CN109641984A - Maleimide resin formed body, the manufacturing method of maleimide resin formed body, maleimide resin constituent and its solidfied material - Google Patents
Maleimide resin formed body, the manufacturing method of maleimide resin formed body, maleimide resin constituent and its solidfied material Download PDFInfo
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- CN109641984A CN109641984A CN201780050109.8A CN201780050109A CN109641984A CN 109641984 A CN109641984 A CN 109641984A CN 201780050109 A CN201780050109 A CN 201780050109A CN 109641984 A CN109641984 A CN 109641984A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/04—Homopolymers or copolymers of nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
One kind is provided in high-reliable semiconductor sealing material purposes, electrically, electronic component insulating materials purposes, it and take laminated plates (the glass fiber-reinforced composite material of printed wiring) or CFRP (carbon fiber-reinforced composite material) as the various composite material purposes of representative, various solid purposes, various coating applications, useful workability in construction component etc., the maleimide resin formed body that productivity is excellent and environmental exposure is few, maleimide resin constituent and its solidfied material.Maleimide resin formed body contains maleimide resin and organic solvent, and is membranaceous or fragment shape.
Description
Technical field
The present invention relates to the manufactures of a kind of maleimide resin formed body, maleimide resin formed body
Method, maleimide resin constituent and its solidfied material.Specifically, it is related to a kind of close for high-reliable semiconductor
Seal material purposes, electrical, electronic component insulating materials purposes and with laminated plates (the glass fiber-reinforced composite material of printed wiring) or
CFRP (carbon fiber-reinforced composite material) be the various composite material purposes of representative, various solid purposes, various coating applications,
Useful workability, productivity are excellent in construction component etc. and environmental exposure is few maleimide resin formed body,
Manufacturing method, maleimide resin constituent and its solidfied material of maleimide resin formed body.
Background technique
Maleimide resin is and to have same with epoxy resin with the heat resistance for being more than epoxy resin
Formability, and then the compound of the property also with low linear expansion coefficient, high Tg.Poly- maleimide compounds can pass through
It is individually crosslinked, or is reacted with various maleimide compounds or crosslinking agent, and heat resistance, fire retardant is provided
The excellent material of property, thus it is used for the various uses such as sealing material, substrate material, insulating materials.Especially being used for must be simultaneous
The heat resistance of Gu Jigao and high heat resistance substrate material, flexible substrate material, the high heat resistance dielectric materials, high heat resistance of formability
CFRP material (carbon fibre composite), suitable for vehicle-mounted SiC power device high heat resistance sealant use.
In the past, maleimide resin is due to self-reactive, therefore with crystal powders such as recrystallizations in its acquisition
The form of body obtains, or in the form of the toner shape formed by the reprecipitation commercially available more (referring to patent document 1), because making
Used time powder drifts, and not there is only workability, productive problem, there is also the pollutions to environment (dirt and to be sucked into people
Body) the problems such as.In turn, sucking solvent etc. when being present in crystallization, precipitating, the problem of can not completely removing, and when sucking manufacture
Used acetic acid class, the foul smell of remaining acetic acid in made product, the problem of becoming the safety for being related to operator.
Under such background, the excellent maleimide formed body of workability, productivity, environmental safety is expected.For example, patent
Document 2 discloses the melting acquisition methods of the maleimide resin solution using evaporator.
[prior art document]
[patent document]
Patent document 1: Japanese Patent Publication 6-86425 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2009-001783 bulletin
Summary of the invention
[the problem of invention is to be solved]
However, in patent document 2, will not be varied widely under a small amount of scale, but in the situation for increasing synthetic quantity
When, the distillation removal of solvent needs for a long time, therefore has the problem of this period carrying out auto polymerization.Therefore, in actual production
Manufacture in, the dangerous of polymerization or gelation, there are problems for formability, the viewpoint of steady production, such as glutinous
Degree increases and rising and characteristic difference etc. in each production with molecular weight.In addition, if being reduced molten to inhibit the polymerization
Agent recovered temperature, then especially in the situation of the maleimide resin of the softening point with 50 DEG C or more, it is difficult to remove
Solvent, the residual of solvent increase (the especially more than residual of the solvent of 30000ppm), thus have forming when generate gap or
The problem of slight crack, and there are also problems to safeties such as the exposures of operator.In turn, in these maleimide resins
In synthesis, there is a situation using the substance influential on human body such as acetic acid or toluene, dimethylbenzene, thus the residual of solvent especially at
For problem.
Therefore, the purpose of the present invention is to provide a kind of workability, productivity are excellent, and the maleic two that environmental exposure is few
Imide resin formed body.
[means solved the problems, such as]
The present inventor makes great efforts research to solve the above-mentioned problems, as a result, it has been found that by not with crystalloid or powder before
Shape and in the form of membranaceous or fragment shape formed body obtain, workability, productivity etc. are excellent, and environmental exposure tails off, thus
Complete the present invention.
That is, the present invention relates to:
[1] a kind of maleimide resin formed body, containing maleimide resin and organic solvent, and
For membranaceous or fragment shape；
[2] the maleimide resin formed body as described in preceding paragraph [1], wherein the content of above-mentioned organic solvent is
30000ppm or less；
[3] the maleimide resin formed body as described in preceding paragraph [1] or [2], wherein above-mentioned organic solvent is choosing
From at least one of the aromatic hydrocarbon of carbon number 3~10, ketone, esters and ethers；
[4] the maleimide resin formed body as described in any one of preceding paragraph [1] to [3], with a thickness of 10 μm
~3mm；
[5] the maleimide resin formed body as described in any one of preceding paragraph [1] to [4], wherein above-mentioned suitable fourth
Alkene imidodicarbonic diamide resin is the phenolic varnish type maleimide tree for the repetitive unit for being 2~20 with average function radix
Rouge；
[6] the maleimide resin formed body as described in any one of preceding paragraph [1] to [5], wherein above-mentioned suitable fourth
The softening point of alkene imidodicarbonic diamide resin is 50~150 DEG C；
[7] a kind of manufacturing method of maleimide compounds formed body, will make maleimide resin
Solution coating made of organic solvent is dissolved on the surface of support and being dried；
[8] manufacturing method of the maleimide compounds formed body as described in preceding paragraph [7], wherein above-mentioned organic
Solvent is at least one of aromatic hydrocarbon selected from carbon number 3~10, ketone, esters, ethers；
[9] manufacturing method of the maleimide compounds formed body as described in preceding paragraph [7] or [8], wherein dry
Temperature is 80~200 DEG C；
[10] a kind of maleimide resin formed body, to pass through system described in any one of preceding paragraph [7] to [9]
It makes method and obtains；
[11] a kind of maleimide resin constituent, it includes any one of preceding paragraph [1] to [6] and preceding paragraphes [10]
The maleimide resin formed body；
[12] the maleimide resin constituent as described in preceding paragraph [11], and then include selected from can be with maleic
The compound and at least any one in curing accelerator that imidodicarbonic diamide resin carries out cross-linking reaction；
[13] a kind of solidfied material is the solidification of maleimide resin constituent described in preceding paragraph [11] or [12]
Object.
