JPWO2018043380A1 - Molded maleimide resin, method for producing molded maleimide resin, maleimide resin composition and cured product thereof - Google Patents

Abstract

Highly reliable semiconductor encapsulation material applications, electrical and electronic component insulation material applications, and various composite material applications including laminates (printed wiring glass fiber reinforced composite materials) and CFRP (carbon fiber reinforced composite materials), various adhesives The present invention provides a maleimide resin molded product excellent in workability, productivity, and useful for various coating applications, structural members, etc. and having little environmental exposure, a maleimide resin composition and a cured product thereof. The maleimide resin molding contains a maleimide resin and an organic solvent, and is in the form of a film or flake.

Description

  The present invention relates to a maleimide resin molded body, a method for producing a maleimide resin molded body, a maleimide resin composition and a cured product thereof. Specifically, applications for high-reliability semiconductor encapsulation materials, applications for electrical and electronic component insulation materials, and applications for various composite materials including laminates (printed wiring glass fiber reinforced composite materials) and CFRP (carbon fiber reinforced composite materials) A maleimide resin molded product excellent in workability and productivity useful for various adhesive applications, various paint applications, structural members and the like, the method for producing a maleimide resin molded product, a maleimide resin composition and a cured product thereof .

  The maleimide resin is a compound having heat resistance exceeding that of an epoxy resin, having a moldability equivalent to that of an epoxy resin, and further having properties of low linear expansion coefficient and high Tg. The polymaleimide compound can be crosslinked alone or reacted with various maleimide compounds or crosslinking agents to give a material excellent in heat resistance and flame resistance, and a sealing material, a base material, an insulating material, etc. It has been used in various applications. In particular, high heat resistant base materials, flexible substrate materials, high heat resistant low dielectric materials, high heat resistant CFRP materials (carbon fiber composite materials), which are required to simultaneously achieve extremely high heat resistance and moldability, SiC high power devices for automotive use Used in heat-resistant sealing material applications.

  Since maleimide resins have self-reactivities in the past, many of them are commercially available in the form of resin powder by recrystallization, such as recrystallization, or reprecipitation, as resin powder (see Patent Document 1). At the time of use, not only workability and productivity but also problems such as pollution to the environment (dirt and inhalation to the human body) due to powder flying and the like. Furthermore, there is a problem that the solvent and the like are incorporated during crystallization and precipitation and can not be removed, acetic acid used during production is taken in, the odor of acetic acid remains in the product, and the worker's safety Be an issue related to From such a background, a maleimide molded product 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 Examined Patent 6-86425 Japan JP 2009-001783

However, in Patent Document 2, although there is no significant change in a small amount scale, when the amount of synthesis is increased, it takes a long time to distill off the solvent, and in the meantime, there is a possibility that self polymerization may proceed. Therefore, in production in actual production, the risk of polymerization and gelation is extremely large, and there are problems from the viewpoint of moldability and stable productivity, such as the increase in viscosity due to the increase in molecular weight and the different characteristics each time it is produced. In addition, if the solvent recovery temperature is lowered to suppress this polymerization, removal of the solvent becomes difficult particularly in the case of a maleimide resin having a softening point of 50 ° C. or more, and the solvent remains more (especially the solvent residue exceeding 30000 ppm) Therefore, there are problems with the safety such as the possibility of formation of voids and cracks during molding, and exposure to workers. Furthermore, in the synthesis of these maleimide resins, since substances such as acetic acid, toluene and xylene may be used which have an influence on the human body, the remaining of the solvent is particularly problematic.
Then, an object of this invention is to provide the maleimide resin molding which is excellent in workability | operativity and productivity, and there are few environmental exposures.

