TW201815919A - Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof - Google Patents

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

   A maleimide resin imide, a method for producing a maleimide resin imide, a maleimide resin composition, and a cured product thereof   

The present invention relates to a maleimide resin imide, a method for producing a maleimide resin imide, a maleimide resin composition, and a cured product thereof. Specifically, it relates to a variety of composites represented by high-reliability semiconductor sealing materials, electrical and electronic component insulation materials, and laminated boards (printed wiring glass fiber reinforced composite materials) or CFRP (carbon fiber reinforced composite materials). Material applications, various adhesive applications, various coating applications, structural members, etc. useful cisbutadiene diimide resin moldings, excellent workability, low environmental exposure, and cisbutadiene diimide resin molding A method for producing a body, a maleimide resin composition, and a cured product thereof.

The maleimide resin is a compound that has heat resistance that exceeds that of epoxy resins, has the same moldability as epoxy resins, and has properties of low linear expansion coefficient and high Tg. Polymaleimide compounds can be cross-linked individually or reacted with various maleimide compounds or cross-linking agents to provide materials with excellent heat resistance and flame resistance. For various applications such as sealing materials, substrate materials, and insulating materials. Especially used for high heat-resistant substrate materials, flexible substrate materials, high heat-resistant low-dielectric materials, high heat-resistant CFRP materials (carbon fiber composite materials), and SiC suitable for automotive applications, which must have both high heat resistance and moldability. Use of high heat-resistant sealing materials for power devices.

In the past, because cis-butene diimide resins are self-reactive, they were obtained in the form of crystalline powders such as recrystals during their acquisition, or as resin powders formed by reprecipitation. Refer to Patent Document 1), due to powder scattering during use, there are not only problems with workability and productivity, but also problems with environmental pollution (dirt and inhalation into the human body) and the like. Furthermore, there is a problem that the solvent cannot be completely removed by inhaling the solvent during crystallization and precipitation, and the acetic acid used in the production is inhaled, and the odor of acetic acid remains in the finished product, which is related to the safety of the operator. Subject. Under such a background, a cis-butene diimide molded article excellent in workability, productivity, and environmental safety is expected. For example, Patent Document 2 discloses a method for obtaining a melt of a maleimide resin solution using an evaporator.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Publication No. 6-86425

Patent Document 2: Japanese Patent Application Laid-Open No. 2009-001783

However, in Patent Document 2, a large change does not occur on a small scale, but when the amount of synthesis is increased, it takes a long time to remove the solvent by distillation, so there is a possibility that self-polymerization is performed during this period. Therefore, in the actual production, there is a great risk of polymerization or gelation. From the viewpoint of moldability and stable productivity, there are problems, for example, the viscosity increases with an increase in molecular weight, and the characteristics are different at each production. . In addition, if the solvent recovery temperature is lowered in order to suppress the polymerization, particularly in the case of a cis butylene diimide resin having a softening point of 50 ° C or higher, it is difficult to remove the solvent, and the residual amount of the solvent increases (especially in excess of 30,000 ppm) Residual solvents), therefore, there may be voids or cracks during molding, and there are also problems with safety such as exposure to operators. Furthermore, in the synthesis of these maleimide resins, there are cases where substances that affect the human body such as acetic acid, toluene, and xylene are used. Therefore, the residual solvent is a problem.

Therefore, an object of the present invention is to provide a cis-butadieneimide resin molded body which is excellent in workability and productivity and has a low environmental exposure.

The present inventors have made intensive research in order to solve the above-mentioned problems, and as a result, they have found that they are excellent in workability, productivity, etc., and are not exposed to the environment by being obtained as a film-like or chip-like shaped body instead of a conventional crystalline or powdery form It is reduced, thereby completing the present invention.

That is, the present invention relates to: [1] a maleimide resin imine formed body comprising a maleimide resin and an organic solvent, and having a film shape or a chip shape; [2] as described in the foregoing item [ 1] A molded article of maleimide resin according to [1], wherein the content of the organic solvent is 30,000 ppm or less; [3] A resin of maleimide resin described in [1] or [2] above A formed body, wherein the organic solvent is at least one selected from the group consisting of aromatic hydrocarbons having 3 to 10 carbons, ketones, esters, and ethers; [4] as in any one of the foregoing items [1] to [3] The cisbutadiene diimide resin molded body according to the description, which has a thickness of 10 μm to 3 mm; [5] The cis butadiene diimide resin molded body according to any one of the foregoing items [1] to [4] Wherein, the above-mentioned maleimide resin is a novolak-type maleimide resin having repeating units having an average number of functional groups of 2 to 20; [6] as in the above items [1] to [5] The molded article of maleimide resin according to any one of the preceding claims, wherein the softening point of the maleimide resin is 50 to 150 ° C; [7] molding of a maleimide compound System A method in which a solution obtained by dissolving a maleimide resin in an organic solvent is coated on a surface of a support and dried; [8] the maleimide as described in [7] above. The method for producing an imine compound molded body, wherein the organic solvent is at least one selected from the group consisting of aromatic hydrocarbons having 3 to 10 carbons, ketones, esters, and ethers; [9] as described in the above item [7] or [ 8] The method for producing a molded article of maleimide compound according to [8], wherein the drying temperature is 80 to 200 ° C; [10] A molded article of maleimide resin, which is based on the above item [ 7] Obtained by the production method described in any one of [9]; [11] A maleimide resin composition comprising any of the items [1] to [6] and [10] The maleimide resin imine according to one item; [12] The maleimide resin imide resin composition according to the item [11], further comprising a compound selected from the group consisting of maleimide At least one of a compound that undergoes a cross-linking reaction with an imine resin and a hardening accelerator; [13] A hardened product, which is the cis-butenedifluorene imine resin according to the item [11] or [12] A hardened composition.

