds, and then by carrying out pre-curing at 150-200°C After hardening for 2 to 15 hours, the hardened product of the present invention can be obtained for sufficient hardening reaction. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and then cured after removing the solvent.

The curable resin composition of the present invention obtained in this way has heat resistance and mechanical properties, and also has good dielectric properties after absorbing water. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, low dielectric constant, and low dielectric tangent. Specifically, it can be used as insulating materials, laminated boards (printed wiring boards, BGA substrates, build-up substrates, etc.), packaging materials, resists, and other materials for electrical/electronic components. In addition, in addition to molding materials and composite materials, it can also be used in the fields of coating materials, adhesives, 3D printing, and the like. In particular, it contributes to reflow resistance in semiconductor packages.

A semiconductor device is packaged with the curable resin composition of the present invention. Semiconductor devices include, for example, Dual Inline Package (DIP, Dual Inline Package), Quad Flat Package (QFP, Quad Flat Package), Ball Grid Array (BGA, Ball Grid Array), Chip Size Package (CSP, Chip Size Package), Small Package (SOP, Small Outline Package), Thin Small Outline Package (TSOP, Thin Small Outline Package), Thin Quad Flat Package (TQFP, Thin Quad Flat Package), etc.

The preparation method of the curable resin composition of the present invention is not particularly limited, but as described above, it can be prepared by dispersing or dissolving each component in a solvent or the like, mixing them uniformly, and distilling off the solvent if necessary, or, Prepolymerization is possible. For example, by heating component (A) and component (B) in the presence or absence of a catalyst, in the presence or absence of a solvent, to Perform prepolymerization. Similarly, in addition to component (A) and component (B), hardeners such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenol resins, acid anhydride compounds, and other additives can also be added. Perform prepolymerization. For mixing or prepolymerization of the components, for example, extruders, kneaders, rolls, etc. are used in the absence of solvents, and reactors with stirring devices are used in the presence of solvents.

The method of uniformly mixing without using solvents is to knead at a temperature in the range of 50 to 100°C using kneaders, rollers, planetary mixers, etc., to form a uniform curable resin composition things. The obtained curable resin composition can also be formed into a cylindrical ingot by a molding machine such as a tablet press after being pulverized, or formed into a granular powder or a powdery molded body, or the composition can be made The material is melted on the surface support, and molded into a sheet with a thickness of 0.05 mm to 10 mm to form a curable resin composition molded body. The obtained molding system becomes a non-stick molding at 0 to 20°C, and even if it is stored at -25 to 0°C for more than one week, the fluidity and hardening properties will hardly decrease.

The obtained molding system can be molded into a cured product by a transfer molding machine or a compression molding machine.

An organic solvent may be added to the curable resin composition of the present invention to form a varnish-like composition (hereinafter, also simply referred to as a varnish.). Make the curable resin composition of the present invention dissolve in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N- The prepreg is formed into a varnish by solvents such as methylpyrrolidone, impregnated with substrates such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and then heated and dried. By press molding, a hardened product of the curable resin composition of the present invention can be formed. The solvent at this time is used in the mixture of the curable resin composition of the present invention and the solvent usually in an amount of 10 to 70% by weight, preferably in an amount of 15 to 70% by weight. The amount by weight %. If the amount of the solvent is less than this range, the viscosity of the varnish becomes high, and the workability becomes poor. If the amount of the solvent is large, it becomes the cause of generation of holes in the cured product. Also, if it is a liquid composition, it is also possible to directly obtain a cured resin containing carbon fiber by, for example, RTM.

Moreover, the curable resin composition of this invention can also be used as a modifier of a film type composition. Specifically, it can be used to improve the flexibility in the A-stage, etc. Such a film-type curable resin composition is formed by forming the curable resin composition of the present invention into the above-mentioned curable resin composition varnish and coating it on a release film. After removing the solvent under heating, the A-stage is performed. In this way, the adhesive agent can be obtained as a sheet. This sheet adhesive can be used as an interlayer insulating layer on multilayer substrates and the like.

The curable resin composition of the present invention can be melted by heating to lower its viscosity and impregnated with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, etc. to obtain 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. or polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by Dupont Co., Ltd.), wholly aromatic polyamide, polyester; and polyparaphenylene benzoxazole, polyimide and organic fibers such as carbon fibers, but are not limited thereto. Although the shape of a base material is not specifically limited, For example, a woven fabric, a nonwoven fabric, a roving, a cut mat, etc. are mentioned. In addition, plain weave, basket weave, twill weave, etc. are known as the weaving method of the woven fabric, and can be appropriately selected and used from such known ones depending on the intended use or performance. In addition, glass woven fabrics that have been subjected to fiber opening treatment or surface-treated with silane coupling agents are suitable. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. In addition, a prepreg can also be obtained by impregnating the reinforcing fiber with the aforementioned varnish and drying it with heat.

