WO2018043380A1

WO2018043380A1 - Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof

Info

Publication number: WO2018043380A1
Application number: PCT/JP2017/030694
Authority: WO
Inventors: 隆行遠島; 政隆中西; 一貴松浦
Original assignee: 日本化薬株式会社
Priority date: 2016-08-31
Filing date: 2017-08-28
Publication date: 2018-03-08
Also published as: TW201815919A; CN109641984A; JPWO2018043380A1; KR20190046815A; KR20220106227A; TWI724229B; JP7011589B2; KR102601953B1

Abstract

Provided are a maleimide resin mold, a maleimide resin composition, and a cured product thereof with less environmental exposure which have excellent workability and production efficiency, for example, in highly reliable semiconductor sealing material applications, electric and electronic part insulating material applications, various composite material applications including laminates (printed wiring glass fiber reinforced composite material) and carbon fiber reinforced composite material (CFRP), various adhesive applications, various coating applications, and structural members. The maleimide resin mold includes a maleimide resin and an organic solvent, and is film-shaped or flake-shaped.

Description

Maleimide resin molded body, method for producing maleimide resin molded body, maleimide resin composition and cured product thereof

The present invention relates to a maleimide resin molding, a method for producing a maleimide resin molding, a maleimide resin composition, and a cured product thereof. Specifically, for high-reliability semiconductor encapsulant use, electrical / electronic component insulation material use, and various composite materials use such as laminate (printed wiring glass fiber reinforced composite material) and CFRP (carbon fiber reinforced composite material), Useful for various adhesive applications, various paint applications, structural members, etc., with excellent workability and productivity, with less environmental exposure, maleimide resin moldings, methods for producing maleimide resin moldings, maleimide resin compositions and cured products thereof .

Maleimide resin is a compound having heat resistance exceeding that of epoxy resin, moldability equivalent to that of epoxy resin, and also having properties of low linear expansion coefficient and high Tg. Polymaleimide compounds can be cross-linked alone or reacted with various maleimide compounds or cross-linking agents to give materials with excellent heat resistance and flame retardancy, sealing materials, base materials, insulating materials, etc. Has been used in various applications. High heat resistant base materials, flexible substrate materials, high heat resistant low dielectric materials, high heat resistant CFRP materials (carbon fiber composite materials), high power for automotive SiC power devices, especially where extremely high heat resistance and moldability are required Used for heat-resistant sealing materials.

Conventionally, since maleimide resin has self-reactivity, in many cases it is commercially available as a resin powder by taking out a crystal powder such as recrystallization or by reprecipitation (see Patent Document 1). When used, there were problems such as contamination of the environment (dirt and inhalation to the human body) as well as workability and productivity due to powder flying. Furthermore, there is a problem that solvent and other substances are taken up during crystallization and precipitation, and cannot be completely removed. Acetic acids used during production are taken in, and the odor of acetic acid remains in the resulting product. It becomes a problem related to. From such a background, a maleimide molded article excellent in workability, productivity, and environmental safety is desired. For example, Patent Document 2 discloses a method for melting and taking out a maleimide resin solution using an evaporator.

Japanese Patent Publication No. 6-86425 Japanese Unexamined Patent Publication No. 2009-001783

However, in Patent Document 2, although there was no significant change on a small scale, when the amount of synthesis is increased, it takes a long time to evaporate the solvent, and thus self-polymerization may proceed during that time. Therefore, in the production in actual production, there is a problem from the viewpoint of moldability and stable productivity, such that the risk of polymerization and gelation is extremely high, the viscosity increases due to the increase in molecular weight, and the characteristics differ every time it is produced. Also, if the solvent recovery temperature is lowered to suppress this polymerization, particularly in the case of a maleimide resin having a softening point of 50 ° C. or higher, it becomes difficult to remove the solvent, and the residual solvent increases (especially, the residual solvent exceeding 30000 ppm). Therefore, there is a problem in safety such as the possibility of generation of voids and cracks during molding and exposure to workers. Furthermore, in the synthesis of these maleimide resins, there are cases where substances having an effect on the human body such as acetic acid, toluene, and xylene are used, so that the remaining of the solvent becomes a problem.
Therefore, an object of the present invention is to provide a maleimide resin molded article that is excellent in workability and productivity and has little environmental exposure.