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

That is, the present invention
[1] A maleimide resin molded product containing a maleimide resin and an organic solvent and in the form of a film or flake,
[2] The maleimide resin molded product according to the above [1], wherein the content of the organic solvent is 30000 ppm or less,
[3] The maleimide resin molded product according to the above [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 molding according to any one of the above-mentioned [1] to [3], which has a thickness of 10 μm to 3 mm,
[5] The maleimide resin molded product according to any one of the above [1] to [4], wherein the maleimide resin is a novolac maleimide resin having a repeating unit having an average number of functional groups of 2 to 20,
[6] The maleimide resin molding according to any one of the above [1] to [5], wherein the softening point of the maleimide resin is 50 to 150 ° C.
[7] A method for producing a molded maleimide compound, wherein a solution obtained by dissolving a maleimide resin in an organic solvent is coated on the surface of a support and dried.
[8] The method for producing a maleimide compound molded body according to the above item [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 molded maleimide compound as recited in the aforementioned Item [7] or [8], wherein the drying temperature is 80 to 200 ° C.,
[10] A maleimide resin molded article obtained by the method according to any one of the above [7] to [9],
[11] A maleimide resin composition comprising the maleimide resin molded product according to any one of [1] to [6] and [10],
[12] The maleimide resin composition according to the above [11], further comprising at least one selected from a compound capable of undergoing a crosslinking reaction with a maleimide resin and a curing accelerator.
[13] A cured product of the maleimide resin composition according to the preceding item [11] or [12],
About.

  The maleimide resin molded product of the present invention is molded in a film or flake form, so the content of organic solvent can be suppressed, and the maleimide resin molded product is excellent in workability and productivity, and less in environmental exposure. be able to. Furthermore, since the amount of the organic solvent can be suppressed, the formation of voids and cracks during molding can be prevented.

It is a figure showing the molecular weight distribution of the maleimide resin solution (V1) at the end of the polymerization reaction obtained from the synthesis example 2. It is a figure showing the molecular weight distribution of the maleimide resin molding (M1) obtained from Example 1. It is a figure showing molecular weight distribution of maleimide resin (B1) after solvent distillation at the time of large-scale synthesis obtained from comparative example 1. It is a figure showing the quantification of the acetic acid of maleimide resin (C1) of comparative example 4.

Hereinafter, the present invention will be described in detail.
The maleimide resin molding of the present invention is characterized in that it contains a maleimide resin and an organic solvent, and is molded in the form of a film or flake.
It is possible to supply a film-like or flake-like molded product as compared with a maleimide resin that has conventionally been generally supplied in the form of crystals or powders, so problems such as dust occur 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 molding refers to a resin solution applied on the surface of a support, then the solvent is removed under heating and drying conditions, and the support is peeled off while maintaining its shape, for example, a film, a sheet, etc. Shape, fibrous shape, plate shape, rod shape and the like.
Here, the film form refers to the 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 flaky form is not particularly limited as long as it is a size that does not scatter like powdery at the time of handling work, but specifically, it is preferable that the average of the major diameter part is 0.1 cm to 5 cm More preferably, it is 0.1-3 cm.
The average thickness can be determined by stacking a plurality of sheets or films, measuring an arbitrary 10 points with a caliper, and dividing the obtained thickness by the number of stacked sheets.

Next, for the convenience of explanation, the method for producing the molded maleimide resin of the present invention will be described.
The maleimide resin molded product of the present invention is formed by applying a solution of a maleimide resin in an organic solvent (hereinafter, also referred to as "maleimide resin solution" or "resin solution") on the surface of a support to form a film or 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 method for producing a molded maleimide resin of the present invention is carried out by the steps of applying a resin solution on the surface of a support, drying by heating, and peeling from the support.

(Maleimide resin)
Although a well-known thing can be used as maleimide resin which can be used in this invention, From the viewpoint of a viscosity and a softening point, the novolak-type maleimide resin which has a repeating unit whose average functional group number is 2-20 is preferable.
As a maleimide resin which can be used in the present invention, for example, it has a structure represented by the following formula (1).

(Wherein a plurality of R's are independently present 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, although mixtures of maleimide resins may also be mentioned, the present invention is not limited thereto.

  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 a maleimide resin. As a specific manufacturing method, for example, it is preferable to use a method such as Japanese Patent Application Laid-Open No. 2009-001783.

(Maleimide resin solution)
The maleimide resin solution in the present invention means that the maleimide resin is dissolved in an organic solvent.
The maleimide resin solution is not particularly limited as long as the maleimide resin is dissolved in an organic solvent, and in addition to polymer solutions synthesized by a known solution polymerization method or various controlled polymerization methods, solid weight during polymerization can be obtained. The polymer may be partially precipitated, or the polymer may be precipitated by adding a precipitant to a solution in which the polymerization is completed.
It does not specifically limit as an organic solvent which can be used, For example, a C3-C10 aromatic hydrocarbon, ketones, esters, At least 1 type of organic solvent chosen from 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.