The laminated board of this embodiment is equipped with the said prepreg of 1 or more sheets. The laminate is not particularly limited as long as it includes one or more prepregs, and may have any other layers. Generally, a known method can be suitably applied to the manufacturing method of a laminated board, and it is not specifically limited. For example, when forming a metal foil laminate, it is possible to use a multi-stage extruder, a multi-stage vacuum extruder, a continuous molding machine, an autoclave molding machine, etc., to laminate the above-mentioned prepregs on each other, and perform heating and pressure molding. to obtain laminates. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. Also, the pressure for pressurization is not particularly limited, but if the pressure is too high, it will be difficult to adjust the solid content of the resin of the laminate, and the quality will not be stable, and if the pressure is too small, the air bubbles or the adhesion between the laminates will deteriorate. , so 2.0 to 5.0MPa is preferred, and 2.5 to 4.0MPa is more preferred. The laminated board of this embodiment can be suitably used as a metal foil-clad laminated board mentioned later by having the layer which consists of metal foils.

Cut the above prepreg into the desired shape, and laminate it with copper foil as needed, and harden it while applying pressure to the laminate by extrusion molding, autoclave molding, sheet winding molding, etc. The permanent resin composition is heated and hardened, thereby obtaining a laminated board (printed wiring board) for electrical electronics or a carbon fiber reinforced material.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and coatings. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, so it is suitable for use in packaging materials for semiconductor elements, packaging materials for liquid crystal display elements, packaging materials for organic EL elements, and printed wiring boards Composite materials for light-weight and high-strength structural materials such as laminated boards and other electronic components or carbon fiber reinforced plastics and glass fiber reinforced plastics.

[Example]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. In addition, "part" and "%" mean "part by weight" and "% by weight" here, respectively. The softening point and melt viscosity were measured according to the following methods.

‧GPC (gel permeation chromatography) analysis

Manufacturer: Waters

Column: SHODEXGPCKF-601 (2 copies), KF-602, KF-602.5, KF-603

Flow rate: 0.5ml/min.

Column temperature: 40°C

Solvent used: THF (tetrahydrofuran)

Detector: RI (Differential Refractive Detector)

‧HPLC (High Speed Liquid Chromatography) analysis

Column: InertsilODS-2

Flow rate: 1.0ml/min.

Column temperature: 40°C

Solvent used: acetonitrile‧water

Detector: photodiode array (225nm)

‧Amine equivalent

According to JIS K-7236 Appendix A (correction method of glycidylamine), the obtained value was made into amine equivalent.

‧DMA analysis

Manufacturer: TA Instruments

Device: DMAQ800

Measurement Mode: Tensile

Heating rate: 2°C/min.

Measuring temperature range: 25°C to 350°C

Measurement frequency: 10Hz

The temperature at which the value of tan δ becomes the maximum was taken as Tg.

‧Mechanical strength

Manufacturer: Shimadzu Corporation

Device: Autograph AGS-X

Tensile speed: 0.5mm/min

The test piece was clamped so that the length of the test piece became 5 cm, and the tensile measurement was performed at the above-mentioned test speed in the 180° direction.

‧Water absorption test

After immersing in water for 24 hours, take it out, measure the weight after leaving it in an environment of 25°C and 30% for 24 hours, and calculate it.

‧Dielectric Permittivity Test, Dielectric Tangent Test

Manufacturer: AET Co., Ltd.

Device: 10GHz cavity resonator

Measurement was performed after drying a test piece with a width of 2.5 mm and a length of 5 cm at 120° C. with a dryer for 2 hours. Furthermore, after immersing the test piece in water for 24 hours, it was taken out, and after leaving it to stand in 25 degreeC and 30% environment for 24 hours, it measured again.

