KR20190046815A - Maleimide resin molded article, method of producing maleimide resin molded article, maleimide resin composition and cured product thereof - Google Patents

Abstract

Applications of high reliability semiconductor sealing materials, applications of electric and electronic parts insulation materials, various composite materials including laminated boards (printed wiring glass fiber reinforced composite materials) and CFRP (carbon fiber reinforced composite materials), various adhesive applications, The present invention provides a maleimide resin molded article, a maleimide resin composition and a cured product thereof which are excellent in workability and productivity which are useful for members and the like and are less exposed to the environment. The maleimide resin molded article contains a maleimide resin and an organic solvent, and is in the form of a film or a flake.

Description

Maleimide resin molded article, method of producing maleimide resin molded article, maleimide resin composition and cured product thereof

The present invention relates to a maleimide resin molded article, a method for producing a maleimide resin molded article, a maleimide resin composition and a cured product thereof. Specifically, the present invention relates to the use of a high-reliability semiconductor sealing material, an insulating material for electrical and electronic parts, and various composite materials including a laminate (printed wiring glass fiber reinforced composite material) or CFRP (carbon fiber reinforced composite material) A maleimide resin molded article, a maleimide resin composition, and a cured product thereof, which are excellent in workability and productivity, which are useful for coating materials and structural members, and are less exposed to the environment.

The maleimide resin is a compound having a heat resistance exceeding an epoxy resin, a moldability equivalent to that of an epoxy resin, and a low coefficient of linear expansion and high Tg. The poly (maleimide) compound has been used for various purposes such as a sealing material, a base material, and an insulating material because it can give a material excellent in heat resistance and flame retardancy by crosslinking alone, or reacting with various maleimide compounds or crosslinking agents. Heat-resistant base material, high heat-resistant low-k dielectric material, high heat-resistant CFRP material (carbon fiber composite material), and high heat-resistant sealing material for in-vehicle SiC power devices Used for applications.

Conventionally, since maleimide resins have self-reactivity, most of them are commercially available as drawn resin powders by drawing or recrystallization from crystal powders such as recrystallization (see Patent Document 1), and when used, (Contamination and inhalation to the human body) as well as workability, productivity, and the like. In addition, there is a problem that a solvent or the like is mixed at the time of crystallization and precipitation, so that it is impossible to remove all of them, and acetic acid used in the production is mixed, and a stench of acetic acid is generated in the produced product, . From these backgrounds, there is a demand for a maleimide molded article excellent in workability, productivity, and environmental safety. For example, Patent Document 2 discloses a melt drawing method of a maleimide resin solution using this dilator.

Japanese Patent Publication No. Hei 6-86425 Japanese Patent Application Laid-Open No. 2009-001783

However, in Patent Document 2, there has been no significant change in the small scale scale, but when the amount of synthesis is increased, it takes a long time to distill and remove the solvent, and there is a possibility that the self-polymerization progresses during this period. Therefore, there is a problem in terms of moldability and stable productivity, such as an increase in viscosity due to an increase in the molecular weight, and different properties each time the product is produced. When the solvent recovery temperature is lowered in order to suppress the polymerization, in particular, in the case of a maleimide resin having a softening point of 50 캜 or more, it becomes difficult to remove the solvent, so that the solvent remains (in particular, the solvent remaining in excess of 30,000 ppm) , There is also a problem in safety such as generation of a void or crack at the time of molding, exposure to an operator, and the like. In addition, in the synthesis of these maleimide resins, there is a case where a substance having an influence on the human body such as acetic acid, toluene, and xylene is used, so that the residual solvent is particularly problematic.

Therefore, the object of the present invention is to provide a maleimide resin molded article excellent in workability and productivity, and having little environmental exposure.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the problems described above and found that not only a conventional crystal phase or a powder phase but also a film or a flake-like molded body is pulled out to provide excellent workability and productivity, .