[The effect of invention]
Maleimide resin formed body of the invention can inhibit organic solvent with membranaceous or broken sheet-like formed
Content, it is possible to provide the maleimide resin formed body that workability, productivity are excellent and environmental exposure is few.In turn, due to
It can inhibit the amount of organic solvent, therefore can prevent from generating gap or slight crack in forming.
Detailed description of the invention
Fig. 1 is to indicate by the maleimide resin solution (V1) at the end of the polymerization reaction obtained of synthesis example 2
Molecular weight distribution figure.
Fig. 2 is the molecular weight distribution indicated by the maleimide resin formed body (M1) obtained of embodiment 1
Figure.
Fig. 3 be indicate by comparative example 1 it is obtained it is a large amount of synthesize when solvent distillation removal after maleimide tree
The figure of the molecular weight distribution of rouge (B1).
Fig. 4 is the quantitative figure for indicating the acetic acid of maleimide resin (C1) of comparative example 4.
Specific embodiment
Hereinafter, the present invention is described in detail.
Maleimide resin formed body of the invention is characterized in that: containing maleimide resin and being had
Solvent, and with membranaceous or broken sheet-like formed.
With in the past usually with crystalloid or the maleimide resin of powdered supply compared with, can membranaceous or fragment
The formed body of shape supplies, therefore the problems such as will not generate in terms of workability dust, extremely easy to operate.That is, of the invention is suitable
Butylmaleimide resin molded body can easily prepare maleimide resin constituent.
So-called resin molded body, refers to after resin solution is coated on the surface of support, in the case where overheating drying condition
Solvent is removed, and maintains shape invariance and the removing of self-supporting body and winner, such as membranaceous, sheet, threadiness, plate can be enumerated
Shape, rodlike etc..
Herein, so-called membranaceous, refer to that average thickness is the form of the piece of the thickness of 10 μm~3mm.So-called fragment shape, refers to
By the membranaceous broken state of formed body.In addition, so-called fragment shape, as long as that will not fly as powdered when operating operation
The size of scattered degree, then be not particularly limited, specifically, that major diameter part is averagely preferably 0.1cm~5cm, more preferably
For 0.1~3cm.
In addition, average thickness can measure at any 10 points using vernier caliper, and will be obtained by being overlapped muti-piece piece or film
The thickness obtained is found out divided by overlapping block number.
Secondly, being said for convenience of explanation to the manufacturing method of maleimide resin formed body of the invention
It is bright.
Maleimide resin formed body of the invention can obtain in the following way, that is, will make maleoyl-
Imide resin is dissolved in solution made of organic solvent, and (hereinafter also referred to as " maleimide resin solution " or " resin is molten
Liquid ") it is coated on the surface of support, and after being configured to membranaceous or sheet, in a heated condition (if necessary in reduced pressure
Under) remove solvent, and self-supporting body is by film stripping.That is, the manufacturer of maleimide resin formed body of the invention
Method be by step that resin solution is coated on the surface of support, be thermally dried the step of and the stripping of self-supporting body
From the step of and carry out.
(maleimide resin)
It is usable well known as maleimide resin for use in the present invention, but with regard to the sight of viscosity, softening point
For point, it is however preferred to have the maleimide tree of the phenolic varnish type for the repetitive unit that average function radix is 2~20
Rouge.
As maleimide resin for use in the present invention, such as with structure represented by following formula (1).
[changing 1]
(in formula, existing multiple R separately exist, and indicate the alkyl or phenyl of hydrogen atom, carbon number 1~10.
Represented by X is by following structural formula (a)~(e).N is average value, and indicates 1 n≤5 <).
[changing 2]
Alternatively, the mixture of maleimide resin can also be enumerated, but the present invention is not limited to these.
The preparation method of maleimide resin represented by above-mentioned formula (1) is not particularly limited, using as along fourth
The synthetic method of alkene imidodicarbonic diamide resin and well known any means manufacture.It is used as specific manufacturing method, such as preferably
Such as the method for Japanese Unexamined Patent Publication 2009-001783 bulletin.
(maleimide resin solution)
In the present invention, so-called maleimide resin solution, it is intended that dissolve above-mentioned maleimide resin
Made of organic solvent.
Made of if maleimide resin is is dissolved in organic solvent by maleimide resin solution,
Then it is not particularly limited, in addition to through polymer solution synthesized by well known solution polymerization process or various control polymerizations,
It can be precipitated made of a part, can also make in polymerization to add precipitating reagent into the solution of polymerization end for solid shaped polymer
Made of polymer precipitating.
As workable organic solvent, be not particularly limited, for example, be preferably selected from carbon number 3~10 aromatic hydrocarbon,
At least one of ketone, esters, ethers organic solvent.Furthermore it is preferred that carrying out the processing such as washing to the reaction solution after polymerization.
The usage amount of organic solvent is usually 10~70 weights in the mixture of maleimide resin and the solvent
Measure %, preferably 15~70 weight %.
Maleimide resin can be used with fusing point, softening point.Especially in the situation with fusing point, preferably
For 200 DEG C hereinafter, in addition, in the situation with softening point, preferably 50~150 DEG C.