As a result of intensive studies to solve the above-mentioned problems, the present inventors are excellent in workability, productivity, etc. by taking out as a film-like or flake-like molded body instead of the conventional crystalline or powdery form, and the environment. It has been found that exposure is reduced, and the present invention has been completed.

That is, the present invention
[1] A maleimide resin molded article containing a maleimide resin and an organic solvent and having a film shape or flake shape,
[2] The maleimide resin molded article according to [1], wherein the content of the organic solvent is 30000 ppm or less,
[3] The maleimide resin molded article according to [1] or [2], wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers,
[4] The maleimide resin molded article according to any one of [1] to [3], wherein the thickness is 10 μm to 3 mm.
[5] The maleimide resin molded article according to any one of [1] to [4], wherein the maleimide resin is a novolak maleimide resin having a repeating unit having an average functional group number of 2 to 20.
[6] The maleimide resin molding according to any one of [1] to [5] above, wherein the softening point of the maleimide resin is 50 to 150 ° C.
[7] A method for producing a maleimide compound molded body, in which a solution obtained by dissolving a maleimide resin in an organic solvent is applied on the surface of a support and dried.
[8] The method for producing a maleimide compound molded article according to [7], wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers,
[9] The method for producing a maleimide compound molded article according to the above [7] or [8], wherein the drying temperature is 80 to 200 ° C.
[10] A maleimide resin molded article obtained by the production method according to any one of [7] to [9],
[11] A maleimide resin composition comprising the maleimide resin molded article according to any one of [1] to [6] and [10]
[12] The maleimide resin composition according to [11] above, further comprising at least one selected from a compound capable of crosslinking reaction with a maleimide resin and a curing accelerator,
[13] A cured product of the maleimide resin composition according to [11] or [12],
About.

Since the maleimide resin molding of the present invention is molded in the form of a film or flakes, the organic solvent content can be suppressed, the workability and productivity are excellent, and a maleimide resin molding with less environmental exposure is provided. be able to. Furthermore, since the amount of the organic solvent can be suppressed, generation of voids and cracks during molding can be prevented.

It is a figure showing molecular weight distribution of the maleimide resin solution (V1) at the time of completion | finish of the polymerization reaction obtained from the synthesis example 2. FIG. 2 is a view showing a molecular weight distribution of a maleimide resin molded body (M1) obtained from Example 1. FIG. It is a figure showing the molecular weight distribution of the maleimide resin (B1) after the solvent distillation at the time of mass synthesis obtained from Comparative Example 1. It is a figure showing fixed_quantity | quantitative_assay of the acetic acid of the maleimide resin (C1) of the comparative example 4.

Hereinafter, the present invention will be described in detail.
The maleimide resin molding of the present invention contains a maleimide resin and an organic solvent, and is characterized by being molded in a film or flake shape.
Compared with the maleimide resin that has been generally supplied in the form of crystals or powder, it can be supplied in the form of a film or flake, which causes problems such as dust in terms of workability. It is extremely easy to handle. That is, the maleimide resin molding of the present invention can easily prepare a maleimide resin composition.

The resin molded body refers to a resin solution that has been applied on the surface of the support, and then removed from the support while removing the solvent under superheated drying conditions. For example, a film or sheet Shape, fiber shape, plate shape, rod shape and the like.
Here, the film form means a form of a sheet having an average thickness of 10 μm to 3 mm. The flake shape refers to a state in which a film-like molded body is crushed. The flake shape is not particularly limited as long as it is a size that does not scatter like a powder during handling operations, but specifically, the average of the long diameter portion is preferably 0.1 cm to 5 cm. More preferably, it is 0.1 to 3 cm.
The average thickness can be obtained by stacking a plurality of sheets or films, measuring arbitrary 10 points with calipers, and dividing the obtained thickness by the number of stacked sheets.