That is,

[1] A maleimide resin molding comprising a maleimide resin and an organic solvent and being in a film or flake form,

[2] The maleimide resin molded article according to [1], wherein the content of the organic solvent is 30,000 ppm or less,

[3] The maleimide resin molded article according to [1] or [2], wherein the organic solvent is at least one selected from aromatic hydrocarbons, ketones, esters and ethers having 3 to 10 carbon atoms,

[4] The maleimide resin molded article described in any one of [1] to [3], wherein the maleimide resin molded article has a thickness of 10 μm to 3 mm,

[5] The maleimide resin molded article according to any one of the items [1] to [4], wherein the maleimide resin is a novolak type maleimide resin having a repeating unit having an average number of functional groups of 2 to 20,

[6] The maleimide resin molded article described in any one of [1] to [5], wherein the maleimide resin has a softening point of 50 to 150 ° C,

[7] A process for producing a maleimide compound molded article in which a solution prepared by dissolving a maleimide resin in an organic solvent is applied on the surface of a support and dried,

[8] The method for producing a maleimide compound molded article according to [7], wherein the organic solvent is at least one selected from aromatic hydrocarbons, ketones, esters and ethers having 3 to 10 carbon atoms,

[9] The method for producing a maleimide compound molded article described in [7] or [8], wherein the drying temperature is 80 to 200 ° C,

[10] A maleimide resin molded article obtained by the production method described in any one of the items [7] to [9]

[11] A maleimide resin composition comprising the maleimide resin molded article described in any one of the items [1] to [6] and [10]

[12] The maleimide resin composition according to [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 item [11] or [12]

.

(Effects of the Invention)

Since the maleimide resin molded article of the present invention is formed into a film or a flake form, it is possible to provide a maleimide resin molded article which can suppress the organic solvent content and is excellent in workability, productivity, and environmental exposures. In addition, since the amount of the organic solvent can be suppressed, generation of voids and cracks during molding can be prevented.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the molecular weight distribution of the maleimide resin solution (V1) obtained at the completion of the polymerization reaction obtained from Synthesis Example 2. FIG.
2 is a diagram showing the molecular weight distribution of the maleimide resin molded article (M1) obtained from Example 1. Fig.
3 is a diagram showing the molecular weight distribution of the maleimide resin (B1) after solvent distillation removal in the mass synthesis obtained from Comparative Example 1. Fig.
4 is a diagram showing the quantitative determination of acetic acid in the maleimide resin (C1) of Comparative Example 4. Fig.

Hereinafter, the present invention will be described in detail.

The maleimide resin molded article of the present invention is characterized by containing a maleimide resin and an organic solvent and being formed into a film or a flake.

It is possible to supply the resin composition to a film or a flaky molded body in comparison with the maleimide resin which has been conventionally supplied in the form of a crystalline phase or a powder phase so that problems such as dust do not occur in terms of workability and it is very easy to handle. That is, the maleimide resin molded article of the present invention can easily prepare the maleimide resin composition.

The term " resin molded product " refers to a product obtained by applying a resin solution on the surface of a support, removing the solvent under superheated drying conditions, and peeling off the support while maintaining its shape. For example, And the like.

Here, the film phase means a sheet having an average thickness of 10 mu m to 3 mm in thickness. The flake phase refers to a state in which a molded body in a film is broken. The shape of the flakes is not particularly limited as long as the flakes do not scatter like a powder during handling, but the average of the long-diameter portions is preferably 0.1 cm to 5 cm, more preferably 0.1 to 3 cm Cm.

The average thickness can be obtained by overlapping a plurality of sheets or films, measuring arbitrary ten points with nog- ness, and dividing the obtained thickness by the number of overlapped sheets.

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

The maleimide resin molded article of the present invention is obtained by applying a solution of a maleimide resin dissolved in an organic solvent (hereinafter also referred to as a " maleimide resin solution " or " resin solution ") onto the surface of a support to form a film or a sheet , Removing the solvent under a heating condition (under a reduced pressure condition if necessary), and peeling the film from the support. That is, the method for producing a maleimide resin molded article of the present invention is carried out by a step of applying a resin solution onto the surface of a support, a step of heating and drying, and a step of peeling from the support.