The viscosity (cone-plate method, 150 DEG C of melting viscosities) of maleimide resin solution be preferably 5.0mPas~
10000Pas, more preferably 10mPas~100Pas, especially preferably 10mPas~10Pas.If utilizing cone-plate
150 DEG C of melting viscosities of method are 10000Pas hereinafter, not having the case where coating operations reduce then, are therefore preferred.
(in the step of being coated on support surface)
Secondly, by maleimide resin solution coating obtained in the surface of support, and be configured to membranaceous
Or sheet.
It is not particularly limited as the support for maleimide resin solution coating as long as smooth surface,
It is preferred that metal, PET film, acid imide film that demoulding processing is not carried out etc. can be enumerated.
Preferably with when the surface of support is coated film thickness and area in the every 100cm in the surface of support2Point
It Cheng Wei not 10 μm~3mm of dry film thickness, area 100cm2Mode below carries out.
The WET film thickness of film when coating is preferably 10 μm~5mm, more preferably 10 μm~4.5mm, especially preferably 200 μ
M~4.3mm.If being more than above range, there is the situation for not obtaining sufficiently and reducing the effect of residual solvent, if being lower than the range,
The situation for then thering is the productivity of maleimide resin formed body to reduce.
(the step of sur-face peeling of the step of being thermally dried and self-supporting body)
Secondly, after the surface of support is coated with maleimide resin solution, (depending on needing under the conditions of heat drying
Will be at reduced pressure conditions) solvent is removed, the surface of self-supporting body will be shaped to membranaceous or sheet dry coating removing and obtain
It takes.
Drying temperature is preferably 80~250 DEG C, and more preferably 80 DEG C~200 DEG C, especially preferably 100 DEG C~200 DEG C.It closes
In drying temperature, if resin is easy to produce deterioration, therefore is set according to required processing characteristics more than 250 DEG C.This
Outside, it if not up to 80 DEG C, is difficult to remove solvent, the residual quantitative change of solvent is more, therefore while having a forming generates gap or slight crack, has
Glutinous soapy feeling, is unable to maintain that the shape of film, the situation that can not be removed and crush.
The sur-face peeling of self-supporting body and the film thickness of membranaceous maleimide resin formed body obtained has no spy
It does not limit, preferably 10 μm~3mm, more preferably 30 μm~1mm.If film thickness is more than 3mm, it is unable to fully obtain and reduces residual
The effect of quantity of solvent.
In addition, membranaceous maleimide resin formed body obtained can also be by crushing with the shape of fragment shape
The form of the maleimide resin formed body of shape uses.
The residual solvent of maleimide resin formed body obtained is 30000ppm or less through the above steps.
Preferably 5000ppm hereinafter, more preferably 3000ppm hereinafter, especially preferably 1000ppm hereinafter, especially preferably 600ppm
Below.In addition, as measurement detectable limit, lower limit value 5ppm.
In addition, maleimide resin formed body obtained preferably dissolves in solvent.Be completely dissolved mean it is suitable
Butylmaleimide resin does not carry out molecular weight reaction.
The maleimide resin formed body that obtains by this method and previous with crystalloid or powdered supply
Maleimide resin is compared, and workability, productivity are excellent, therefore can easily prepare maleimide resin group
At object.
Secondly, being illustrated to maleimide resin constituent of the invention.
Maleimide resin constituent of the invention may include can with maleimide resin formed body into
The compound of row cross-linking reaction.The compound that can be crosslinked is that crosslinking is generated with maleimide resin formed body instead
It answers, the curing agent as maleimide resin plays a role.As the compound that can be crosslinked, can enumerate with amine
Base, phenolic hydroxyl group, alcohol hydroxyl group, allyl, methacrylic, acrylic, methacrylic acid group, vinyl, is total to cyanic acid base
The compound etc. of yoke dialkylene.For example, it is desired to preferably blend amine compounds, when needing dielectric property, preferably when heat resistance
Blend cyanate esters.Due to maleimide resin can also auto polymerization, therefore also can be used alone.
In maleimide resin constituent of the invention, catalyst (the solidification promotion of solidification can be optionally blended
Agent).Such as it can enumerate: 2-methylimidazole, 2- ethyl imidazol(e), 2- phenylimidazole, 2-ethyl-4-methylimidazole, 2- undecyl
The imidazoles such as imidazoles, 1- cyano ethyl -2-ethyl-4-methylimidazole；Triethylamine, triethylenediamine, 2- (dimethylamino methyl) benzene
The Ammonias such as bicyclic (the 5,4,0) -7- hendecene of phenol, bis- a word used for translation of 1,8-, three (dimethylamino methyl) phenol, dimethylamino benzylidene ammonia；Triphenylphosphine,
The phosphines such as tributylphosphine, tri octyl phosphine；Stannous octoate, zinc octoate, two dibutyl tin maleates, zinc naphthenate, aphthenic acids
The organic metal salts such as cobalt, oleic acid tin；The metal chlorides such as zinc chloride, aluminium chloride, stannic chloride；It is dual-tert-butyl peroxide, double different
The organic peroxides such as phenylpropyl peroxide；The azo-compounds such as azodiisobutyronitrile, azobis dimethyl valeronitrile；Hydrochloric acid,
The inorganic acids such as sulfuric acid, phosphoric acid；Salts such as the lewis acids such as boron trifluoride, sodium carbonate or lithium chloride etc..Solidify the blending with catalyst
Amount is preferably 10 parts by weight or less, more preferably 5 relative to 100 parts by weight of maleimide resin formed body of the invention
Parts by weight range below.
Organic solvent can be added in maleimide resin constituent of the invention and the composition of varnish shape is made
Object (hreinafter referred to as varnish).Maleimide resin constituent of the invention is optionally set to be dissolved in toluene, diformazan
Benzene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethylformamide, dimethyl acetamide, N- methylpyrrole pyridine ketone etc. are molten
Agent and maleimide resin constituent varnish is made, so that it is impregnated in carbon fiber, glass fibre, carbon fiber, polyester fine
The substrates such as dimension, Fypro, alumina fibre, paper are simultaneously thermally dried and obtain prepreg, carry out heat to the prepreg
Pressing formation can be made into the solidfied material of maleimide resin constituent of the invention with this.