Next, the manufacturing method of the maleimide resin molding of this invention is demonstrated for convenience of explanation.
The maleimide resin molding of the present invention is obtained by coating a solution of maleimide resin in an organic solvent (hereinafter also referred to as “maleimide resin solution” or “resin solution”) on the surface of the support to form a film or a sheet. After molding, it can be obtained by removing the solvent under heating conditions (under reduced pressure if necessary) and peeling the film from the support. That is, the manufacturing method of the maleimide resin molding of the present invention is performed by a step of applying a resin solution on the surface of a support, a step of heat drying, and a step of peeling from the support.

(Maleimide resin)
As the maleimide resin that can be used in the present invention, known ones can be used, but from the viewpoint of viscosity and softening point, a novolak-type maleimide resin having a repeating unit having an average functional group number of 2 to 20 is preferable.
As maleimide resin which can be used in this invention, it has a structure represented by following formula (1), for example.

(Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. X is represented by the following structural formulas (a) to (e)). n is an average value and represents 1 <n ≦ 5).

Alternatively, a mixture of maleimide resins may also be mentioned, but the present invention is not limited to these.

The method for producing the maleimide resin represented by the formula (1) is not particularly limited, and may be produced by any method known as a method for synthesizing the maleimide resin. As a specific manufacturing method, for example, a method such as Japanese Patent Application Laid-Open No. 2009-001783 is preferably used.

(Maleimide resin solution)
The maleimide resin solution in the present invention means a solution obtained by dissolving the maleimide resin in an organic solvent.
The maleimide resin solution is not particularly limited as long as the maleimide resin is dissolved in an organic solvent. In addition to a polymer solution synthesized by a known solution polymerization method or various control polymerization methods, a solid state resin is polymerized during the polymerization. A part of the polymer may be precipitated, or a polymer may be precipitated by adding a precipitating agent to the polymerized solution.
The organic solvent that can be used is not particularly limited. For example, at least one organic solvent selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers is preferable. Moreover, it is preferable to process the reaction liquid after polymerization, such as washing with water.
The amount of the organic solvent used is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of maleimide resin and the solvent.

A maleimide resin having a melting point and a softening point can be used. In particular, when it has a melting point, it is preferably 200 ° C. or lower, and when it has a softening point, it is preferably 50 to 150 ° C.
The viscosity (cone plate method, 150 ° C. melt viscosity) of the maleimide resin solution is preferably 5.0 mPa · s to 10,000 Pa · s, more preferably 10 mPa · s to 100 Pa · s, and particularly preferably 10 mPa · s to 10 Pa · s. If the 150 ° C. melt viscosity in the corn plate method is 10000 Pa · s or less, the coating workability is not lowered, which is preferable.

(Process to apply on the support surface)
Next, the obtained maleimide resin solution is applied to the surface of the support and molded into a film or sheet.
The support on which the maleimide resin solution is applied is not particularly limited as long as the surface is smooth, but preferably includes a metal, a PET film not subjected to a release treatment, an imide film, and the like.

The film thickness and area when applied to the surface of the support are preferably such that the dry film thickness is 10 μm to 3 mm and the area is 100 cm ² or less per 100 cm ² of the surface of the support.

The WET film thickness of the film during coating is preferably 10 μm to 5 mm, more preferably 10 μm to 4.5 mm, and particularly preferably 200 μm to 4.3 mm. If the above range is exceeded, the residual solvent reducing effect may not be sufficiently obtained, and if it is below the productivity of the maleimide resin molded product, the productivity may be lowered.

(Process to heat dry and process to peel from the surface of the support)
Next, after applying the maleimide resin solution to the surface of the support, the solvent is removed under heating and drying conditions (under reduced pressure if necessary), and the dried coating is formed into a film or sheet from the surface of the support. The film is peeled off and removed.

The drying temperature is preferably 80 to 250 ° C, preferably 80 to 200 ° C, particularly preferably 100 to 200 ° C. If the drying temperature exceeds 250 ° C., the deterioration of the resin is likely to proceed, so that the drying temperature is set according to the required processing characteristics. If the temperature is lower than 80 ° C., it is difficult to remove the solvent, and the remaining amount of the solvent increases. Therefore, voids and cracks at the time of molding and stickiness are formed, the shape of the film cannot be maintained, and it may be peeled off and pulverized. There are cases where it is not possible.