(Maleimide resin)

As the maleimide resin which can be used in the present invention, known resins can be used, but novolak type maleimide resins having repeating units having an average number of functional groups of 2 to 20 are preferable from the viewpoints of viscosity and softening point.

The maleimide resin that can be used in the present invention has, for example, a structure represented by the following formula (1).

(Wherein R represents a plurality of R's present independently and 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 < / = 5).

Or a mixture of maleimide resins, but 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 known method as a method for synthesizing a maleimide resin. As a concrete manufacturing method, for example, a method similar to that disclosed in JP-A-2009-001783 is preferably used.

(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. In addition to the polymer solution synthesized by a known solution polymerization method or various control polymerization methods, a solid phase polymer may be partially precipitated during polymerization, Or a polymer precipitated by adding a precipitant to the solution after the polymerization is completed.

The organic solvent that can be used is not particularly limited, and for example, at least one organic solvent selected from aromatic hydrocarbons, ketones, esters, and ethers having 3 to 10 carbon atoms is preferable. It is also preferable that the reaction solution after polymerization is subjected to treatment such as washing with water.

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

As the maleimide resin, those having a melting point and a softening point can be used. Particularly, when it has a melting point, it is preferably 200 DEG C or lower, and when it has a softening point, it is preferably 50 DEG C to 150 DEG C.

The viscosity of the maleimide resin solution (cone plate method, 150 캜 melt viscosity) 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 desirable. When the melt viscosity at 150 캜 in the cone plate method is 10000 Pa · s or less, the coating workability is not lowered, which is preferable.

(A step of applying on the surface of the support)

Next, the maleimide resin solution obtained is applied to the surface of the support and molded into a film or a sheet.

The support on which the maleimide resin solution is applied is not particularly limited as long as the surface is smooth. Preferably, the support is a PET film, an imide film, or the like which is not subjected to the release treatment.

It is preferable that the film thickness and the area when applied to the surface of the support are each 10 탆 to 3 탆 in dry film thickness and 100 cm 2 or less in area per 100 cm 2 of the surface of the support.

The WET film thickness of the film at the time of coating is preferably 10 탆 to 5 mm, more preferably 10 탆 to 4.5 탆, and particularly preferably 200 탆 to 4.3 mm. If the amount exceeds the above range, the residual solvent reducing effect may not be sufficiently obtained, and when it is lowered, the productivity of the maleimide resin molded article may be lowered.

(A step of heat drying and a step of peeling off from the surface of the support)

Subsequently, the maleimide resin solution is coated on the surface of the support, and then the solvent is removed under heating and drying conditions (under reduced pressure, if necessary), and the dried film formed into a film or sheet from the surface of the support is peeled off Withdraw.

The drying temperature is preferably 80 to 250 占 폚, preferably 80 to 200 占 폚, particularly preferably 100 to 200 占 폚. When the drying temperature exceeds 250 DEG C, deterioration of the resin tends to proceed, and therefore, it is set according to the required processing characteristics. If the temperature is lower than 80 ° C, it is difficult to remove the solvent and the residual amount of the solvent increases, so that voids, cracks, stickiness, and film shape can not be maintained during the molding.

The film thickness of the maleimide resin molded article on the drawn film peeled off from the surface of the support is not particularly limited, but is preferably 10 m to 3 mm, and more preferably 30 m to 1 mm. If the film thickness exceeds 3 mm, the effect of reducing the residual solvent amount can not be sufficiently obtained.

The obtained film-shaped maleimide resin molded article can be used as a flaky maleimide resin molded article by pulverization.

The maleimide resin molded article obtained by the above process has a residual agent of 30,000 ppm or less. Preferably 5000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1000 ppm or less, particularly preferably 600 ppm or less. The lower limit of the measurement limit is 5 ppm.

The obtained maleimide resin molded article is preferably soluble in a solvent. When it is completely dissolved, it means that the maleimide resin is not undergoing the high molecular weight reaction.

The maleimide resin molded article thus obtained is excellent in workability and productivity as compared with the maleimide resin supplied in the conventional crystalline phase or powder form, so that the maleimide resin composition can be easily prepared.