The cis butadiene diimide resin molding system of the present invention is formed in a film shape or chip shape, so it can suppress the content of organic solvents, and can provide cis butadiene diimide resin molding with excellent workability, productivity, and little environmental exposure. body. Further, since the amount of the organic solvent can be suppressed, it is possible to prevent voids or cracks from being generated during molding.

FIG. 1 is a graph showing a molecular weight distribution of a cis-butenediimine resin solution (V1) at the end of the polymerization reaction obtained in Synthesis Example 2. FIG.

FIG. 2 is a graph showing the molecular weight distribution of the maleimide resin molded article (M1) obtained in Example 1. FIG.

FIG. 3 is a graph showing the molecular weight distribution of the maleimide resin (B1) after the solvent is distilled off during the large-scale synthesis obtained in Comparative Example 1. FIG.

FIG. 4 is a graph showing the quantification of acetic acid in the maleimide resin (C1) of Comparative Example 4. FIG.

Hereinafter, the present invention will be described in detail.

The molded article of maleimide resin of the present invention includes a maleimide resin and an organic solvent, and is formed into a film shape or a chip shape.

Compared with conventional cis-butadieneimide resins which are usually supplied in crystalline or powder form, they can be supplied in the form of a film or chip, so they do not cause problems such as dust in terms of workability and are extremely easy to handle. That is, the maleimide resin imide of the present invention can easily prepare a maleimide resin composition.

The resin molded body refers to a product obtained by applying a resin solution to the surface of a support, removing the solvent under overheating and drying conditions, and peeling off the support while maintaining the same shape. Shape, fiber shape, plate shape, rod shape, etc.

Here, the term “film-like” refers to the form of a sheet having an average thickness of 10 μm to 3 mm. The term "fragmented" refers to a state where a film-like formed body is broken. In addition, the so-called chip shape is not particularly limited as long as it does not scatter like a powder during operation. Specifically, the average of the long diameter portion is preferably 0.1 cm to 5 cm, and more preferably It is 0.1 ~ 3cm.

In addition, the average thickness can be obtained by overlapping a plurality of sheets or films, measuring an arbitrary 10 points using a vernier caliper, and dividing the obtained thickness by the number of overlapping blocks.

Next, for convenience of explanation, a method for producing a maleimide resin imide of the present invention will be described.

The maleimide resin of the present invention can be obtained by dissolving a maleimide resin in an organic solvent (hereinafter, also referred to as "maleimide" Diamine imine resin solution "or" resin solution ") is coated on the surface of the support and formed into a film or sheet shape, and the solvent is removed under heating conditions (under reduced pressure if necessary), and The film was peeled from the support. That is, the method for producing a cis-butene diimide resin molded article of the present invention is performed by a step of applying a resin solution on the surface of a support, a step of heating and drying, and a step of peeling from the support. .

(Cis-butene diimide resin)

As the cis-butene diimide resin usable in the present invention, a known one can be used, but from the viewpoints of viscosity and softening point, a novolak type having repeating units having an average number of functional groups of 2 to 20 is preferred. Maleimide resin.

As a maleimide resin which can be used for this invention, it has the structure represented by following formula (1), for example.

(In the formula, a plurality of Rs each exist independently and represent a hydrogen atom, an alkyl group or a phenyl group having 1 to 10 carbon atoms. X is represented by the following structural formulae (a) to (e). N Is an average value, and represents 1 <n ≦ 5).

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

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

(Cis-butene diimide resin solution)

In the present invention, the maleicimide resin solution refers to a product obtained by dissolving the maleicimide resin in an organic solvent.

The maleimide resin solution is not particularly limited as long as the maleimide resin solution is dissolved in an organic solvent, except that it is synthesized by a known solution polymerization method or various controlled polymerization methods. Other than the polymer solution, a solid polymer may be precipitated during the polymerization, or a polymer may be precipitated by adding a precipitating agent to the solution after the polymerization.