Solvent at this time usually accounts in the mixture of maleimide resin constituent and the solvent of the invention
10~70 weight %, 15~70 weight % are preferably accounted for.In addition, if liquid constituent, then it can also be directly for example in a manner of RTM
Obtain the solidfied material of the maleimide resin constituent containing carbon fiber.
In addition, maleimide resin constituent of the invention can also be used as to the modification agent of film shape constituent.Tool
For body, it can be used for improving the situation of the pliability in B- stage etc..About such film shape resin combination, by suitable fourth of the invention
Alkene imidodicarbonic diamide resin combination is made above-mentioned maleimide resin constituent varnish and is coated on stripping film, and in
Solvent is removed under heating, B-stage is then carried out, is obtained in the form of the solid of sheet by this.The sheet solid can
Interlayer insulating film as multilager base plate etc..
It can carry out low-viscosity by by maleimide resin constituent heating melting of the invention and contain it
The reinforcing fibers such as glass fibre, carbon fiber, polyester fiber, Fypro, alumina fibre are dipped in, and obtain prepreg.
Also, prepreg can also be obtained and making above-mentioned varnish be impregnated in reinforcing fiber and heat drying.
Maleimide resin constituent of the invention is set to be impregnated in the method for these reinforcing fibers also without special limit
System, the method for not using solvent preferably, therefore preferably following hot melt, that is, by maleimide tree of the invention
Fat composition is heated up to 60~110 DEG C, makes it with the state impregnation with mobility.
Maleimide resin constituent (contains maleimide resin constituent in prepreg obtained
Be dipped in reinforcing fiber and winner) in the form of shared ratio view reinforcing fiber and different, usually 20 weight % or more and 80
Weight % hereinafter, preferably 25 weight % or more and 65 weight % hereinafter, more preferably 50% or less 30 weight % or more and.If
The ratio of maleimide resin constituent is more than the range, then can not obtain because the ratio of reinforcing fiber is with respect to reduction
Sufficient reinforcing effect, conversely, if maleimide resin constituent is less than the range, the feelings for having formability impaired
Shape.
The prepreg can make its solidification that final formed products be made by well known method.For example, volume layer can will be presoaked,
2 are pressurised into autoclave to 10kgf/cm2, and carry out in 150 DEG C to 200 DEG C being heating and curing and making for 30 minutes to 3 hours
Make formed body, but in order to further increase heat resistance, one side can heat step by step one within the temperature range of 180 DEG C to 280 DEG C
Face carries out processing in 1 hour to 12 hours as rear curing process, and fiber reinforced composite material formed products are made with this.
Above-mentioned prepreg is cut into required shape, and optionally and after the laminations such as copper foil, using compression moulding method or
Autoclave forming process, piece winding shaping method etc., one applies pressure in face of laminate makes laminated plates maleimide on one side
Resin combination is heating and curing, and can get laminated plates with this.
In turn, laminated plates made of copper foil can be overlapped on surface and forms circuit, be overlapped prepreg or copper foil etc. simultaneously thereon
It repeats aforesaid operations and obtains the circuit substrate of multilayer.
The solidfied material of prepreg of the invention can be widely applied to liquid crystal glass base conveying manipulator purposes, Silicon Wafer
Conveying disc purposes, the component purposes suitable for aerospace, engine component purposes of automobile etc. require light weight and high intensity and
The component of high-fire resistance.
It as the particular use of maleimide resin constituent of the invention, can enumerate: solid, coating, painting
Cloth agent, moulding material (including piece, film, FRP etc.), electronic material (include the close of printed base plate, electric wire coatings etc. with insulating materials
The cyanate resin fat composition that Feng Cai and sealing material, substrate are used) or as resist curing agent acrylic ester resin
Deng the additive etc. to other resins etc..Especially in FRP on the way, light of environmental concerns and defect caused by gap
Queueing problem, in recent years, solvent free are greatly promoted.Gap or cob webbing, proof voltage when in turn, for forming
The problems such as reduction, in encapsulating semiconductor with also there is the solvent to cannot be introduced into the environment in step on the way.
[embodiment]
Hereinafter, the contents of the present invention are specifically described based on embodiment, but the present invention is not limited to this.In addition,
As long as not specified, " part " and " % " herein respectively indicates " parts by weight " and " weight % ".In embodiment, softening point and
Melting viscosity is measured using following methods.
Softening point: it is measured using the method according to JISK-7234
Melting viscosity: the viscosity using cone-plate method at 150 DEG C
The quantitative gas chromatograph GC-2010 manufactured using company, Shimadzu Seisakusho Ltd. of residual solvent amount is carried out, and is used
DB-WAX (manufacture of Agilene Technologies company) length 30m, internal diameter 0.25mm is as tubing string.
As temperature program, after being kept for 5 minutes at 70 DEG C and being warming up to 140 DEG C with the heating rate of 10 DEG C/min,
220 DEG C are warming up to the heating rate of 20 DEG C/min and in the program of 220 DEG C of holdings 5 minutes.
The data acquisition of molecular weight uses hydrogel permeation layer analyzer (GPC, the LC- of company, Shimadzu Seisakusho Ltd. manufacture
20AD).Tubing string uses KF-603, KF-602.5, KF-602, KF-601, and in 40 DEG C of tubing string temperature, mobile phase is set as to THF, stream
Under conditions of fast 0.5ml/min, measured by RI detector.
(synthesis example 1)
Benzene is added in the flask for being equipped with thermometer, cooling tube, Dean-Rodney Stark azeotropic distillation separator, blender
559 parts of amine and 500 parts of toluene, in room temperature with 1 hour 167 parts of 35% hydrochloric acid of dropwise addition.Heating is carried out after completion of dropwise addition and by azeotropic
Water and toluene is cooling, liquid separation, be back to the toluene as organic layer in system and be dehydrated.Then, by 4,
Bis- 251 parts of (chloromethyl) biphenyl of 4'- are held in 60~70 DEG C and last 1 hour and are added, and then carry out 2 in mutually synthermal
Hour reaction.After reaction, toluene distillation is removed when heating up and 190~200 DEG C will be set as in system, in the temperature
Degree react within 15 hours.Then, 30% hydroxide is not slowly added dropwise in a manner of vigorous reflux in system while cooling
500 parts of sodium water solution, the toluene for removing distillation in 80 DEG C or less is back in system and stands in 70 DEG C~80 DEG C.It will separation
Lower layer water layer removal, and repeat reaction solution washing until detergent remover become neutrality.Then, from oil reservoir under heating decompression
By superfluous aniline and toluene distillation removal, 335 parts of aromatic amine resin (A1) are obtained with this.Aromatic amine resin (A1) it is soft
Changing point is 59 DEG C, melting viscosity 0.05Pas.