Next, the maleimide resin composition of the present invention will be described.

The maleimide resin composition of the present invention may contain a compound capable of undergoing a crosslinking reaction with the maleimide resin molded article. The crosslinkable compound causes a crosslinking reaction with the maleimide resin molded article 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 acryl group, a methacrylic group, a vinyl group and a conjugated diene group. For example, when heat resistance is required, it is preferable to blend an amine compound and a cyanate ester compound when dielectric properties are required. Since the maleimide resin can be self-polymerized, it can be used alone.

In the maleimide resin composition of the present invention, a catalyst for curing (curing accelerator) may be incorporated if necessary. Such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl- Imidazoles such as triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) -7 Amines such as undecene, tris (dimethylaminomethyl) phenol and benzyldimethylamine, phosphines such as triphenylphosphine, tributylphosphine and trioctylphosphine, tin octylate, zinc octylate, dibutyltin di Maleic acid, maleate, zinc naphthenate, cobalt naphthenate and tin oleate; metal chlorides such as zinc chloride, aluminum chloride and tin chloride; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; Azo compounds such as acetonitrile, butyronitrile and azobisdimethylvaleronitrile, mines such as hydrochloric acid, sulfuric acid and phosphoric acid, Lewis acids such as boron trifluoride, There may be mentioned the salts of an acid, such as sodium or lithium chloride. The blending amount of the catalyst for curing is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the maleimide resin molded article of the present invention.

An organic solvent may be added to the maleimide resin composition of the present invention to form a varnish-like composition (hereinafter referred to simply as 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, dimethyl formamide, dimethylacetamide or N-methylpyrrolidone, A prepreg obtained by impregnating a substrate such as carbon fiber, glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like by heating and drying is used as a varnish to obtain a maleimide resin composition By weight.

The solvent at this time usually accounts for from 10 to 70% by weight, preferably from 15 to 70% by weight, in the mixture of the maleimide resin composition of the present invention and the above-mentioned solvent. Further, in the case of a liquid composition, a cured product of a maleimide resin composition containing a carbon fiber can be obtained, for example, by the RTM method.

The maleimide resin composition of the present invention can also be used as a modifier of a film-like composition. More specifically, it can be used for improving the flexibility in the B-stage. The film-like resin composition is obtained as a sheet-like adhesive by applying the maleimide resin composition of the present invention to a release film as the maleimide resin composition varnish, removing the solvent under heating, and then carrying out B staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The maleimide resin composition of the present invention is heated and melted to have a low viscosity to impregnate reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber and alumina fiber to obtain a prepreg.

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

The method of impregnating the maleimide resin composition of the present invention with these reinforcing fibers is not particularly limited. However, since the method which does not use a solvent is preferable, the maleimide resin composition of the present invention is heated to 60 to 110 캜, A hot melt method is preferred.

The proportion of the maleimide resin composition in the obtained prepreg (impregnated with the maleimide resin composition in the reinforcing fiber) is usually 20% by weight or more and 80% by weight or less, preferably 25% by weight or more, 65% by weight or less, and more preferably 30% by weight or more and 50% or less. If the ratio of the maleimide resin composition is higher than the above range, the reinforcing fiber ratio is relatively decreased, and sufficient reinforcing effect can not be obtained. Conversely, if the maleimide resin composition is too small, the moldability may be impaired.

This prepreg can be cured by a known method to be a final molded product. For example, a prepreg can be laminated, pressurized in an autoclave at 2 to 10 kgf / cm < 2 >, and heated and cured at 150 DEG C to 200 DEG C for 30 minutes to 3 hours to form a molded article. In order to further improve heat resistance, Treated at a temperature ranging from 180 DEG C to 280 DEG C for 1 hour to 12 hours while gradually warming the temperature.

After the prepreg is cut into a desired shape, if necessary, laminated with a copper foil or the like, and a maleic resin composition for laminate is thermally cured while pressure is applied to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method or the like .