The film thickness of the film-like maleimide resin molding that is peeled off from the surface of the support is not particularly limited, but is preferably 10 μm to 3 mm, more preferably 30 μm to 1 mm. When the film thickness exceeds 3 mm, the effect of reducing the residual solvent amount cannot be obtained sufficiently.
Moreover, the obtained film-like maleimide resin molding can be used as a flake-shaped maleimide resin molding by pulverization.

The maleimide resin molding obtained by the above process has a residual solvent of 30000 ppm or less. Preferably it is 5000 ppm or less, More preferably, it is 3000 ppm or less, Especially preferably, it is 1000 ppm or less, Especially 600 ppm or less is preferable. Note that the lower limit of the measurement detection limit is 5 ppm.
Moreover, it is preferable that the obtained maleimide resin molding is soluble in a solvent. The complete dissolution means that the maleimide resin has not progressed in the high molecular weight reaction.

The maleimide resin molding obtained in this way is superior in workability and productivity compared to the maleimide resin supplied in the conventional crystalline or powder form, so that a maleimide resin composition can be easily prepared. Can do.

Next, the maleimide resin composition of the present invention will be described.
The maleimide resin composition of the present invention can contain a compound capable of undergoing a crosslinking reaction with the maleimide resin molded article. The crosslinkable compound causes a cross-linking reaction with the maleimide resin molding and acts as a curing agent for the maleimide resin. Examples of the crosslinkable compound include compounds having an amino group, a cyanate group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an allyl group, a methallyl group, an acrylic group, a methacryl group, a vinyl group, or a conjugated diene group. For example, an amine compound is preferably blended when heat resistance is required, and a cyanate ester compound is blended when dielectric properties are required. The maleimide resin can be self-polymerized and can be used alone.

The maleimide resin composition of the present invention can be blended with a curing catalyst (curing accelerator) as necessary. For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, Amines such as triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) -7-undecene, tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine , Phosphines such as tributylphosphine and trioctylphosphine, organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, zinc chloride, aluminum chloride Metal chlorides such as tin chloride, organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide, azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, hydrochloric acid, sulfuric acid, Examples thereof include mineral acids such as phosphoric acid, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride. The amount of the curing catalyst is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the maleimide resin molding of the present invention.

An organic solvent can be added to the maleimide resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the maleimide resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a maleimide resin composition varnish, and carbon fiber. A cured product of the maleimide resin composition of the present invention by hot press molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be.
The solvent at this time usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the maleimide resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the hardened | cured material of the maleimide resin composition which contains a carbon fiber by RTM system as it is can also be obtained as it is.

The maleimide resin composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the maleimide resin composition of the present invention on the release film as the maleimide resin composition varnish, removing the solvent under heating, and then performing B-stage formation. Obtained as an adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

A prepreg can be obtained by heating and melting the maleimide resin composition of the present invention to lower the viscosity and impregnating the fiber with a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber.
Moreover, a prepreg can also be obtained by impregnating the varnish into a reinforcing fiber and drying by heating.

There is no particular limitation on the method for impregnating the maleimide resin composition of the present invention into these reinforcing fibers, but since a method that does not use a solvent is preferable, the maleimide resin composition of the present invention is heated to 60 to 110 ° C, A hot melt method of impregnation in a fluid state is preferred.

The proportion of the maleimide resin composition in the prepreg obtained (impregnated with the maleimide resin composition in the reinforcing fiber) is usually 20% by weight to 80% by weight, preferably 25% by weight, although it depends on the form of the reinforcing fiber. The content is 65% by weight or less, more preferably 30% by weight or more and 50% or less. If the ratio of the maleimide resin composition is larger than this range, a sufficient reinforcing effect cannot be obtained because the ratio of the reinforcing fibers is relatively reduced. Conversely, if the maleimide resin composition is small, the moldability may be impaired. .