As the maleimide resin, one having a melting point and a softening point can be used. In particular, when it has a melting point, 200 ° C. or less is preferable, and when it has a softening point, it is preferably 50 to 150 ° C.
The viscosity (corn-plate method, 150 ° C. melt viscosity) of the maleimide resin solution is preferably 5.0 mPa · s to 10000 Pa · s, more preferably 10 mPa · s to 100 Pa · s, and particularly preferably 10 mPa · s to 10 Pa · s. If the melt viscosity at 150 ° C. in the cone and plate method is 10000 Pa · s or less, the coating workability is preferable without deterioration.

(Step of applying on the surface of support)
Next, the resulting maleimide resin solution is applied to the surface of a 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, a metal, a PET film not subjected to releasing treatment, an imide film, etc. may be mentioned.

Thickness and area when applied to the surface of the support, each surface 100 cm ² per substrate, a dry film thickness 10Myuemu～3mm, it is preferably carried out such that the area of 100 cm ² or less.

  10 micrometers-5 mm are preferable, as for the WET film thickness of the film at the time of application | coating, 10 micrometers-4.5 mm are more preferable, and 200 micrometers-4.3 mm are especially preferable. If the above range is exceeded, the residual solvent reducing effect may not be obtained sufficiently, and if below the range, the productivity of the molded maleimide resin may be lowered.

(Step of heating and drying and step of peeling from the surface of the support)
Next, a maleimide resin solution is applied to the surface of the support, and then the solvent is removed under heating and drying conditions (under reduced pressure if necessary), and a dry coating is formed from the surface of the support into a film or sheet. Peel and remove the membrane.

  The drying temperature is preferably 80 to 250 ° C., preferably 80 ° C. to 200 ° C., particularly preferably 100 ° C. to 200 ° C. The drying temperature is set according to the required processing characteristics because deterioration of the resin tends to proceed if the temperature exceeds 250 ° C. If the temperature is less than 80 ° C., removal of the solvent is difficult, and the residual amount of solvent increases, so voids and cracks are formed and stickiness at the time of molding, and the shape of the film can not be maintained. It may not be possible.

Although the film thickness of the film-like maleimide resin molded body peeled off from the surface of the support and taken out is not particularly limited, it is preferably 10 μm to 3 mm, more preferably 30 μm to 1 mm. If the film thickness exceeds 3 mm, the effect of reducing the amount of residual solvent can not be sufficiently obtained.
Moreover, the film-like maleimide resin molding obtained can be used as a flake-like maleimide resin molding by crushing.

The maleimide resin molded product obtained by the above process has a residual solvent of 30,000 ppm or less. It is preferably 5000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1000 ppm or less, and particularly preferably 600 ppm or less. The lower limit is 5 ppm as a measurement detection limit.
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 to the high molecular weight formation reaction.

  Since the maleimide resin molding thus obtained is excellent in workability and productivity as compared with the conventional maleimide resin supplied in a crystalline or powdery state, the maleimide resin composition can be easily prepared. Can.

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 a maleimide resin molding. The crosslinkable compound causes a crosslinking 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 methacrylic group, a vinyl group and a conjugated diene group. For example, it is preferable to blend an amine compound when heat resistance is required and a cyanate ester compound when dielectric properties are required. The maleimide resin can also be used alone because it can also be self-polymerized.

  In the maleimide resin composition of the present invention, a catalyst for curing (curing accelerator) can be blended, if 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, Triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) -7-undecene, amines such as tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine Phosphines such as tributyl phosphine and trioctyl phosphine, tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, organic metal salts such as tin oleate, zinc chloride, aluminum chloride , Metal chlorides such as tin chloride, organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, hydrochloric acid, sulfuric acid, Examples include mineral acids such as phosphoric acid, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride. The compounding amount of the curing catalyst is preferably in the range of 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 form a varnish-like composition (hereinafter simply referred to as a varnish). 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, dimethyl acetamide, N-methyl pyrrolidone, etc. as necessary to make a maleimide resin composition varnish, carbon fiber , A cured product of the maleimide resin composition of the present invention by heat press forming a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like and heating and drying It can be done.
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, for example can also be obtained.