Further, a multilayer circuit board can be obtained by forming a circuit on a laminate formed by laminating a copper foil on the surface thereof, and then repeating the above operation by laminating a prepreg, a copper foil or the like thereon.

The cured product of the prepreg of the present invention is a lightweight, high-strength, high heat-resistant member such as a robot hand for transporting a liquid crystal glass substrate, a disk for transporting a silicon wafer, .

Specific examples of the use of the maleimide resin composition of the present invention include adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like), insulating materials for electronic materials (including printed boards, A sealant, a cyanate resin composition for a substrate), an acrylate ester resin as a curing agent for a resist, and an additive to other resins. Particularly, in the FRP application, there has been a significant progress in the non-solvent application due to consideration of the environment and the problem of defects due to voids. In addition, there is an environment in which the solvent can not enter the process during the process even in the use of semiconductor sealing due to problems such as voids during molding, defective molding, and lowering of withstand voltage.

(Example)

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following description, " part (s) " and "% " In Examples, the softening point and the melting point were measured by the following methods.

· Softening point: Measured according to JISK-7234

Melt viscosity: Viscosity at 150 ° C measured by cone plate method

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

The temperature-rising program was held at 70 ° C for 5 minutes, heated to 140 ° C at a rate of 10 ° C / min, then increased to 220 ° C at a rate of 20 ° C / min and held at 220 ° C for 5 minutes did.

Gel-permeation chromatography (LC-20AD manufactured by GPC Shimazu Seisakusho Co., Ltd.) was used for data acquisition of the molecular weight. The column was subjected to measurement with an RI detector under conditions of KF-603, KF-602.5, KF-602 and KF-601 at a column temperature of 40 캜 and a mobile phase of THF at a flow rate of 0.5 ml / 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 azimetric distillation trap and a stirrer, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature for 1 hour. After completion of the dropwise addition, water and toluene which had been heated by azeotropy were cooled and separated, and then dehydration was carried out by returning only toluene which is an organic layer back into the system. Then, 251 parts of 4,4'-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C, and the reaction was further continued at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, the system was maintained at 190 to 200 캜, and the reaction was carried out at this temperature for 15 hours. Then, while cooling, 500 parts of a 30% sodium hydroxide aqueous solution was added dropwise slowly so that the system did not vigorously reflux. Toluene distilled off at 80 占 폚 or lower was returned to the system and allowed to stand at 70 占 폚 to 80 占 폚. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing liquid became neutral. Subsequently, excess 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 aromatic amine resin (A1) had a softening point of 59 ° C and a melt viscosity of 0.05 Pa · s.

(Synthesis Example 2)

88 parts of maleic anhydride and 300 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer. After cooling and separating the water and toluene which had been heated and heated, only the organic toluene And dehydration was performed. Next, a resin solution obtained by dissolving 116 parts of the aromatic amine resin (A1) in 116 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the temperature of the system at 80 to 85 캜. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, and 2 parts of p-toluenesulfonic acid was added. After condensation water and toluene were cooled and separated by azeotroping under refluxing conditions, only toluene as the organic layer was returned to the system and dehydration The reaction was carried out for 10 hours. After completion of the reaction, 120 parts of toluene was added, and p-toluenesulfonic acid and excess maleic anhydride were removed by repeatedly washing with water, and water was removed from the system by heating by azeotropy. Subsequently, the reaction solution was concentrated to obtain a maleimide resin solution (V1) containing 70% of 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 azimetric distillation trap and a stirrer, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature for 1 hour. After completion of the dropwise addition, water and toluene which had been heated by azeotropy were cooled and separated, and then dehydration was carried out by returning only toluene which is an organic layer back into the system. Subsequently, 175 parts of 4,4'-bis (chloromethyl) benzene was added over 1 hour while maintaining the temperature at 60 to 70 ° C, and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, the system was maintained at 190 to 200 캜, and the reaction was carried out at this temperature for 15 hours. Then, while cooling, 500 parts of a 30% sodium hydroxide aqueous solution was slowly added dropwise so that the system did not reflux vigorously, and the toluene distilled off at 80 ° C or lower was returned to the system and allowed to stand at 70 ° C to 80 ° C. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing liquid became neutral. Subsequently, 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 a semi-solid resin.