This prepreg can be cured by a known method to obtain a final molded product. For example, a prepreg can be laminated, pressurized to ² to 10 kgf / cm ² in an autoclave, and cured by heating at 150 ° C. to 200 ° C. for 30 minutes to 3 hours. Therefore, a fiber reinforced composite material molded article can be obtained by treating for 1 hour to 12 hours while heating stepwise in the temperature range of 180 ° C. to 280 ° C. as a post cure.
The above prepreg is cut into the desired shape, laminated with copper foil if necessary, and then the maleimide resin composition for laminates is heated and cured while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, etc. By doing so, a laminated board can be obtained.
Furthermore, a circuit can be formed on a laminated board made by superimposing copper foil on the surface, and a multilayer circuit board can be obtained by superimposing a prepreg or copper foil thereon and repeating the above operation.

The cured product of the prepreg of the present invention is required to have light weight, high strength, and high heat resistance, such as a robot hand for transferring a liquid crystal glass substrate, a disk for transferring a silicon wafer, an aerospace member, and an automobile engine member. It can be widely applied to members.

Specific uses of the maleimide resin composition of the present invention include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials for electronic materials (including printed boards, wire coatings, etc.) In addition to the encapsulant, an encapsulant, a cyanate resin composition for a substrate), and an additive for other resins such as an acrylate ester resin as a curing agent for a resist. In particular, in the FRP application, in recent years, the use of solvent-free has greatly progressed due to environmental considerations and the problem of eliminating defects due to voids. Furthermore, due to problems such as voids during molding, molding defects, and low voltage resistance, there is an environment where the solvent cannot enter the process even for semiconductor sealing applications.

The contents of the present invention will be specifically described below based on examples, but the present invention is not limited thereto. In the text, “part” and “%” represent “part by weight” and “% by weight”, respectively, unless otherwise specified. In the examples, the softening point and melt viscosity were measured by the following methods.
-Softening point: measured by a method according to JISK-7234-Melt viscosity: Viscosity at 150 ° C by cone plate method-Residual solvent amount was determined using a gas chromatograph GC-2010 manufactured by Shimadzu Corporation. DB-WAX (manufactured by Agilent Technologies) having a length of 30 m and an inner diameter of 0.25 mm was used.
As a temperature raising program, hold at 70 ° C. for 5 minutes, raise the temperature to 140 ° C. at a temperature raising rate of 10 ° C./min, then increase the temperature to 220 ° C. at a temperature raising rate of 20 ° C./min, A minute retention program was used.
-Gel permeation chromatography (LC-20 AD manufactured by Shimadzu Corporation) was used for molecular weight data acquisition. KF-603, KF-602.5, KF-602, KF-601 are used for the column, the column temperature is 40 ° C., the mobile phase is THF, and the flow rate is 0.5 ml / min. Measurements were made.

(Synthesis Example 1)
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 559 parts of aniline and 500 parts of toluene, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Next, 251 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to bring the system to 190 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Thereafter, while cooling, 500 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise so that the system did not vigorously reflux, and toluene distilled off at 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Subsequently, 335 parts of aromatic amine resin (A1) was obtained by distilling off excess aniline and toluene from the oil layer under heating and reduced pressure. The softening point of the aromatic amine resin (A1) was 59 ° C., and the melt viscosity was 0.05 Pa · s.

(Synthesis Example 2)
A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 88 parts of maleic anhydride and 300 parts of toluene, and heated to cool and separate the azeotropic water and toluene. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution in which 116 parts of the aromatic amine resin (A1) was dissolved in 116 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the system at 80 to 85 ° C. After completion of dropping, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 10 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added, and washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating to remove water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a maleimide resin solution (V1) containing 70% maleimide resin. When the molecular weight distribution of the obtained maleimide resin solution (V1) was measured by GPC, the result shown in FIG. 1 was obtained.

(Synthesis Example 3)
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 559 parts of aniline and 500 parts of toluene, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Subsequently, 175 parts of 4,4′-bis (chloromethyl) benzene was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to bring the system to 190 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Thereafter, while cooling, 500 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise so that the system did not vigorously reflux, and toluene distilled off at 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Subsequently, 280 parts of aromatic amine resin (A2) was obtained by distilling off excess aniline and toluene from the oil layer under heating and reduced pressure. The aromatic amine resin (A2) was a semi-solid resin.