The usable organic solvent is not particularly limited. For example, it is preferably at least one organic solvent selected from aromatic hydrocarbons having 3 to 10 carbons, ketones, esters, and ethers. Further, it is preferable to perform treatment such as washing with water on the reaction solution after polymerization.

The amount of the organic solvent used is usually 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the maleimide resin and the solvent.

As the maleimide resin, those 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 of the maleimide resin solution (cone-plate method, 150 ° C melt viscosity) is preferably 5.0 mPa. s ~ 10000Pa. s, more preferably 10mPa. s ~ 100Pa. s, particularly preferably 10mPa. s ~ 10Pa. s. If the cone viscosity at 150 ℃ is 10,000Pa. Below s, coating workability is not likely to decrease, so it is preferable.

(Procedure for coating on the surface of the support)

Next, the obtained maleimide resin solution is coated on the surface of the support, and formed into a film shape or a sheet shape.

The support for coating a solution of a maleimide resin is not particularly limited as long as the surface is smooth, and preferably, a metal, a PET film that has not been subjected to a release treatment, a film of imine, and the like are mentioned.

It is preferable to perform the film thickness and area when apply | coated on the surface of a support body so that it may become a dry film thickness of 10 micrometers-3 mm, and an area of 100 ^cm2 or less per 100 ^cm2 of the surface of a support body.

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 even more preferably 200 μm to 4.3 mm. If it exceeds the said range, the effect of reducing a residual solvent may not fully be acquired, and if it is less than this range, the productivity of a maleimide resin molded body may fall.

(The step of heating and drying and the step of peeling from the surface of the support)

Secondly, after coating the maleimide resin solution on the surface of the support, the solvent is removed under heating and drying conditions (under reduced pressure if necessary), and the surface of the support will be formed into a film or sheet. The dried coating film was peeled and obtained.

The drying temperature is preferably 80 to 250 ° C, more preferably 80 to 200 ° C, and even more preferably 100 to 200 ° C. Regarding the drying temperature, if it exceeds 250 ° C, the resin is likely to be deteriorated. Therefore, it is set according to the required processing characteristics. In addition, if the temperature is lower than 80 ° C, it is difficult to remove the solvent, and the residual amount of the solvent is increased. Therefore, voids or cracks may occur during molding, and there is a sticky feeling.

The film thickness of the film-shaped maleimide resin molded body obtained by peeling from the surface of the support is not particularly limited, but is preferably 10 μm to 3 mm, and more preferably 30 μm to 1 mm. If the film thickness exceeds 3 mm, the effect of reducing the amount of residual solvent cannot be sufficiently obtained.

Further, the obtained film-like maleimide resin imine product can also be used in the form of a chip-like maleimide resin imine product by pulverization.

The residual solvent of the cis-butene diimide resin molded body obtained by the above steps is 30,000 ppm or less. It is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, even more preferably 1000 ppm or less, and even more preferably 600 ppm or less. In addition, as a measurement detection limit, the lower limit is 5 ppm.

The obtained maleimide resin imide is preferably soluble in a solvent. Completely dissolved means that the maleimide resin has not undergone a high molecular weight reaction.

The maleimide resin imide obtained in this way has superior workability and productivity compared with conventional maleimide resins that have been supplied in a crystalline or powder form, and thus can be easily prepared. Butene difluorene imide resin composition.

Next, the maleimide resin composition of this invention is demonstrated.

The maleimide resin composition of this invention may contain the compound which can perform a crosslinking reaction with a maleimide resin molding. The cross-linkable compound system cross-links with the maleimide resin imide, and functions as a hardener for the maleimide resin. Examples of compounds that can be crosslinked include amino groups, cyano groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, allyl groups, methallyl groups, acrylic groups, methacrylic groups, vinyl groups, and conjugated dihydroxy groups. Alkenyl compounds and the like. For example, when heat resistance is required, an amine compound is preferably blended, and when dielectric properties are required, a cyanate compound is blended. Since the maleimide resin can also be self-polymerized, it can be used alone.

A catalyst (hardening accelerator) for hardening may be blended into the maleimide resin composition of the present invention as necessary. Examples include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole and other imidazoles; triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diazinebicyclo (5,4,0) -7- Amines such as undecene, tris (dimethylaminomethyl) phenol, dimethylbenzylamine; phosphines such as triphenylphosphine, tributylphosphine, trioctylphosphine; stannous octoate, zinc octoate, dicis Organometallic salts such as dibutyltin butenoate, zinc naphthenate, cobalt naphthenate, tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; bis-third butyl peroxide, Organic peroxides such as bisisophenylpropyl peroxide; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Lewis acids such as boron trifluoride , Sodium carbonate or lithium chloride. The blending amount of the curing catalyst is preferably in a range of 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the cisbutadieneimide resin molded article of the present invention.