(Synthesis Example 4)

88 parts of maleic anhydride and 300 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer. After cooling and separating the water and toluene which had been heated and heated, only the organic toluene And dehydration was performed. Next, a resin solution obtained by dissolving 91.7 parts of the aromatic amine resin (A2) in 91.7 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the temperature of the system at 80 to 85 캜. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, and 2 parts of p-toluenesulfonic acid was added. After condensation water and toluene were cooled and separated by azeotroping under refluxing conditions, only toluene as the organic layer was returned to the system and dehydration The reaction was carried out for 10 hours. After completion of the reaction, 120 parts of toluene was added, and p-toluenesulfonic acid and excess maleic anhydride were removed by repeatedly washing with water, and water was removed from the system by heating by azeotropy. Subsequently, 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 in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness: 200 占 퐉) The solvent was removed by drying the resin film at 180 DEG C for 15 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 125 탆, and was peeled and pulverized to obtain a maleimide resin molded article M1 of the present invention having a flake shape.

The residual solvent of the maleimide resin molded article (M1) thus obtained was 0.236% (2360 ppm). The molecular weight distribution of the obtained maleimide resin molded article (M1) was measured by GPC, and the results shown in Fig. 2 were obtained. As a result of comparison with the molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2, the change of the molecular weight distribution by this step was not shown (measurement by GPC).

(Example 2) (Support: imide film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness: 200 占 퐉) The solvent was removed by drying the resin film at 200 DEG C for 15 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 125 탆 and was peeled and pulverized to obtain a maleimide resin molded article M2 of the present invention having a flake shape.

The residual solvent of the obtained maleimide resin molded article (M2) was 0.293% (2930 ppm). In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 3) (Support: imide film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness: 200 占 퐉) The solvent was removed by drying the resin film at 200 DEG C for 10 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 125 탆 and was peeled and pulverized to obtain a maleimide resin molded article M3 of the present invention having a flake shape.

The residual solvent of the obtained maleimide resin molded article (M3) was 0.398% (3980 ppm). In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 4) (Support: imide film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness: 200 占 퐉) The solvent was removed by drying the resin film at 200 DEG C for 5 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 125 mu m, and was peeled and pulverized to obtain a maleimide resin molded article (M4) of the present invention having a flake shape.

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

In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 5) (Support: SUS plate)

The solvent was removed by applying the maleimide resin solution (V1) obtained in Synthesis Example 2 to the SUS plate using an applicator (WET film thickness: 200 mu m) and drying the coated resin film at 180 DEG C for 15 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 113 mu m, and was peeled and pulverized to obtain a maleimide resin molded article M5 of the present invention having a flake shape.

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

In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 6) (Support: SUS plate)

The solvent was removed by applying the maleimide resin solution (V2) obtained in Synthesis Example 4 to the SUS plate by using an applicator (WET film thickness: 200 mu m) and drying the applied resin film at 180 DEG C for 15 minutes.

The obtained maleimide resin molded article was in the form of a film having a thickness of 113 mu m, and was peeled and ground to obtain a maleimide resin molded article (M6) of the present invention having a flake shape.

The residual solvent of the obtained maleimide resin molded article (M6) was 0.3%? (3000 ppm?). In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 7) (Support: mirror copper foil)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to the mirror surface of an electrolytic copper foil (18 占 electrolytic copper foil CF-T9FZ-HTE manufactured by Fukuda Kinko Co., Ltd.) (WET film thickness 200 占 퐉 ), And the applied resin film was dried at 180 DEG C for 15 minutes to remove the solvent.

The obtained maleimide resin molded article was in the form of a film having a thickness of 152 mu m, and was peeled and pulverized to obtain a maleimide resin molded article (M7) of the present invention having a flake shape.

The residual solvent of the obtained maleimide resin molded article (M6) was 0.0728% (728 ppm).