(Synthesis Example 4)
A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 88 parts of maleic anhydride and 300 parts of toluene, and heated to cool and separate the azeotropic water and toluene. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution obtained by dissolving 91.7 parts of the aromatic amine resin (A2) in 91.7 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the system at 80 to 85 ° C. After completion of dropping, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 10 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added, and washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating to remove water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a maleimide resin solution (V2) containing 70% maleimide resin.

(Example 1) (Support: Imide film)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast and applied (WET film thickness 200 μm) onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator. The solvent was removed by drying the resulting resin film at 180 ° C. for 15 minutes.
The obtained maleimide resin molding was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M1) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M1) was 0.236% (2360 ppm). When the molecular weight distribution of the obtained maleimide resin molding (M1) was measured by GPC, the result shown in FIG. 2 was obtained. When compared with the molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2, no change in the molecular weight distribution was observed in this step (measurement by GPC).

(Example 2) (Support: Imide film)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast and applied (WET film thickness 200 μm) onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator. The solvent was removed by drying the resulting resin film at 200 ° C. for 15 minutes.
The obtained maleimide resin molding was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M2) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M2) was 0.293% (2930 ppm). In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 3) (Support: Imide film)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast and applied (WET film thickness 200 μm) onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator. The solvent was removed by drying the resulting resin film at 200 ° C. for 10 minutes.
The obtained maleimide resin molding was a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M3) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M3) was 0.398% (3980 ppm). In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 4) (Support: Imide film)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast and applied (WET film thickness 200 μm) onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator. The solvent was removed by drying the resulting resin film at 200 ° C. for 5 minutes.
The obtained maleimide resin molding was a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M4) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M4) was 0.0901% (901 ppm).
In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 5) (Support: SUS plate)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast and applied to a SUS plate using an applicator (WET film thickness 200 μm), and the applied resin film was dried at 180 ° C. for 15 minutes to obtain a solvent. Was removed.
The obtained maleimide resin molding was a film having a thickness of 113 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M5) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M5) was 0.163% (1638 ppm).
In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 6) (Support: SUS plate)
The maleimide resin solution (V2) obtained in Synthesis Example 4 was cast applied to a SUS plate using an applicator (WET film thickness 200 μm), and the applied resin film was dried at 180 ° C. for 15 minutes to obtain a solvent. Was removed.
The obtained maleimide resin molded body was a film having a thickness of 113 μm, and was peeled off and pulverized to obtain a maleimide resin molded body (M6) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M6) was 0.3% ≦ (3000 ppm ≦). In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 7) (Support: Mirror surface copper foil)
The maleimide resin solution (V1) obtained in Synthesis Example 2 is casted onto the mirror surface of electrolytic copper berth (18μ electrolytic copper foil CF-T9FZ-HTE manufactured by Fukuda Metal Foil Powder Co., Ltd.) using an applicator (WET) The solvent was removed by drying the applied resin film at 180 ° C. for 15 minutes.
The obtained maleimide resin molding was a film having a thickness of 152 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M7) of the present invention having a flaky shape.
The residual solvent of the obtained maleimide resin molding (M6) was 0.0728% (728 ppm).
In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Example 8) (Support: PET film)
The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast-applied (WET film thickness 200 μm) onto a PET film (Lumirror 38-S10 manufactured by Panac Co., Ltd.) that was not subjected to release treatment using an applicator. The applied resin film was dried at 160 ° C. for 1 hour to remove the solvent.
The obtained maleimide resin molding was a film having a thickness of 146 μm, and was peeled off and pulverized to obtain a maleimide resin molding (M7) of the present invention having a flake shape.
The residual solvent of the obtained maleimide resin molding (M8) was 0.0571% (571 ppm). In addition, the change of molecular weight distribution by this process was not seen (measurement by GPC).