  The maleimide resin composition of the present invention can also be used as a film type composition modifier. Specifically, it can be used to improve the flexibility and the like in the B-stage. Such a film-type resin composition is applied to the release film as the maleimide resin composition varnish of the present invention as the maleimide resin composition varnish, and after removing the solvent under heating, the sheet is obtained by B-stage formation. Is obtained as a solid 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 it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers and alumina fibers.
Moreover, a prepreg can also be obtained by impregnating the said varnish in a reinforcement fiber and making it heat-dry.

  The method for impregnating these reinforcing fibers with the maleimide resin composition of the present invention is not particularly limited, but a method not using a solvent is preferable, so the maleimide resin composition of the present invention is heated to 60 to 110 ° C. The hot melt method of impregnating in a fluid state is preferred.

  The proportion of the maleimide resin composition in the resulting prepreg (the reinforcing fiber impregnated with the maleimide resin composition) is usually 20% by weight to 80% by weight, preferably 25% by weight, although it depends on the form of the reinforcing fiber It is at least 65% by weight, more preferably at least 30% by weight and at most 50%. If the proportion of the maleimide resin composition is larger than this range, a sufficient reinforcing effect can not be obtained by relatively decreasing the proportion of the reinforcing fiber, and conversely, if the amount of the maleimide resin composition is small, the moldability may be impaired. .

This prepreg can be cured by a known method to form a final molded product. For example, the prepreg can be laminated, pressurized to ² to 10 kgf / cm ² in an autoclave, and heat cured at 150 ° C. to 200 ° C. for 30 minutes to 3 hours to form a molded body, but the heat resistance is further improved In order to make it possible, it is possible to obtain a fiber-reinforced composite molded article by treating it as a post cure in the temperature range of 180 ° C. to 280 ° C. while stepwise heating the temperature for 1 hour to 12 hours.
The above prepreg is cut into a desired shape, and if necessary laminated with copper foil etc., the laminate is heat-cured while applying pressure by press molding, autoclave molding, sheet winding molding, etc. By doing this, a laminate can be obtained.
Furthermore, a circuit is formed on a laminate obtained by stacking copper foils on the surface, and prepregs, copper foils and the like are stacked thereon, and the above operation can be repeated to obtain a multilayer circuit board.

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

  Specific applications of the maleimide resin composition of the present invention include adhesives, paints, coatings, molding materials (including sheets, films, FRPs, etc.), insulating materials for electronic materials (printed substrates, wire coating, etc.) In addition to the sealing material, additives such as a sealing material, a cyanate resin composition for a substrate), an acrylic ester-based resin as a curing agent for a resist, and the like to other resins may be mentioned. In particular, in FRP applications, solventlessness has greatly progressed in recent years due to environmental considerations and the problem of void defect removal. Furthermore, due to problems such as voids and molding defects at the time of molding and a decrease in voltage resistance, there is an environment where the solvent can not enter into the process even in applications of semiconductor encapsulation.

The contents of the present invention will be specifically explained based on the following examples, but the present invention is not limited thereby. In the following description, "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified. In the examples, the softening point and the melt viscosity were measured by the following methods.
Softening point: Measured by a method according to JIS K-7234 Melt viscosity: Viscosity at 150 ° C. by cone plate method Quantitative determination of residual solvent amount is performed using a gas chromatograph GC-2010 manufactured by Shimadzu Corp. DB-WAX (made by Agile Technologies) 30 m in length and 0.25 mm in internal diameter were used.
As a temperature rising program, the temperature is maintained at 70 ° C. for 5 minutes, raised to 140 ° C. at a temperature rising rate of 10 ° C./min, then raised to 220 ° C. at a temperature rising rate of 20 ° C./min. The program used to hold the minutes was used.
-The gel permeation chromatography (GPC Shimadzu Corporation LC-20AD) was used for data acquisition of molecular weight. The column uses KF-603, KF-602.5, KF-602, KF-601, column temperature 40 ° C, mobile phase is THF, and RI detector at flow rate 0.5 ml / min. It measured.

Synthesis Example 1
Into a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 559 parts of aniline and 500 parts of toluene were charged, and 167 parts of 35% hydrochloric acid was added dropwise over 1 hour at room temperature. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the toluene which was the organic layer was returned to the system for dehydration. Then, 251 parts of 4,4'-bis (chloromethyl) biphenyl was added over 1 hour while maintaining at 60 to 70 ° C., and reaction was further performed 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. After that, 500 parts of a 30% aqueous solution of sodium hydroxide was slowly added dropwise while cooling so that the system was not vigorously refluxed, the toluene distilled off at 80 ° C. or less was returned to the system, and left at 70 ° C. to 80 ° C. The lower aqueous layer separated was removed, and the reaction solution was repeatedly washed with water until the washing solution became neutral. Next, an excess of aniline and toluene were distilled off from the oil layer under heating and reduced pressure to obtain 335 parts (A1) of an aromatic amine resin. The softening point of the aromatic amine resin (A1) was 59 ° C., and the melt viscosity was 0.05 Pa · s.