A varnish-like composition (hereinafter, simply referred to as a varnish) may be added to the maleimide resin composition of the present invention by adding an organic solvent. If necessary, the maleimide resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamidine Amine, N-methylpyrrolidone and other solvents to make cis-butadieneimine resin composition varnish, impregnated with carbon fiber, glass fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. The substrate is heated and dried to obtain a prepreg, and the prepreg is hot-pressed to form a cured product of the cis-butene diimide resin composition of the present invention.

The solvent at this time usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight of 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 containing carbon fiber can also be obtained, for example by RTM method directly.

Moreover, the cis-butene diimide resin composition of the present invention can be used as a modifier for a film-shaped composition. Specifically, it can be used in the case of improving the flexibility of the B-stage and the like. With regard to such a film-shaped resin composition, the maleimide diimide resin composition of the present invention is made into the above maleimide diimide resin composition varnish and applied to a release film, and the film is heated under heating. The solvent is removed and then B-staged to obtain a sheet-like adhesive. This sheet-shaped adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

By heating and melting the maleimide resin composition of the present invention, the viscosity can be reduced and impregnated with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. And a prepreg was obtained.

Further, the varnish may be impregnated with the reinforcing fiber and heated and dried to obtain a prepreg.

The method for impregnating the cisbutadiene diimide resin composition of the present invention with these reinforcing fibers is also not particularly limited. A method without using a solvent is preferred, and therefore the following hot-melt method is preferred, that is, the present invention The cis-butene diimide resin composition is heated to 60 to 110 ° C, so that it is impregnated in a fluid state.

The proportion of the maleimide resin composition in the obtained prepreg (made by impregnating a maleimide resin composition with a reinforcing fiber) differs depending on the form of the reinforcing fiber, It is usually 20% by weight or more and 80% by weight or less, preferably 25% by weight or more and 65% by weight or less, and more preferably 30% by weight or more and 50% or less. If the ratio of the maleimide diimide resin composition is more than this range, a sufficient reinforcing effect cannot be obtained because the ratio of the reinforcing fibers is relatively reduced. On the contrary, if the maleimide diimide resin composition is less than this range, Range, the formability may be impaired.

This prepreg can be hardened by a well-known method, and it can be set as a final molded article. For example, a prepreg volume layer can be pressurized in an autoclave to 2 to 10 kgf / cm ² and heat-hardened at 150 ° C. to 200 ° C. for 30 minutes to 3 hours to produce a shaped body, but in order to further improve heat resistance In the temperature range of 180 ° C to 280 ° C, the fiber-reinforced composite material molded product can be produced by performing a treatment for 1 to 12 hours while gradually heating it.

After cutting the above prepreg into a desired shape, and laminating it with copper foil, etc., if necessary, using a press forming method, an autoclave forming method, a sheet winding forming method, etc., the laminated sheet is pressed while applying pressure to the laminated sheet. A laminated board can be obtained by heat-hardening with a maleimide resin composition.

Furthermore, a multilayer board formed by laminating a copper foil on the surface can form a circuit, and a prepreg, a copper foil, or the like can be stacked thereon and the above operations can be repeated to obtain a multilayer circuit board.

The hardened material of the prepreg of the present invention can be widely used in robotic manipulators for liquid crystal glass substrate transfer, disc applications for silicon wafer transfer, component applications suitable for aerospace, and automotive engine component applications. Strength and high heat resistance.

Specific applications of the butadiene diimide resin composition of the present invention include adhesives, coatings, coating agents, molding materials (including sheets, films, FRP, etc.), and insulating materials for electronic materials (including printing Additives such as sealing materials for substrates, wire coatings, etc., and sealing materials, cyanate resin compositions for substrates, or acrylic resins as hardeners for resists, and other resins. Especially in FRP applications, for the consideration of the environment and the elimination of defects caused by voids, in recent years, no solvent has been greatly promoted. Furthermore, due to problems such as voids during molding, poor molding, and reduced voltage resistance, there are also environments in which solvents cannot enter the steps during semiconductor sealing applications.

    [Example]    

Hereinafter, the content of the present invention will be specifically described based on examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "parts" and "%" in this text mean "parts by weight" and "% by weight", respectively. In the examples, the softening point and the melt viscosity were measured by the following methods.

． Softening point: measured by the method according to JISK-7234

． Melt viscosity: viscosity at 150 ℃ by cone-plate method

． The amount of residual solvent was quantified using a gas chromatograph GC-2010 manufactured by Shimadzu Corporation, and a DB-WAX (manufactured by Agilene Technologies) having a length of 30 m and an inner diameter of 0.25 mm was used as a column.