(Comparative Example 1)
300 mL of the maleimide resin solution (V1) obtained in Synthesis Example 2 was distilled off using a rotary evaporator at 160 ° C. under heating and reduced pressure to obtain a maleimide resin (B1) in the form of a resin block. When the molecular weight distribution of the obtained maleimide resin (B1) was measured by GPC, the result shown in FIG. 3 was obtained. When compared with the molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2, the maleimide resin (B1) after evaporation of the solvent during mass synthesis has a high molecular weight. It was confirmed. The residual solvent of the obtained maleimide resin (B1) was 0.1% (1000 ppm) or less.

(Comparative Example 2)
It was confirmed that 1.0 L of the maleimide resin solution (V1) obtained in Synthesis Example 2 was gelated when the solvent was distilled off at 180 ° C. under heating and reduced pressure using a rotary evaporator. The obtained maleimide resin (B2) lost fluidity.

<Comparison of drying temperature in the manufacturing method of maleimide resin molding>
(Comparative Example 3)
As in Example 1, the maleimide resin solution (V1) obtained in Synthesis Example 2 was cast onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator (WET). The solvent was removed by heating and drying the applied resin film with hot air at 50 ° C. for 1 hour.
The obtained maleimide resin molding was sticky, could not maintain the shape of the film, and could not be peeled off and pulverized.

(Comparative Example 4)
As in Example 1, the maleimide resin solution (V1) obtained in Synthesis Example 2 was cast onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator (WET). The solvent was removed by heating and drying the applied resin film with hot air at 250 ° C. for 1 hour.
The obtained maleimide resin molding was in the form of a film and was peeled off and formed into flakes, but the molecular weight increased and became insoluble in various solvents such as acetone.

<Odor comparison>
(Example 9, Comparative Example 5)
The maleimide resin molding (M1) obtained in Example 1 and 4,4′-bismaleimide diphenylmethane (manufactured by TCI, hereinafter referred to as C1) were prepared for comparison, and the odors were compared.
The acetic acid was quantified using a gas chromatograph GC-2010Plus manufactured by Shimadzu Corporation, and a DB-WAX (Agilene Technologies) length 30 m and an inner diameter of 0.25 mm were used as a column. As the temperature raising program, a program was used that was held at 60 ° C. for 7 minutes, heated to 220 ° C. at a temperature rising rate of 20 ° C./min, and held at 220 ° C. for 5 minutes.

As a result, it was confirmed that the odor of acetic acid was found in Comparative Example 5, and no odor was felt in Example 9.
Further, when measured by gas chromatography, acetic acid was detected in Comparative Example 5 (see FIG. 4, retention time 11.298 minutes). Moreover, when the acid value was measured, it was confirmed that the acid value was 10 mgKOH / g, corresponding to 1% acetic acid.

<Comparison of shape and solvent solubility>
(Examples 10 to 14, Comparative Examples 6 and 7)
Using maleimide resin moldings (M1, M5 to M8) obtained in Examples 1, 5, 6, 7, and 8 and maleimide resin C1 for comparison and maleimide resin (B2) described in Comparative Example 2 to acetone The dissolution test was conducted.
As a result of investigations with a resin concentration of 50%, the maleimide resin moldings M1 and M5 to M8 were completely dissolved, but the maleimide resin (C1) and the maleimide resin (B2) were not completely dissolved.

From the above, it can be seen that in Examples 10 to 14, the maleimide resin moldings (M1, M5 to M8) did not undergo a high molecular weight reaction because they were completely dissolved. On the other hand, since it was not able to completely dissolve in Comparative Examples 6 and 7, it can be seen that the maleimide resin (C1, B2) is undergoing a high molecular weight reaction.

<Preparation of maleimide resin composition, comparison of cured product properties>
(Example 15)
10 parts of the maleimide resin molding (M1) obtained in Example 1 and 0.21 part of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator were mixed and mixed uniformly by stirring. -Kneaded to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cast applied (WET film thickness 200 μm) onto a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by Toray DuPont) using an applicator, and the applied resin film was cured under a curing condition 160. A cured product was obtained by curing while removing the solvent at ℃ × 2 h + 180 ℃ × 6 h. Table 1 shows the results of evaluating the physical properties of the obtained cured product.