(Composition example 2)
88 parts of maleic anhydride and 300 parts of toluene are charged into a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, heated, and azeotropically cooled water and toluene are separated and separated. Then, only the toluene which is the organic layer was returned to the system for dehydration. Next, a resin solution in which 116 parts of aromatic amine resin (A1) was dissolved in 116 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the inside of the system at 80 to 85 ° C. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added, condensation water and toluene which are azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer is separated. The reaction was carried out for 10 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and heating was performed to azeotropically remove water from the system. Then, the reaction solution was concentrated to obtain a maleimide resin solution (V1) containing 70% of 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.

(Composition example 3)
Into a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 559 parts of aniline and 500 parts of toluene were charged, and 167 parts of 35% hydrochloric acid was added dropwise over 1 hour at room temperature. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the toluene which was the organic layer was returned to the system for dehydration. Then, 175 parts of 4,4'-bis (chloromethyl) benzene was added over 1 hour while maintaining at 60 to 70 ° C, and the reaction was further performed 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. After that, 500 parts of a 30% aqueous solution of sodium hydroxide was slowly added dropwise while cooling so that the system was not vigorously refluxed, the toluene distilled off at 80 ° C. or less was returned to the system, and left at 70 ° C. to 80 ° C. The lower aqueous layer separated was removed, and the reaction solution was repeatedly washed with water until the washing solution became neutral. Then, the excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure to obtain 280 parts (A2) of an aromatic amine resin. The aromatic amine resin (A2) was in the form of a semisolid resin.

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

(Example 1) (Support: imide film)
The maleimide resin solution (V1) obtained according to Synthesis Example 2 is cast coated (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 resulting maleimide resin molded product was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molded product (M1) of the present invention in the form of flakes.
The residual solvent of the resulting molded maleimide resin (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 molecular weight distribution was observed in this step (measurement by GPC).

(Example 2) (Support: imide film)
The maleimide resin solution (V1) obtained according to Synthesis Example 2 is cast coated (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 resulting maleimide resin molded product was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to form a maleimide resin molded product (M2) of the present invention in the form of flakes.
The residual solvent of the obtained maleimide resin molded product (M2) was 0.293% (2930 ppm). In addition, the change of the molecular weight distribution by this process was not seen (measurement by GPC).

(Example 3) (Support: imide film)
The maleimide resin solution (V1) obtained according to Synthesis Example 2 is cast coated (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 resulting maleimide resin molded product was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to form a maleimide resin molded product (M3) of the present invention in the form of flakes.
The residual solvent of the resulting molded maleimide resin (M3) was 0.398% (3980 ppm). In addition, the change of the molecular weight distribution by this process was not seen (measurement by GPC).

(Example 4) (Support: imide film)
The maleimide resin solution (V1) obtained according to Synthesis Example 2 is cast coated (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 resulting maleimide resin molded product was in the form of a film having a thickness of 125 μm, and was peeled off and pulverized to obtain a maleimide resin molded product (M4) of the present invention in the form of flakes.
The residual solvent of the obtained maleimide resin molded product (M4) was 0.0901% (901 ppm).
In addition, the change of the molecular weight distribution by this process was not seen (measurement by GPC).

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

(Example 6) (Support: SUS plate)
The maleimide resin solution (V2) obtained according to Synthesis Example 4 is cast applied (WET film thickness 200 μm) onto a SUS plate using an applicator, and the applied resin film is dried at 180 ° C. for 15 minutes to obtain a solvent. Was removed.
The resulting maleimide resin molded product was in the form of a film having a thickness of 113 μm, and was peeled off and pulverized to form a maleimide resin molded product (M6) of the present invention in the form of flakes.
The residual solvent of the resulting molded maleimide resin (M6) was 0.3% ≦ (3000 ppm ≦). In addition, the change of the 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 by Synthesis Example 2 is cast coated (WET) onto a mirror surface of electrolytic copper foil (18 μ electrolytic copper foil CF-T9FZ-HTE manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) using an applicator The solvent was removed by drying the applied resin film at 180 ° C. for 15 minutes.
The obtained maleimide resin molded product was a film having a thickness of 152 μm, and was peeled off and pulverized to obtain a maleimide resin molded product (M7) of the present invention in the form of a flake.
The residual solvent of the resulting molded maleimide resin (M6) was 0.0728% (728 ppm).
In addition, the change of the molecular weight distribution by this process was not seen (measurement by GPC).