(synthesis example 2)
It is added in the flask for being equipped with thermometer, cooling tube, Dean-Rodney Stark azeotropic distillation separator, blender suitable
88 parts of anhydride maleique and 300 parts of toluene carry out heating and the cooling, liquid separation by the water of azeotropic and toluene, then only make as having
The toluene of machine layer is back in system and is dehydrated.Secondly, 116 parts of aromatic amine resin (A1) will be made to be dissolved in N- methyl-
Resin solution made of 116 parts of 2- Pyrrolizidine ketone is added dropwise in being held in 80~85 DEG C in system and last 1 hour.It is added dropwise
After, react within 2 hours in mutually synthermal, add 2 parts of p-methyl benzenesulfonic acid, under counterflow condition by the condensation water of azeotropic and
Toluene cooling, liquid separation, are back to the toluene as organic layer in system and are dehydrated, and carry out 10 hours instead
It answers.After reaction, additional 120 parts of toluene, repeats washing and removes the maleic anhydride of p-methyl benzenesulfonic acid and surplus
It removes, and is heated and removed water from system by azeotropic.Then, by reaction solution be concentrated and obtain containing 70% it is suitable
The maleimide resin solution (V1) of butylmaleimide resin.By GPC to maleimide obtained
The molecular weight distribution of resin solution (V1) measures, and obtains result shown in FIG. 1.
(synthesis example 3)
Benzene is added in the flask for being equipped with thermometer, cooling tube, Dean-Rodney Stark azeotropic distillation separator, blender
559 parts of amine and 500 parts of toluene, in room temperature with 1 hour 167 parts of 35% hydrochloric acid of dropwise addition.Heating is carried out after completion of dropwise addition and by azeotropic
Water and toluene is cooling, liquid separation, be back to the toluene as organic layer in system and be dehydrated.Then, by 4,
Bis- 175 parts of (chloromethyl) benzene of 4'- are held in 60~70 DEG C and last 1 hour and are added, and then to carry out 2 small in mutually synthermal
Shi Fanying.After reaction, toluene distillation is removed when heating up and 190~200 DEG C will be set as in system, and in the temperature
Degree react within 15 hours.Then, 30% hydroxide is not slowly added dropwise in a manner of vigorous reflux in system while cooling
500 parts of sodium water solution, the toluene for removing distillation in 80 DEG C or less is back in system and stands in 70 DEG C~80 DEG C.It will separation
Lower layer water layer removal, and repeat reaction solution washing until detergent remover become neutrality.Then, from oil reservoir under heating decompression
By superfluous aniline and toluene distillation removal, 280 parts of aromatic amine resin (A2) are obtained with this.Aromatic amine resin (A2) is half
The resin-like of solid.
(synthesis example 4)
It is added in the flask for being equipped with thermometer, cooling tube, Dean-Rodney Stark azeotropic distillation separator, blender suitable
88 parts of anhydride maleique and 300 parts of toluene carry out heating and the cooling, liquid separation by the water of azeotropic and toluene, then only make as having
The toluene of machine layer is back in system and is dehydrated.Secondly, 91.7 parts of aromatic amine resin (A2) will be made to be dissolved in N- methyl-
Resin solution made of 91.7 parts of 2- Pyrrolizidine ketone is added dropwise in being held in 80~85 DEG C in system and last 1 hour.Drop
After adding, react within 2 hours in mutually synthermal, 2 parts of p-methyl benzenesulfonic acid are added, by the condensation water of azeotropic under counterflow condition
And toluene is cooling, liquid separation, is back to the toluene as organic layer in system and is dehydrated, and carries out 10 hours
Reaction.After reaction, additional 120 parts of toluene, repeat washing and by p-methyl benzenesulfonic acid and the maleic anhydride of surplus
Removal, and heated and removed water from system by azeotropic.Then, reaction solution is concentrated and obtains and contains 70%
The maleimide resin solution (V2) of maleimide resin.
(embodiment 1) (support: acid imide film)
Using applicator (flow will be cast by the maleimide resin solution (V1) obtained of synthesis example 2
Casting) it is coated on commercially available acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (WET film
It is 200 μm thick), and by removing be coated with resin film and 180 DEG C 15 minutes dry by solvent.
Maleimide resin formed body obtained is 125 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M1) of the invention.
The residual solvent of maleimide resin formed body (M1) obtained is 0.236% (2360ppm).Pass through
GPC measures the molecular weight distribution of maleimide resin formed body (M1) obtained, obtains knot shown in Fig. 2
Fruit.Pass through molecular weight distribution measured by GPC with by the maleimide resin solution (V1) obtained of synthesis example 2
(Fig. 1) is compared, and does not find the variation of the molecular weight distribution based on this step (using the measurement of GPC).
(embodiment 2) (support: acid imide film)
It will be by maleimide resin solution (V1) cast coat obtained of synthesis example 2 in city using applicator
The acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (200 μm of WET film thickness) sold, and by making
The resin film being coated with is dried 15 minutes in 200 DEG C and removes solvent.
Maleimide resin formed body obtained is 125 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M2) of the invention.
The residual solvent of maleimide resin formed body (M2) obtained is 0.293% (2930ppm).This
Outside, the variation of the molecular weight distribution based on this step is not found (using the measurement of GPC).
(embodiment 3) (support: acid imide film)
Maleimide resin solution (V1) cast coat obtained of synthesis example 2 to city will be passed through using applicator
The acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (200 μm of WET film thickness) sold, and by making
The resin film being coated with is dried 10 minutes in 200 DEG C and removes solvent.