In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Example 8) (Support: PET film)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a PET film (Lamier 38-S10 manufactured by Panakusha Co., Ltd.) which had not been subjected to release treatment using an applicator (WET film thickness: 200 m) The applied resin film was dried at 160 DEG C for 1 hour to remove the solvent.

The obtained maleimide resin molded article was in the form of a film having a thickness of 146 mu m, and was peeled and pulverized to obtain a maleimide resin molded article (M7) of the present invention having a flake shape.

The residual solvent of the obtained maleimide resin molded article (M8) was 0.0571% (571 ppm). In addition, no change in the molecular weight distribution by this step was observed (measurement by GPC).

(Comparative Example 1)

300 mL of the maleimide resin solution (V1) obtained in Synthesis Example 2 was distilled off under heating and depressurization at 160 占 폚 using a rotary evaporator to obtain the maleimide resin (B1) as a resin block. The molecular weight distribution of the obtained maleimide resin (B1) was measured by GPC, and the results shown in Fig. 3 were obtained. As a result of comparison with the molecular weight distribution (FIG. 1) of the maleimide resin solution (V1) obtained in Synthesis Example 2, as measured by GPC, it was found that the maleimide resin (B1) Confirmed. The residual solvent of the obtained maleimide resin (B1) was 0.1% (1000 ppm) or less.

(Comparative Example 2)

1.0 L of the maleimide resin solution (V1) obtained in Synthesis Example 2 was subjected to distillation and removal of the solvent at 180 占 폚 under heating and depressurization using a rotary evaporator, and it was confirmed that the solution was gelled. The resulting maleimide resin (B2) lost its fluidity.

≪ Comparison of the drying temperature in the method of producing the maleimide resin molded article &

(Comparative Example 3)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness 200 탆), and the applied resin film was heated and dried by hot air at 50 캜 for 1 hour to remove the solvent.

The resulting maleimide resin molded article had stickiness, could not maintain the shape of the film, and could not be peeled and pulverized.

(Comparative Example 4)

The maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to a commercially available imide film (Capton (registered trademark) 100H manufactured by Toray DuPont) using an applicator (WET film thickness 200 탆), and the applied resin film was heated and dried for 1 hour by hot air at 250 캜 to remove the solvent.

The obtained maleimide resin molded article was in the form of a film and could be peeled and flaked, but the molecular weight became higher and 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'-bismaleimide diphenylmethane (hereinafter referred to as C1 product manufactured by TCI Corporation) for comparison were prepared and the odor was compared.

The amount of acetic acid was determined using gas chromatography GC-2010Plus manufactured by Shimadzu Seisakusho Co., Ltd. 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 temperature increasing program, a program was used in which the temperature was maintained at 60 캜 for 7 minutes, the temperature was raised to 220 캜 at a heating rate of 20 캜 / min, and the temperature was maintained at 220 캜 for 5 minutes.

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

Further, as a result of measurement by gas chromatography, acetic acid was detected in Comparative Example 5 (see Fig. 4, retention time 11.298 min). As a result of acid value measurement, it was confirmed that the acid value was 10 mgKOH / g, which corresponds to 1% of acetic acid.

<Comparison of Solubility of Shape and Solvent>

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

The maleimide resin molded articles (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) A dissolution test was conducted.

When the resin concentration was adjusted to 50%, the maleimide resin molded articles M1 and M5 to M8 were completely dissolved, but the maleimide resin (C1) and the maleimide resin (B2) were not completely dissolved.

From the above, it can be seen that the maleimide resin molded articles (M1, M5 to M8) did not undergo a high molecular weight reaction because they were completely dissolved in Examples 10 to 14. On the other hand, it was found that the maleimide resins (C1, B2) underwent a high molecular weight reaction because they could not be completely dissolved in Comparative Examples 6 and 7.