(Example 8) (Support: PET film)
The maleimide resin solution (V1) obtained according to Synthesis Example 2 is cast-coated (WET film thickness 200 μm) onto a PET film (Lumirror 38-S10 manufactured by PANAC Co., Ltd.) which has not been subjected to release treatment using an applicator. The solvent was removed by drying the applied resin film at 160 ° C. for 1 hour.
The resulting maleimide resin molded product was in the form of a film having a thickness of 146 μm, and was peeled off and pulverized to form a maleimide resin molded product (M7) of the present invention in the form of flakes.
The residual solvent of the obtained maleimide resin molded product (M8) was 0.0571% (571 ppm). In addition, the change of the molecular weight distribution by this process was not seen (measurement by GPC).

(Comparative example 1)
Using a rotary evaporator, 300 mL of the maleimide resin solution (V1) obtained in Synthesis Example 2 was distilled off at 160 ° C. under heating and reduced pressure using a rotary evaporator 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. Comparison with molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2; It was confirmed. The residual solvent of the obtained maleimide resin (B1) was 0.1% (1000 ppm) or less.

(Comparative example 2)
The solvent was removed by distillation at 180 ° C. under heating and reduced pressure using a rotary evaporator, and it was confirmed that 1.0 L of the maleimide resin solution (V1) obtained in Synthesis Example 2 was gelled. The obtained maleimide resin (B2) lost its fluidity.

<Comparison of drying temperature in the method for producing a molded maleimide resin>
(Comparative example 3)
Similarly to Example 1, the maleimide resin solution (V1) obtained by Synthesis Example 2 was cast-coated (WET) onto a commercially available imide film ("Kapton (registered trademark) 100H" manufactured by Toray-DuPont) using an applicator. The solvent was removed by heating and drying the applied resin film with hot air at 50 ° C. for 1 hour.
The resulting maleimide resin molded product was sticky, could not maintain the shape of the film, and could not be peeled and crushed.

(Comparative example 4)
Similarly to Example 1, the maleimide resin solution (V1) obtained by Synthesis Example 2 was cast-coated (WET) onto a commercially available imide film ("Kapton (registered trademark) 100H" manufactured by Toray-DuPont) using an applicator. The solvent was removed by heating and drying the applied resin film with a hot air of 250 ° C. for 1 hour.
The resulting maleimide resin molded product was in the form of a film and was able to be peeled off and flaked, but the high molecular weight progressed and it became insoluble in various solvents such as acetone.

<Comparison of odor>
(Example 9, Comparative Example 5)
The maleimide resin molded product (M1) obtained in Example 1 and 4,4′-bismaleimidodiphenylmethane (hereinafter referred to as C1 manufactured by TCI) for comparison were prepared, and their odors were compared.
The acetic acid was quantified using a gas chromatograph GC-2010 Plus manufactured by Shimadzu Corporation. As a column, DB-WAX (manufactured by Agilene Technologies) 30 m in length and 0.25 mm in inner diameter were used. As a temperature rising program, a program 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 was used.

As a result, in Comparative Example 5, it was confirmed that the odor of acetic acid was generated, and in Example 9, no odor was felt.
In addition, when measured by gas chromatography, acetic acid was detected in Comparative Example 5 (see FIG. 4. Retention time 11.298 minutes). In addition, when the acid value was measured, the acid value was 10 mg KOH / g, and it was confirmed that it corresponds to 1% equivalent of acetic acid.

Comparison of shape and solvent solubility
(Examples 10-14, Comparative Examples 6 and 7)
Using the maleimide resin moldings (M1, M5 to M8) obtained in Examples 1, 5, 6, 7 and 8 and the maleimide resin C1 for comparison and the maleimide resin (B2) described in Comparative Example 2 to acetone Dissolution test was conducted.
When the resin concentration was adjusted to 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 understood that the maleimide resin molded product (M1, M5 to M8) does not proceed with the high molecular weight formation reaction from the complete dissolution in Examples 10 to 14. On the other hand, in Comparative Examples 6 and 7, it was found that the copolymerization with the maleimide resin (C1, B2) was advanced because complete dissolution was not possible.