As the heating program, a program held at 70 ° C. for 5 minutes, heated to 140 ° C. at a heating rate of 10 ° C./min, and heated to 220 ° C. at a heating rate of 20 ° C./min, and held at 220 ° C. for 5 minutes.

． The molecular weight information was obtained using a gel permeation chromatography (GPC, LC-20AD manufactured by Shimadzu Corporation). The column system is KF-603, KF-602.5, KF-602, KF-601. The column temperature is 40 ° C, the mobile phase is THF, and the flow rate is 0.5ml / min. .

(Synthesis example 1)

559 parts of aniline and 500 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation separator, and a stirrer, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the azeotropic water and toluene were cooled and liquid-separated, and then only toluene as an organic layer was returned to the system to perform dehydration. Then, 251 parts of 4,4'-bis (chloromethyl) biphenyl was maintained at 60-70 degreeC, it added over 1 hour, and it was made to react at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, and the inside of the system was set at 190 to 200 ° C, and the reaction was performed at this temperature for 15 hours. Then, while cooling, slowly add 500 parts of a 30% sodium hydroxide aqueous solution in a manner that does not cause a severe reflux in the system, return the distilled toluene to the system below 80 ° C, and leave it to stand at 70 ° C to 80 ° C. The water layer separated from the lower layer was removed, and the water washing of the reaction solution was repeated until the washing solution became neutral. Then, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure, thereby obtaining 335 parts of an aromatic amine resin (A1). Aromatic amine resin (A1) has a softening point of 59 ° C and a melt viscosity of 0.05Pa. s.

(Synthesis example 2)

To a flask equipped with a thermometer, a cooling pipe, a Dean-Stark azeotropic distillation separator, and a stirrer, 88 parts of maleic anhydride and 300 parts of toluene were added, and the azeotropic water and toluene were cooled and separated. Then, only toluene, which is an organic layer, is returned to the system and dehydrated. Next, a resin solution prepared by dissolving 116 parts of the aromatic amine resin (A1) in 116 parts of N-methyl-2-pyrrolidone was maintained in the system at 80 to 85 ° C. and dripped for 1 hour. After the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid was added, and the azeotropic condensation water and toluene were cooled and separated under reflux conditions, and then only the toluene as the organic layer was returned to the system. Instead, dehydration was performed, and a reaction was performed for 10 hours. After completion of the reaction, 120 parts of toluene was added, and water washing was repeatedly performed to remove p-toluenesulfonic acid and excess maleic anhydride, and heating was performed to remove water from the system by azeotropy. Then, the reaction solution was concentrated to obtain a maleimide resin solution (V1) containing 70% of a maleimide resin. The molecular weight distribution of the obtained maleimide resin solution (V1) was measured by GPC, and the results shown in FIG. 1 were obtained.

(Synthesis example 3)

559 parts of aniline and 500 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation separator, and a stirrer, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the azeotropic water and toluene were cooled and separated, and then only the toluene as the organic layer was returned to the system to perform dehydration. Then, 175 parts of 4,4'-bis (chloromethyl) benzene was maintained at 60-70 degreeC, it added over 1 hour, and it was made to react at the same temperature for 2 hours. After the reaction was completed, toluene was distilled off while raising the temperature, and the inside of the system was set to 190 to 200 ° C, and the reaction was performed at this temperature for 15 hours. Then, while cooling, slowly add 500 parts of a 30% sodium hydroxide aqueous solution in such a manner that the system does not reflux violently, return the distilled toluene to the system below 80 ° C, and leave it at 70 ° C to 80 ° C. The water layer separated from the lower layer was removed, and the water washing of the reaction solution was repeated until the washing solution became neutral. Then, 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) is a semi-solid resin.

(Synthesis example 4)

To a flask equipped with a thermometer, a cooling pipe, a Dean-Stark azeotropic distillation separator, and a stirrer, 88 parts of maleic anhydride and 300 parts of toluene were added, and the azeotropic water and toluene were cooled and separated. Then, only toluene, which is an organic layer, is returned to the system and dehydrated. 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 maintained in the system at 80 to 85 ° C. and dripped for 1 hour. After the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid was added, and the azeotropic condensation water and toluene were cooled and separated under reflux conditions, and then only the toluene as the organic layer was returned to the system. Instead, dehydration was performed, and a reaction was performed for 10 hours. After completion of the reaction, 120 parts of toluene was added, and water washing was repeatedly performed to remove p-toluenesulfonic acid and excess maleic anhydride, and heating was performed to remove water from the system by azeotropy. Then, the reaction solution was concentrated to obtain a maleimide resin solution (V2) containing 70% of a maleimide resin.