Maleimide resin formed body obtained is 125 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M3) of the invention.
The residual solvent of maleimide resin formed body (M3) obtained is 0.398% (3980ppm).This
Outside, the variation of the molecular weight distribution based on this step is not found (using the measurement of GPC).
(embodiment 4) (support: acid imide film)
It will be by maleimide resin solution (V1) cast coat obtained of synthesis example 2 in city using applicator
The acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (200 μm of WET film thickness) sold, and by making
The resin film being coated with is dried 5 minutes in 200 DEG C and removes solvent.
Maleimide resin formed body obtained is 125 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M4) of the invention.
The residual solvent of maleimide resin formed body (M4) obtained is 0.0901% (901ppm).
In addition, not finding the variation of the molecular weight distribution based on this step (using the measurement of GPC).
(embodiment 5) (support: SUS plate)
Using applicator will by maleimide resin solution (V1) cast coat obtained of synthesis example 2 in
SUS plate (200 μm of WET film thickness), and by removing be coated with resin film and 180 DEG C 15 minutes dry by solvent.
Maleimide resin formed body obtained is 113 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M5) of the invention.
The residual solvent of maleimide resin formed body (M5) obtained is 0.163% (1638ppm).
In addition, not finding the variation of the molecular weight distribution based on this step (using the measurement of GPC).
(embodiment 6) (support: SUS plate)
Using applicator will by maleimide resin solution (V2) cast coat obtained of synthesis example 4 in
SUS plate (200 μm of WET film thickness), and by removing be coated with resin film and 180 DEG C 15 minutes dry by solvent.
Maleimide resin formed body obtained is 113 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M6) of the invention.
The residual solvent of maleimide resin formed body (M6) obtained is 0.3%≤(3000ppm≤).This
Outside, the variation (utilizing the measurement of GPC) of the molecular weight distribution based on this step is not found.
(embodiment 7) (support: mirror surface copper foil)
It will be by maleimide resin solution (V1) cast coat obtained of synthesis example 2 in electricity using applicator
Solve mirror surface (the WET film thickness of copper foil (manufacture of Bo Fen Industries, Inc, FUKUDA METAL, 18 μ electrolytic copper foil CF-T9FZ-HTE)
200 μm), and by removing be coated with resin film and 180 DEG C 15 minutes dry by solvent.
Maleimide resin formed body obtained is 152 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M7) of the invention.
The residual solvent of maleimide resin formed body (M6) obtained is 0.0728% (728ppm).
In addition, not finding the variation of the molecular weight distribution based on this step (using the measurement of GPC).
(embodiment 8) (support: PET film)
It will be by maleimide resin solution (V1) cast coat obtained of synthesis example 2 in not using applicator
The PET film (manufacture of Panac limited liability company, Lumirror 38-S10) (200 μm of WET film thickness) of demoulding processing is carried out, and is led to
Crossing dries be coated with resin film 1 hour in 160 DEG C and removes solvent.
Maleimide resin formed body obtained is 146 μm of thickness membranaceous, by removing and crushing and system
Fragmentate shape shape maleimide resin formed body (M7) of the invention.
The residual solvent of maleimide resin formed body (M8) obtained is 0.0571% (571ppm).This
Outside, the variation of the molecular weight distribution based on this step is not found (using the measurement of GPC).
(comparative example 1)
For by maleimide resin solution (V1) 300mL obtained of synthesis example 2, rotary evaporator is used
Solvent is distilled with 160 DEG C under heating decompression and is removed, maleimide resin (B1) is obtained with resin bulk.Pass through
GPC measures the molecular weight distribution of maleimide resin obtained (B1), obtains result shown in Fig. 3.With
By the maleimide resin solution (V1) obtained of synthesis example 2 by molecular weight distribution (Fig. 1) measured by GPC into
Row compares, and high molecular weight occurs for the maleimide resin (B1) when as a result confirming a large amount of synthesis after solvent distillation removal
Change.The residual solvent of maleimide resin (B1) obtained be 0.1% (1000ppm) below.
(comparative example 2)
For by maleimide resin solution (V1) 1.0L obtained of synthesis example 2, rotary evaporator is used
Generation gelation is as a result confirmed by after solvent distillation removal under heating decompression with 180 DEG C.Maleoyl- obtained
Imide resin (B2) loses flowability.
The comparison > of drying temperature in the manufacturing method of < maleimide resin formed body
(comparative example 3)
Similarly to Example 1, the maleimide resin solution obtained of synthesis example 2 will be passed through using applicator
(V1) cast coat is in commercially available acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (WET film
It is 200 μm thick), and by heat be coated with resin film using 50 DEG C of hot wind, dry 1 hour and remove solvent.
Maleimide resin formed body obtained has glutinous soapy feeling, is unable to maintain that the shape of film, can not remove simultaneously
It crushes.
(comparative example 4)
Similarly to Example 1, the maleimide resin solution obtained of synthesis example 2 will be passed through using applicator
(V1) cast coat is in commercially available acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture) (WET film
It is 200 μm thick), and by heat be coated with resin film using 250 DEG C of hot wind, dry 1 hour and remove solvent.
Maleimide resin formed body obtained is membranaceous and peelable and broken flaking, but has carried out high score
Son quantization, insoluble in various solvents such as acetone.
The comparison > of < foul smell
(embodiment 9, comparative example 5)
Prepare maleimide resin formed body (M1) obtained in embodiment 1 and the 4,4'- compared is bis- suitable
Butylmaleimide diphenyl methane (TCI company manufacture, be set as C1 below), carries out the comparison of foul smell.
In addition, the quantitative gas chromatograph GC-2010Plus manufactured using company, Shimadzu Seisakusho Ltd. of acetic acid is carried out, use
DB-WAX (manufacture of Agilene Technologies company) length 30m, internal diameter 0.25mm is as tubing string.As temperature program,
It is kept for 7 minutes using at 60 DEG C, is warming up to 220 DEG C with the heating rate of 20 DEG C/min and in the program of 220 DEG C of holdings 5 minutes.
As a result, confirmation has the foul smell of acetic acid in comparative example 5, foul smell is not felt in embodiment 9.