Preparation of maleimide resin composition, comparison of cured product characteristics
(Example 15)
Ten parts of the maleimide resin molding (M1) obtained in Example 1 and 0.21 parts of 2-ethyl-4-methylimidazole (2E4MZ manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator were mixed and uniformly mixed by stirring -It knead | mixed and obtained the maleimide resin composition of this invention. The maleimide resin composition is cast coated (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 is cured under the conditions 160 A cured product was obtained by curing while removing the solvent at ° C × 2 h + 180 ° C. × 6 h. The results of evaluating the physical properties of the obtained cured product are shown in Table 1.

(Comparative example 8)
61 parts of EPPN-502H (manufactured by Nippon Kayaku Co., Ltd. epoxy equivalent 169 g / eq. Softening point 67.5 ° C. EP 1), 38 parts by weight of phenol novolak (manufactured by Meiwa Kasei Co., Ltd. H-1, hydroxyl equivalent 106 g / eq.), Triphenyl One part by weight of phosphine (TPP genuine chemical reagent) was blended, uniformly mixed and kneaded using a mixing roll, and an epoxy resin composition was obtained. After this epoxy resin composition was tableted, a resin composition molded body was prepared by transfer molding, and a cured product was obtained at 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)
65 parts of EOCN-1020-55 (Nippon Kayaku epoxy equivalent 194 g / eq. Softening point 54.8 ° C. EP 2), 34 parts by weight of phenol novolac (H-1 manufactured by Meiwa Kasei, hydroxyl equivalent 106 g / eq.), One part by weight of TPP (Genuine Chemical Reagent) was blended and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. After this epoxy resin composition was tableted, a resin composition molded body was prepared by transfer molding, and a cured product was obtained at 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 measurements were carried out on the obtained cured product.
・ DMA
Measurement item: Storage modulus of 30 ° C, 200 ° C, 250 ° C,
: Glass transition temperature (temperature at maximum tan δ)
Measurement method: Dynamic viscoelasticity measuring instrument TA-instruments, Q-800
Measurement temperature range: 30 ° C to 350 ° C
Temperature rate: 2 ° C / min
Test piece size: The thing cut out to 5 mm x 50 mm was used (thickness is about 800 micrometers).

  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 of using a high heat resistant epoxy resin, It can be seen that the change in elastic modulus at high temperatures is small.

Although the present invention has been described in detail with reference to particular 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 present invention.
The present application is based on the Japanese Patent Application (Japanese Patent Application No. 2016-169417) filed on August 31, 2016, which is incorporated by reference in its entirety. Also, all references cited herein are taken as a whole.

The maleimide resin molding of the present invention can easily prepare a maleimide resin composition, and 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), automotive It is extremely useful in a wide range of applications such as high heat resistance sealing material applications for SiC power devices.

Claims (13)

  A maleimide resin molded product containing a maleimide resin and an organic solvent and in the form of a film or flake.   The maleimide resin molding according to claim 1, wherein the content of the organic solvent is 30000 ppm or less.   The maleimide resin molding according to claim 1 or 2, wherein the organic solvent is at least one selected from an aromatic hydrocarbon having 3 to 10 carbon atoms, ketones, esters, and ethers.   The maleimide resin molding according to any one of claims 1 to 3, which has a thickness of 10 μm to 3 mm.   The maleimide resin molded body 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 number of functional groups of 2 to 20.   The softening point of the said maleimide resin is 50-150 degreeC, The maleimide resin molding as described in any one of Claims 1-5.   The manufacturing method of the maleimide compound molded object which apply | coats the solution which melt | dissolved maleimide resin in the organic solvent on the surface of a support body, and it dries.   The method for producing a molded maleimide compound 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 molded maleimide compound according to claim 7 or 8, wherein the drying temperature is 80 to 200 ° C.   The maleimide resin molding obtained by the manufacturing method as described in any one of Claims 7-9.   A maleimide resin composition comprising the maleimide resin molding 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 a maleimide resin and a curing accelerator. A cured product of the maleimide resin composition according to claim 11 or 12.

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