(Example 1) (Support: amidine film)

Using a applicator, a flow casting of the cis butylene diimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available fluorimide film ("Kapton (registered) manufactured by TORAY-DUPONT"). Trademark) 100H ″) (WET film thickness 200 μm), and the solvent was removed by drying the applied resin film at 180 ° C. for 15 minutes.

The obtained maleimide diimide resin molded body was a film having a thickness of 125 μm, and was peeled and pulverized to obtain a chip-like maleimide diimide resin molded body (M1) of the present invention.

The residual solvent of the obtained maleimide resin molded body (M1) was 0.236% (2360 ppm). The molecular weight distribution of the obtained maleimide resin imine (M1) was measured by GPC, and the results shown in FIG. 2 were obtained. Compared with the molecular weight distribution (Figure 1) measured by GPC with the cis-butene diimide resin solution (V1) obtained by Synthesis Example 2, no change in the molecular weight distribution based on this step (using GPC) was found. Its measurement).

(Example 2) (Support: hydrazone film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast-coated on a commercially available fluorinimide film ("Kapton (registered trademark) 100H" manufactured by TORAY-DUPONT) using an applicator. ) (WET film thickness 200 μm), and the solvent was removed by drying the applied resin film at 200 ° C. for 15 minutes.

The obtained maleimide diimide resin molded body was a film having a thickness of 125 μm, and the maleimide diimide resin molded body (M2) of the present invention was formed into a chip shape by peeling and pulverizing.

The residual solvent of the obtained maleimide resin imine (M2) was 0.293% (2930 ppm). Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 3) (Support: fluorene imine film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast-coated onto a commercially available fluorinimide film ("Kapton (registered trademark) 100H" manufactured by TORAY-DUPONT) using an applicator. ) (WET film thickness 200 μm), and the solvent was removed by drying the applied resin film at 200 ° C. for 10 minutes.

The obtained maleimide diimide resin molded body was a film having a thickness of 125 μm, and the maleimide diimide resin molded body (M3) of the present invention was formed into a chip shape by peeling and pulverizing.

The residual solvent of the obtained maleimide resin imine (M3) was 0.398% (3980 ppm). Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 4) (Support: hydrazone film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was cast-coated on a commercially available fluorinimide film ("Kapton (registered trademark) 100H" manufactured by TORAY-DUPONT) using an applicator. ) (WET film thickness 200 μm), and the solvent was removed by drying the applied resin film at 200 ° C. for 5 minutes.

The obtained maleimide diimide resin molded body was a film having a thickness of 125 μm, and was peeled and pulverized to obtain a chip-like maleimide diimide resin molded body (M4) of the present invention.

The residual solvent of the obtained maleimide resin imine (M4) was 0.0901% (901 ppm).

Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 5) (Support: SUS board)

Using an applicator, the cisbutadieneimine resin solution (V1) obtained in Synthesis Example 2 was cast-coated on a SUS board (WET film thickness 200 μm), and the applied resin film was 180 ° C. The solvent was removed by drying at 15 ° C for 15 minutes.

The obtained maleimide resin imine product having a film shape of 113 m in thickness was peeled and pulverized to form a chip-like maleimide resin imide product (M5) of the present invention.

The residual solvent of the obtained maleimide resin imine (M5) was 0.163% (1638 ppm).

Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 6) (Support: SUS board)

Using an applicator, the cis-butene diimide resin solution (V2) obtained in Synthesis Example 4 was cast-coated on a SUS board (WET film thickness 200 μm), and the applied resin film was 180 ° C. The solvent was removed by drying at 15 ° C for 15 minutes.

The obtained maleimide diimide resin molded article was a film having a thickness of 113 μm, and was peeled and pulverized to obtain a chip-like maleimide diimide resin molded article (M6) of the present invention.

The residual solvent of the obtained maleimide resin imine (M6) was 0.3% ≦ (3000ppm ≦). Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 7) (Support: Mirror copper foil)

Using an applicator, the cisbutadieneimine resin solution (V1) obtained in Synthesis Example 2 was cast-coated on an electrolytic copper foil (manufactured by Fukuda Metal Foil Industry Co., Ltd., 18 μ electrolytic copper foil CF- T9FZ-HTE), and the solvent was removed by drying the coated resin film at 180 ° C for 15 minutes.

The obtained maleimide resin imide is a film having a thickness of 152 μm, and is peeled and pulverized to form a chip-shaped maleimide resin imide (M7) of the present invention.

The residual solvent of the obtained maleimide resin imine (M7) was 0.0728% (728 ppm).

Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Example 8) (Support: PET film)

Using an applicator, the cis-butadieneimine resin solution (V1) obtained in Synthesis Example 2 was cast-coated on a PET film (made by Panac Corporation, Lumirror 38-S10) without release treatment ( WET film thickness is 200 μm), and the solvent is removed by drying the applied resin film at 160 ° C. for 1 hour.