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

(Example 15)

10 parts of the maleimide resin molded product (M1) obtained in Example 1 and 0.21 parts of 2-ethyl-4-methylimidazole (2E4MZ manufactured by Shikoku Kasei K.K.) as a curing accelerator were mixed and homogeneously mixed . The maleimide resin composition of the present invention was obtained by kneading. This maleimide resin composition was applied to a commercially available imide film (Capton (registered trademark) 100H by Toray DuPont) using an applicator (WET film thickness: 200 占 퐉), and the applied resin film was cured at 160 占 폚 The cured product was obtained by curing while removing the solvent at 2 h + 180 캜 x 6 h. Table 1 shows the results of evaluating physical properties of the obtained cured product.

(Comparative Example 8)

, 61 parts of EPPN-502H (epoxy equivalent 169 g / eq, softening point 67.5 占 폚 EP1, product of Nippon Kayaku), 38 parts of phenol novolac (H-1 manufactured by Meiwa Kasei Corporation, hydroxyl equivalent 106 g / eq), triphenylphosphine Ltd.) were mixed and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was tableted and then molded into a resin composition by transfer molding to obtain a cured product at a curing condition of 160 캜 x 2 h + 180 캜 x 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 (epoxy equivalent weight 194 g / eq, softening point 54.8 占 폚 EP2, product of Nippon Kayaku), 34 parts of phenol novolac (H-1 manufactured by Meiwa Kasei Co., Kagaku reagent) were mixed and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was tableted and then molded into a resin composition by transfer molding to obtain a cured product at a curing condition of 160 캜 x 2 h + 180 캜 x 6 h. The following physical properties of the obtained cured product were evaluated. The results are shown in Table 1.

The following measurements were made on the obtained cured product.

DMA

Measurement items: storage modulus at 30 ° C, 200 ° C and 250 ° C,

        : Glass transition temperature (tan?

Measuring method: Dynamic viscoelasticity measuring instrument TA-instruments product, Q-800

Measuring temperature range: 30 ℃ ~ 350 ℃

On rate: 2 ° C / min

Specimen size: 5 mm × 50 mm cut out (thickness about 800 μm) was used.

It can be seen from Table 1 that the cured product of the maleimide resin composition of the present invention can be molded under the same curing conditions as those of the epoxy resin and that the obtained cured product has a small change in the modulus of elasticity at high temperature Able to know.

Although the present invention has been described in detail with reference to specific embodiments thereof, it is 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 Japanese patent application (Japanese Patent Application No. 2016-169417) filed on August 31, 2016, which is incorporated by reference in its entirety. In addition, all references cited herein are taken as a whole.

(Industrial availability)

The maleimide resin molded article of the present invention can be easily prepared as a maleimide resin composition and can be used for 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) Heat-resistant sealing materials for SiC power devices, and the like.

Claims (13)

A maleimide resin molded article comprising a maleimide resin and an organic solvent and being in the form of a film or a flake. The method according to claim 1,
Wherein the content of the organic solvent is 30000 ppm or less. 3. The method according to claim 1 or 2,
Wherein the organic solvent is at least one selected from aromatic hydrocarbons, ketones, esters and ethers having 3 to 10 carbon atoms. 4. The method according to any one of claims 1 to 3,
A maleimide resin molded article having a thickness of 10 mu m to 3 mm. 5. The method according to any one of claims 1 to 4,
Wherein the maleimide resin is a novolak type maleimide resin having a repeating unit having an average number of functional groups of 2 to 20. 6. The method according to any one of claims 1 to 5,
Wherein the maleimide resin has a softening point of 50 to 150 占 폚. A process for producing a molded body of a maleimide compound in which a solution of a maleimide resin dissolved in an organic solvent is applied on the surface of a support and dried. 8. The method of claim 7,
Wherein the organic solvent is at least one selected from aromatic hydrocarbons, ketones, esters, and ethers having 3 to 10 carbon atoms. 9. The method according to claim 7 or 8,
Wherein the drying temperature is 80 to 200 占 폚. A maleimide resin molded article obtained by the production method according to any one of claims 7 to 9. A maleimide resin composition comprising the maleimide resin molded article according to any one of claims 1 to 6 and 10. 12. The method of claim 11,
A maleimide resin, a compound capable of cross-linking with the maleimide resin, and a curing accelerator. 12. A cured product of the maleimide resin composition according to claim 11 or 12.

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