In addition, measuring by gas chromatograph, as a result detect acetic acid (referring to Fig. 4, retention time in comparative example 5
11.298 minute).In addition, being measured to acid value, as a result confirms as acid value 10mgKOH/g, meet and be equivalent to acetic acid
1%.
The comparison > of < shape and solvent solubility
(embodiment 10~14, comparative example 6,7)
Use maleimide resin formed body obtained in embodiment 1,5,6,7,8 (M1, M5~M8) and ratio
Compared with maleimide resin C1, maleimide resin (B2) is carried out to acetone documented by comparative example 2
Solubility test.
It is unified into resin concentration 50% and is studied, as a result maleimide resin formed body M1, M5~M8 are complete
Fully dissolved, but maleimide resin (C1) and maleimide resin (B2) are not completely dissolved.
According to above situation, it is known that it is completely dissolved in embodiment 10~14, therefore maleimide resin formed body
(M1, M5~M8) does not carry out molecular weight reaction.On the other hand, it is known that can not be completely dissolved in comparative example 6 and 7, Gu Shunding
Alkene imidodicarbonic diamide resin (C1, B2) has carried out molecular weight reaction.
The preparation of < maleimide resin constituent, solidfied material characteristic comparison >
(embodiment 15)
It blends and promotes by 10 parts of the maleimide resin formed body (M1) obtained of embodiment 1, as solidification
0.21 part of the 2-ethyl-4-methylimidazole (2E4MZ, four countries are melted into limited liability company's manufacture) of agent, and by stirring evenly ground
Mixing is kneaded, and obtains maleimide resin constituent of the invention.Using applicator by the maleimide tree
Fat composition cast coat is in commercially available acid imide film (" Kapton (registered trademark) 100H " of TORAY-DUPONT manufacture)
The resin film being coated with is removed solvent one under 160 DEG C × 2h+180 DEG C × 6h of condition of cure by (200 μm of WET film thickness) on one side
Face solidification, obtains solidfied material with this.It carries out the physical property to solidfied material obtained to evaluate resulting result shown in table 1.
(comparative example 8)
Blend 61 parts of EPPN-502H (Japanese chemical drug manufacture, epoxide equivalent 169g/eq., 67.5 DEG C of EP1 of softening point), phenol
Novolaks (it is bright and chemical conversion company manufacture, H-1, hydroxyl equivalent 106g/eq.) 38 parts by weight, triphenylphosphine (the pure chemistry of TPP,
Reagent) 1 parts by weight, it equably mixed, be kneaded using mixing mill, obtain epoxy resin component.By the epoxy resin component
After pastille, using translating into shape for resin combination formed body, and obtained under 160 DEG C × 2h+180 DEG C × 6h of condition of cure
Obtain solidfied material.Following physical property of solidfied material obtained are evaluated.Show the result in table 1.
(comparative example 9)
65 parts of blending EOCN-1020-55 (Japanese chemical drug manufacture, epoxide equivalent 194g/eq., 54.8 DEG C of softening point, EP2),
Phenol novolacs (bright and chemical conversion company manufacture, H-1, hydroxyl equivalent 106g/eq.) 34 parts by weight, TPP (pure chemical reagent)
1 parts by weight are equably mixed using mixing mill, are kneaded, and epoxy resin component is obtained.By the epoxy resin component pastille
Afterwards, using translating into shape for resin combination formed body, and solidified under 160 DEG C × 2h+180 DEG C × 6h of condition of cure
Object.Following physical property of solidfied material obtained are evaluated.Show the result in table 1.
Following measurements are implemented to solidfied material obtained.
·DMA
Measure the item: 30 DEG C, 200 DEG C, 250 DEG C of storage modulus of elasticity,
: glass transition temperature (temperature when tan δ maximum)
Measurement method: dynamic viscoelasticity measuring appliance TA-instruments manufacture, Q-800
Measurement temperature range: 30 DEG C~350 DEG C
Warm speed: 2 DEG C/min
Specimen size: (about 800 μm of the thickness) for being cut into 5mm × 50mm is used.
[table 1]
Table 1
| Embodiment 13 | Comparative example 8 | Comparative example 9 | ||
| DMA Tanδ | ℃ | 225.8 | 245.9 | 185.3 |
| DMA30 DEG C of storage modulus of elasticity | MPa | 3315 | 2550 | 2875 |
| DMA200 DEG C of storage modulus of elasticity | MPa | 2406 | 1534 | 108 |
| DMA250 DEG C of storage modulus of elasticity | Mpa | 1946 | 245 | 84 |
As shown in Table 1, the solidfied material of maleimide resin constituent of the invention can be in identical as epoxy resin
Condition of cure under shape, in addition, bullet of the solidfied material obtained compared with the situation for using high heat epoxy, under high temperature
Property modulus variation it is less.
It is described the invention in detail referring to specific embodiment, but those skilled in the art should understand and can not take off
It makes various changes and corrects from spirit and scope of the present invention.
In addition, Japanese patent application case (the Japanese Patent Application 2016- that the application was filed an application based on August 31st, 2016
169417) its entirety, and in the form of reference is quoted.In addition, cited herein introduce as a whole all referring to document.
[industrial availability]
Maleimide resin formed body of the invention can easily prepare maleimide resin constituent,
In high heat resistance baseplate material, flexible substrate material, high heat resistance dielectric materials, high heat resistance CFRP, with material, (carbon fiber is compound
Material), it is extremely useful on the way with the extensive use such as high heat resistance sealant use suitable for vehicle-mounted SiC power device.
Claims (13)
1. a kind of maleimide resin formed body containing maleimide resin and organic solvent, and is film
Shape or fragment shape.
2. maleimide resin formed body as described in claim 1, wherein the content of above-mentioned organic solvent is
30000ppm or less.
3. maleimide resin formed body as claimed in claim 1 or 2, wherein above-mentioned organic solvent is selected from carbon
At least one of aromatic hydrocarbon, ketone, esters and ethers of number 3~10.
4. maleimide resin formed body as claimed any one in claims 1 to 3, with a thickness of 10 μm~3mm.