The obtained maleimide diimide resin molded body was a film-shaped 146 μm thick film, and was peeled and pulverized to obtain a chip-like maleimide diimide resin molded body (M8) of the present invention.

The residual solvent of the obtained maleimide resin imine (M8) was 0.0571% (571 ppm). Furthermore, no change in the molecular weight distribution (measurement by GPC) based on this step was found.

(Comparative example 1)

With respect to 300 mL of the maleimide resin solution (V1) obtained in Synthesis Example 2, the solvent was distilled off at 160 ° C. using a rotary evaporator under heating and reduced pressure, and maleimide was obtained as a resin block. Imine resin (B1). The molecular weight distribution of the obtained maleimide resin (B1) was measured by GPC, and the results shown in FIG. 3 were obtained. Compared with the molecular weight distribution (Figure 1) measured by GPC with the cis-butene diimine resin solution (V1) obtained in Synthesis Example 2, the results confirmed that cis-butyl was removed by solvent distillation during the synthesis The enediimide resin (B1) has a high molecular weight. The residual solvent of the obtained maleimide resin (B1) was 0.1% (1000 ppm) or less.

(Comparative example 2)

Regarding 1.0 L of the cis butylene diimide resin solution (V1) obtained in Synthesis Example 2, the solvent was distilled off at 180 ° C. under a reduced pressure using a rotary evaporator, and as a result, gelation was confirmed. . The obtained maleimide resin (B2) lost fluidity.

<Comparison of Drying Temperature in the Production Method of the Butylene Diimide Resin Molded Body>

(Comparative example 3)

In the same manner as in Example 1, the maleimide film (V1) obtained in Synthesis Example 2 was cast-coated on a commercially available fluorimide film ("manufactured by TORAY-DUPONT" using an applicator). Kapton (registered trademark) 100H ") (WET film thickness 200 µm), and the applied resin film was heated and dried for 1 hour by hot air at 50 ° C to remove the solvent.

The obtained cis-butene diimide resin molded article had a sticky feeling, could not maintain the shape of the film, and could not be peeled off and crushed.

(Comparative Example 4)

In the same manner as in Example 1, the maleimide film (V1) obtained in Synthesis Example 2 was cast-coated on a commercially available fluorimide film ("manufactured by TORAY-DUPONT" using an applicator). Kapton (registered trademark) 100H ") (WET film thickness 200 µm), and the coated resin film was heated and dried for 1 hour by hot air at 250 ° C to remove the solvent.

The obtained cis-butene diimide resin molded article was film-like, peelable, and fragmented, but was polymerized and was insoluble in various solvents such as acetone.

<Comparison of Smells>

(Example 9 and Comparative Example 5)

Preparation of the cis-butylene diimide resin molded article (M1) obtained in Example 1 and 4,4'-bis-cis-biene diimide diphenylmethane (manufactured by TCI, for comparison, hereinafter C1). Compare the odor.

The acetic acid was quantified using a gas chromatograph GC-2010Plus manufactured by Shimadzu Corporation, and a DB-WAX (manufactured by Agilene Technologies) having a length of 30 m and an inner diameter of 0.25 mm was used as a column. As the heating program, a program held at 60 ° C. for 7 minutes, heated to 220 ° C. at a heating rate of 20 ° C./min, and held at 220 ° C. for 5 minutes.

As a result, the odor of acetic acid was confirmed in Comparative Example 5, and the odor was not felt in Example 9.

Further, measurement by a gas chromatograph revealed that acetic acid was detected in Comparative Example 5 (refer to FIG. 4, and the holding time was 11.298 minutes). The acid value was measured. As a result, it was confirmed that the acid value was 10 mgKOH / g, which corresponds to 1% of acetic acid.

<Comparison of shape and solvent solubility>

(Examples 10 to 14, Comparative Examples 6 and 7)

The cisbutadieneimide resin molded body (M1, M5 to M8) obtained in Examples 1, 5, 6, 7, and 8 and the cisbutadieneimide resin C1 for comparison were used, and Comparative Example 2 was used. The described maleimide resin (B2) was subjected to a dissolution test for acetone.

The concentration of the resin was 50% and the results were studied. As a result, the maleimide resin molded bodies M1, M5 to M8 were completely dissolved, but the maleimide resin (C1) and maleimide resin were completely dissolved. (B2) Not completely dissolved.

Based on the above, it can be seen that in Examples 10 to 14 they were completely dissolved, and therefore the cis-butene diimide resin molded body (M1, M5 to M8) did not undergo a high molecular weight reaction. On the other hand, it can be seen that Comparative Examples 6 and 7 cannot be completely dissolved, and thus the butene bisimine resin (C1, B2) has undergone a high molecular weight reaction.