(Comparative Example 8)
EPPN-502H (Nippon Kayaku Epoxy equivalent 169g / eq. Softening point 67.5 ° C EP1) 61 parts, phenol novolac (Maywa Kasei Co., Ltd. H-1, hydroxyl group equivalent 106g / eq.) 38 parts by weight, triphenyl 1 part by weight of phosphine (TPP Pure Chemical Reagent) was blended and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. After making this epoxy resin composition into a tablet, a resin composition molded body was prepared by transfer molding, and a cured product was obtained under curing conditions of 160 ° C. × 2 h + 180 ° C. × 6 h. The following physical properties of the obtained cured product were evaluated. The results are shown in Table 1.

(Comparative Example 9)
EOCN-1020-55 (Nippon Kayaku Epoxy equivalent 194 g / eq. Softening point 54.8 ° C. EP2) 65 parts, phenol novolac (Maywa Kasei Co., Ltd. H-1, hydroxyl group equivalent 106 g / eq.) 34 parts by weight, 1 part by weight of TPP (Pure Chemical Reagent) was blended and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. After making this epoxy resin composition into a tablet, a resin composition molded body was prepared by transfer molding, and a cured product was obtained under curing conditions of 160 ° C. × 2 h + 180 ° C. × 6 h. The following physical properties of the obtained cured product were evaluated. The results are shown in Table 1.

The following measurement was implemented about the obtained hardened | cured material.
・ DMA
Measurement items: storage elastic modulus at 30 ° C, 200 ° C, 250 ° C,
: Glass transition temperature (temperature at maximum of tan δ)
Measuring method: Dynamic viscoelasticity measuring instrument TA-instruments, Q-800
Measurement temperature range: 30 ° C-350 ° C
Temperature rate: 2 ° C / min
Test piece size: A material cut into 5 mm × 50 mm was used (thickness was about 800 μm).

From Table 1, the cured product of the maleimide resin composition of the present invention can be molded under the same curing conditions as the epoxy resin, and the obtained cured product is compared with the case where a high heat-resistant epoxy resin is used. It can be seen that there is little change in elastic modulus at high temperatures.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on August 31, 2016 (Japanese Patent Application No. 2016-169417), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The maleimide resin molding of the present invention can easily prepare a maleimide resin composition, and is a high heat resistant substrate material, a flexible substrate material, a high heat resistant low dielectric material, a high heat resistant CFRP material (carbon fiber composite material), and a vehicle-mounted material. It is extremely useful for a wide range of applications such as a high heat resistant sealing material for SiC power devices.

Claims

A maleimide resin molding containing a maleimide resin and an organic solvent and having a film or flake shape.
The maleimide resin molded article according to claim 1, wherein the content of the organic solvent is 30000 ppm or less.
3. The maleimide resin molding according to claim 1, wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters and ethers.
The maleimide resin molded article according to any one of claims 1 to 3, wherein the thickness is 10 袖 m to 3 mm.
The maleimide resin molded article according to any one of claims 1 to 4, wherein the maleimide resin is a novolac maleimide resin having a repeating unit having an average functional group number of 2 to 20.
The maleimide resin molding according to any one of claims 1 to 5, wherein the softening point of the maleimide resin is 50 to 150 ° C.
A method for producing a maleimide compound molded body, in which a solution obtained by dissolving a maleimide resin in an organic solvent is applied on the surface of a support and dried.
The method for producing a maleimide compound molded article according to claim 7, wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers.
The method for producing a maleimide compound molded article according to claim 7 or 8, wherein the drying temperature is 80 to 200 ° C.
A maleimide resin molded article obtained by the production method according to any one of claims 7 to 9.
A maleimide resin composition comprising the maleimide resin molded article according to any one of claims 1 to 6 and claim 10.
The maleimide resin composition according to claim 11, further comprising at least one selected from a compound capable of undergoing a crosslinking reaction with the maleimide resin and a curing accelerator.
A cured product of the maleimide resin composition according to claim 11 or 12.