[Synthesis Example 1: Synthesis of Aromatic Amine Resin (A-1)]

192 parts of aniline, 112 parts of toluene, and 100 parts of 1,3-bis(2-hydroxy-2-propyl)benzene are filled in a flask equipped with a thermometer, a cooling tube, a DEAN-STARK azeotropic distillation trap, and a stirrer , 21.5 parts of 35% hydrochloric acid were dripped over 10 minutes. The temperature in the system was raised to 160° C., and the reaction was carried out at the same temperature for 17 hours while distilling off water and toluene. Then, after cooling to 80 degreeC, 124 parts of toluene were added, and 30 parts of 30% sodium hydroxide aqueous solutions were dripped over 10 minutes. Thereafter, it was stirred at the same temperature for 2 minutes and left to stand for 30 minutes. The separated aqueous layer was removed, and the water washing of the reaction solution was repeated until the washing solution became neutral. Then, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure with a rotary evaporator, thereby obtaining 158 parts of aromatic amine resin (A-1) represented by the aforementioned formula (2). The amine equivalent of the aromatic amine resin (A-1) was 186.1 g/eq, and the softening point was 58.8°C. By GPC analysis (RI), the n=1 body was 62.5 area%. The GPC chart is shown in FIG. 1 .

[Synthesis Example 2: Synthesis of Maleimide Resin (M-1)]

73.5 parts of maleic anhydride, 126 parts of toluene, 1.86 parts of methanesulfonic acid, and N-methyl-2-pyrrolidone were filled in a flask equipped with a thermometer, a cooling tube, a DEAN-STARK azeotropic distillation trap, and a stirrer 12.6 parts, formed into a heating reflux state. Next, a resin solution obtained by dissolving 93 parts of aromatic amine resin (A-1) in 55.8 parts of toluene was dropped over 4 hours while maintaining a reflux state. At this time, the condensed water and toluene azeotroped under reflux conditions are cooled/separated in the DEAN-STARK azeotropic distillation trap, the toluene belonging to the organic layer is returned to the system, and the water is discharged out of the system . After the dripping of the resin solution was terminated, the reaction was carried out for 10 hours while maintaining the reflux state and performing a dehydration operation.

After the reaction is terminated, repeat washing with water 4 times to remove methanesulfonic acid and excess maleic anhydride, and remove water from the system by azeotroping toluene and water under heating and reducing pressure below 70°C. Then, add 0.93 parts of methanesulfonic acid were reacted for 4 hours under heating and reflux. After the reaction is terminated, repeat washing with water 4 times until the washing water becomes neutral, remove water from the system by azeotroping toluene and water under heating and reducing pressure below 70°C, and then distill toluene under heating and reducing pressure After removing the solvent until the resin concentration reaches about 70-80%, add toluene to adjust the resin concentration to 60%. Thereby, a maleimide solution (V-1) containing a maleimide resin (M-1) was obtained. According to GPC analysis (RI), the n=1 body of the obtained maleimide resin (M-1) is 57.4 area%, n=2 body is 21.3 area%, and n=3 body is 21.3 area% . The orientation ratio in the n=1 body (ortho-ortho body/para-para body/ortho-para body) was 32.0%/25.4%/42.6% from HPLC analysis (225nm). Also, the softening point was 115.5°C, and the viscosity was 6.0 Pa‧s. The GPC chart is shown in FIG. 2 .

[Synthesis Example 3: Synthesis of Maleimide Resin (B-1)]

110 g of toluene and 36 g of N-methylpyrrolidone were put into a 500 ml round bottom flask equipped with a Teflon (registered trademark)-coated stirring rod. Next, 85.6 g (0.16 mol) of PRIAMINE 1074 (manufactured by CRODA JAPAN Co., Ltd.) was added, and then 15.4 g (0.16 mol) of anhydrous methanesulfonic acid was gradually added to form a salt. Stir and mix for about 10 minutes, then slowly add 1,2,4,5-cyclohexanetetracarboxylic dianhydride (24.5 g, 0.08 mol) to the stirred mixture. A DEAN-STARK trap and condenser were installed in the flask. The mixture was heated to reflux for 6 hours to form the amine terminated diimide. The theoretical amount of water formed from the condensation was available up to this point. The reaction mixture was cooled to below room temperature, and 18.8 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water formed. After cooling to room temperature, 200 ml of toluene was added to the flask. Secondly, wash the diluted with water (100ml×3) The diluted organic layer was used to remove salt or unreacted raw materials. Thereafter, the solvent was removed under vacuum to obtain 108 g of an amber waxy maleimide resin (B-1) (90% yield, Mw=3,600).