<Preparation of maleimide resin composition and comparison of cured product characteristics>

(Example 15)

10 parts of maleimide resin imide (M1) obtained in Example 1 and 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Chemical Co., Ltd.) as a hardening accelerator were blended. (Manufactured) 0.21 parts, and uniformly mixed and kneaded by stirring to obtain the maleimide resin composition of the present invention. This maleimide resin composition was cast-coated onto a commercially available sulfonimide film ("Kapton (registered trademark) 100H" manufactured by TORAY-DUPONT)) (WET film thickness 200 μm) using an applicator. The coated resin film was cured under the curing conditions of 160 ° C × 2h + 180 ° C × 6h while removing the solvent, thereby obtaining a cured product. The results obtained by evaluating the physical properties of the obtained hardened materials are shown in Table 1.

(Comparative Example 8)

Blended with 61 parts of EPPN-502H (manufactured by Nippon Kayaku, epoxy equivalent 169g / eq., Softening point 67.5 ° C EP1), phenol novolak (manufactured by Meiwa Chemical Co., Ltd., H-1, hydroxyl equivalent 106g / eq.) 38 weight Parts, 1 part by weight of triphenylphosphine (TPP pure chemistry, reagents), uniformly mixed and kneaded using a mixing roller 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 under hardening 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)

Blended with 65 parts of EOCN-1020-55 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 194g / eq., Softening point 54.8 ° C, EP2), phenol novolak (manufactured by Meiwa Chemical Co., Ltd., H-1, hydroxyl equivalent 106g / eq. ) 34 parts by weight and 1 part by weight of TPP (pure chemical reagent) were uniformly mixed and kneaded using a mixing roller 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 under hardening 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 obtained hardened | cured material was measured as follows.

． DMA

Measurement items: storage elastic modulus at 30 ° C, 200 ° C, 250 ° C, glass transition temperature (temperature when tanδ is maximum)

Measurement method: Manufactured by TA-instruments, Q-800

Measuring temperature range: 30 ℃ ~ 350 ℃

Heating rate: 2 ℃ / min

Test piece size: A 5 mm × 50 mm cut (thickness of about 800 μm) was used.

As can be seen from Table 1, the cured product of the cis-butene diimide resin composition of the present invention can be formed under the same curing conditions as the epoxy resin, and the obtained cured product is in a case where a highly heat-resistant epoxy resin is used. In comparison, the elastic modulus changes less at high temperatures.

The present invention has been described in detail with reference to specific aspects, but it should be understood by the practitioner that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Furthermore, this application is based on a Japanese patent application filed on August 31, 2016 (Japanese Patent Application No. 2016-169417), and the entirety thereof is incorporated by reference. All references cited herein are incorporated as a whole.

    [Industrial availability]    

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

Claims (13)

    A molded article of maleimide resin containing maleimide resin and an organic solvent, and has a film shape or a chip shape.         For example, the cis-butene diimide resin molded article of the first patent application range, wherein the content of the organic solvent is 30,000 ppm or less.         For example, the cis-butene diimide resin molded article according to item 1 or 2 of the application, wherein the organic solvent is at least one selected from aromatic hydrocarbons, ketones, esters, and ethers having 3 to 10 carbon atoms. One.         For example, the cisbutadieneimide resin molded article according to any one of the claims 1 to 3 has a thickness of 10 μm to 3 mm.         For example, the cis-butadiene-imide resin molded article according to any one of the claims 1 to 4, wherein the cis-butene-diimide resin is a phenol having a repeating unit having an average number of functional groups of 2 to 20 Varnish-type maleimide resin.         For example, the cisbutadieneimide resin molded body according to any one of the claims 1 to 5, wherein the softening point of the cisbutadieneimide resin is 50 to 150 ° C.         A method for producing a molded article of a maleimide compound comprising applying a solution obtained by dissolving a maleimide resin in an organic solvent on a surface of a support and drying the solution.         For example, the method for manufacturing a molded article of cis-butenediimine compound according to item 7 of the application, wherein the organic solvent is selected from aromatic hydrocarbons, ketones, esters, and ethers having 3 to 10 carbon atoms. At least one.         For example, the method for manufacturing a molded article of cis-butenediimine compound according to item 7 or 8 of the scope of patent application, wherein the drying temperature is 80 to 200 ° C.         A molded article of maleimide resin, which is obtained by a manufacturing method according to any one of claims 7 to 9 of a patent application.         A maleimide resin composition comprising a maleimide resin imine according to any one of the scope of claims 1 to 6 and 10 of the scope of a patent application.         For example, the maleimide resin composition of item 11 of the scope of patent application further includes at least any one selected from the group consisting of a compound capable of undergoing a crosslinking reaction with a maleimide resin and a hardening accelerator.         A hardened product, which is a hardened product of a cis-butene diimide resin composition in the scope of patent application No. 11 or 12.