[Examples 1 to 5, Comparative Examples 1 to 8]

Various maleimide resins and thermoplastic resins (SEPTON 2104) were measured in the proportions shown in Table 1, and acetone was added so that the solid content of the resin became 50% by weight, and mixed to prepare a varnish. Furthermore, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) as a hardening accelerator was dissolved in the varnish. The varnish in which the curing accelerator was dissolved was heated in a vacuum dryer at 60°C for 30 minutes and at 150°C for 1 hour to prepare a curable resin composition. The obtained curable resin composition was sandwiched between copper foils, and a pressure of 1 MPa was applied under vacuum, followed by curing at 220° C. for 2 hours. Confirm the curability at this time and evaluate the physical properties. Table 1 shows the results of various measurements on the obtained cured products.

‧M-1 (component (A), obtained by heating and reducing the solvent obtained in Synthesis Example 2)

‧B-1 (component (B), obtained in Synthesis Example 3)

‧MIR-3000 (The solvent of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd.) was distilled off under reduced pressure by heating)

‧SEPTON 2104 (thermoplastic resin, manufactured by KURARAY Co., Ltd.)

‧2E4MZ (hardening accelerator, manufactured by Shikoku Chemical Industry Co., Ltd.)

[Table 1]

As a result of Examples 1 to 5, any one of heat resistance, mechanical properties, water absorption, and dielectric properties was good. In addition, the Tg of Examples 1 to 4 is 200° C. or higher, and the heat resistance is more favorable. On the other hand, the result of Comparative Example 1 is that the dielectric properties after water absorption become poor, the results of Comparative Examples 2 to 4 are poor in heat resistance, and the results of Comparative Examples 5 to 7 are poor in dielectric properties. The result of Comparative Example 8 is that the heat resistance and modulus of elasticity are not good, and all the characteristics cannot be satisfied.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art that this invention pertains that various changes and corrections are possible without departing from the spirit and range of this invention.

Also, this case is based on the Japanese Patent Application (Japanese Patent Application No. 2021-056834) filed on March 30, 2021, and its entire contents are incorporated by reference. In addition, all the contents that should be cited here are taken in as a whole.

Claims (11)

A kind of maleimide resin mixture, is to comprise maleimide resin (B), and this maleimide resin (B) is to make maleimide resin (A) shown in following formula (1) ), diamine (b), and maleic anhydride reaction obtained;

In the formula (1), the plural Rs independently represent a hydrogen atom or an alkyl group with 1 to 5 carbons, m represents an integer from 0 to 3, n is the number of repetitions, and the average value is 1<n< 5. The maleimide resin mixture according to claim 1, wherein the aforementioned component (b) is obtained by reacting diamine (b-1) with 4 to 60 carbon atoms and tetracarboxylic dianhydride (b-2) By. The maleimide resin mixture according to Claim 2, wherein the aforementioned component (b-1) is a diamine (b-1a) derived from a dimer acid. The maleimide resin mixture as described in claim 2 or 3, wherein the aforementioned component (b-2) is represented by the following formula (4),

The maleimide resin mixture as described in any one of claims 1 to 4, wherein the aforementioned component (A) is represented by the following formula (2),

In the formula (2), the plural Rs independently represent a hydrogen atom or an alkyl group with 1 to 5 carbons, m represents an integer from 0 to 3, n is the number of repetitions, and the average value is 1<n< 5. The maleimide resin mixture as described in any one 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 divalent hydrocarbon group (c) derived from a dimer acid, and R ² represents a divalent organic group other than a divalent hydrocarbon group (c) derived from a dimer acid ( d), R ³ represents a divalent organic group (d) selected from divalent hydrocarbon groups (c) derived from dimer acids and divalent hydrocarbon groups (c) derived from dimer acids Any one of the groups, R ⁴ and R ⁵ each independently represent a tetravalent organic group with a carbon number of 4 to 40 having a monocyclic or condensed polycyclic alicyclic structure, a monocyclic The organic group with an alicyclic structure is a tetravalent organic group with 8 to 40 carbon atoms linked directly or via a cross-linked structure, and a semi-alicyclic structure with 8 carbon atoms having both an alicyclic structure and an aromatic ring. One or more organic groups among the tetravalent organic groups ranging from 40 to 40; m is an integer from 1 to 30, n is an integer from 0 to 30, and ^R4 and ^R5 can be the same or different. The maleimide resin mixture according to any one 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. A curable resin composition containing the maleimide resin mixture described in any one of Claims 1 to 7. The maleimide resin mixture as described in claim 8 further contains a hardening accelerator. A prepreg comprising the maleimide resin mixture described in any one of claims 1 to 7, or the curable resin composition described in claim 8 or 9, on a sheet-shaped fiber substrate. A cured product, which is the maleimide resin mixture described in any one of claims 1 to 7, the curable resin composition described in claim 8 or 9, or the prepreg described in claim 10 Harden what you get.

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