5. maleimide resin formed body according to any one of claims 1 to 4, wherein above-mentioned maleic two
Imide resin is the phenolic varnish type maleimide resin for the repetitive unit for being 2~20 with average function radix.
6. the maleimide resin formed body as described in any one of claims 1 to 5, wherein above-mentioned maleic two
The softening point of imide resin is 50~150 DEG C.
7. a kind of manufacturing method of maleimide compounds formed body, will be such that maleimide resin is dissolved in
Solution coating made of organic solvent is on the surface of support and being dried.
8. the manufacturing method of maleimide compounds formed body as claimed in claim 7, wherein above-mentioned organic solvent
For aromatic hydrocarbon, ketone, esters, at least one of ethers selected from carbon number 3~10.
9. the manufacturing method of maleimide compounds formed body as claimed in claim 7 or 8, wherein drying temperature
It is 80~200 DEG C.
10. a kind of maleimide resin formed body, to pass through manufacturer described in any one of claim 7 to 9
Method and obtain.
11. a kind of maleimide resin constituent, it includes any one of claim 1 to 6 and claim 10 institutes
The maleimide resin formed body stated.
It 12. maleimide resin constituent as claimed in claim 11, and then include selected from can be with maleic two
The compound and at least any one in curing accelerator that imide resin carries out cross-linking reaction.
13. a kind of solidfied material is the solidfied material of maleimide resin constituent described in claim 11 or 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016169417 | 2016-08-31 | ||
| JP2016-169417 | 2016-08-31 | ||
| PCT/JP2017/030694 WO2018043380A1 (en) | 2016-08-31 | 2017-08-28 | Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109641984A true CN109641984A (en) | 2019-04-16 |
Family
ID=61300725
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780050109.8A Pending CN109641984A (en) | 2016-08-31 | 2017-08-28 | Maleimide resin formed body, the manufacturing method of maleimide resin formed body, maleimide resin constituent and its solidfied material |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7011589B2 (en) |
| KR (2) | KR20190046815A (en) |
| CN (1) | CN109641984A (en) |
| TW (1) | TWI724229B (en) |
| WO (1) | WO2018043380A1 (en) |
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|---|---|---|---|---|
| US5945503A (en) * | 1996-11-13 | 1999-08-31 | Mitsui Chemicals, Inc. | Polymaleimide resin composition and laminate plate for semiconductor substrate using it |
| JP2006348298A (en) * | 2005-06-15 | 2006-12-28 | E I Du Pont De Nemours & Co | Composition patternable by using amplified light, and useful as application example of electronic circuit type, and method and composition associated therewith |
| CN101669049A (en) * | 2007-04-18 | 2010-03-10 | 东曹株式会社 | Optical compensation films, optically compensating film, and processes for producing these |
| TW201605923A (en) * | 2014-04-02 | 2016-02-16 | Nippon Kayaku Kk | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof |
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| JP2758109B2 (en) | 1992-08-31 | 1998-05-28 | 矢崎総業株式会社 | Lock structure |
| JP2002328232A (en) * | 2001-05-02 | 2002-11-15 | Kanegafuchi Chem Ind Co Ltd | Film, protective film for polarizer and polarizing plate |
| JP2002331574A (en) * | 2001-05-11 | 2002-11-19 | Kanegafuchi Chem Ind Co Ltd | Manufacturing method for optical film |
| JP4120380B2 (en) * | 2002-12-10 | 2008-07-16 | 東ソー株式会社 | Method for producing transparent film |
| JP2004231857A (en) * | 2003-01-31 | 2004-08-19 | Tosoh Corp | Resin composition and optical member using it |
| TW200536891A (en) * | 2004-03-31 | 2005-11-16 | Teijin Dupont Films Japan Ltd | Oriented film, process for producing the same and laminate thereof |
| JP5030297B2 (en) | 2007-05-18 | 2012-09-19 | 日本化薬株式会社 | Laminate resin composition, prepreg and laminate |
| JP2011082559A (en) * | 2010-12-24 | 2011-04-21 | Hitachi Chem Co Ltd | Adhesive film for semiconductor |
| TWI594882B (en) * | 2011-07-22 | 2017-08-11 | Ｌｇ化學股份有限公司 | Thermosetting resin composition and prepreg and metal clad laminate using the same |
| KR101668855B1 (en) * | 2013-09-30 | 2016-10-28 | 주식회사 엘지화학 | Thermosetting resin composition for semiconductor pakage and Prepreg and Metal Clad laminate using the same |
| JP6531910B2 (en) * | 2015-10-09 | 2019-06-19 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board |
| JP6482511B2 (en) | 2016-08-31 | 2019-03-13 | 日本化薬株式会社 | Maleimide resin molded body, method for producing maleimide resin molded body, maleimide resin composition and cured product thereof |
-
2017
- 2017-08-28 KR KR1020197005653A patent/KR20190046815A/en not_active IP Right Cessation
- 2017-08-28 WO PCT/JP2017/030694 patent/WO2018043380A1/en active Application Filing
- 2017-08-28 JP JP2018537246A patent/JP7011589B2/en active Active
- 2017-08-28 KR KR1020227024381A patent/KR102601953B1/en active IP Right Grant
- 2017-08-28 CN CN201780050109.8A patent/CN109641984A/en active Pending
- 2017-08-31 TW TW106129654A patent/TWI724229B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945503A (en) * | 1996-11-13 | 1999-08-31 | Mitsui Chemicals, Inc. | Polymaleimide resin composition and laminate plate for semiconductor substrate using it |
| JP2006348298A (en) * | 2005-06-15 | 2006-12-28 | E I Du Pont De Nemours & Co | Composition patternable by using amplified light, and useful as application example of electronic circuit type, and method and composition associated therewith |
| CN101669049A (en) * | 2007-04-18 | 2010-03-10 | 东曹株式会社 | Optical compensation films, optically compensating film, and processes for producing these |
| TW201605923A (en) * | 2014-04-02 | 2016-02-16 | Nippon Kayaku Kk | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102601953B1 (en) | 2023-11-14 |
| WO2018043380A1 (en) | 2018-03-08 |
| JP7011589B2 (en) | 2022-01-26 |
| KR20190046815A (en) | 2019-05-07 |
| KR20220106227A (en) | 2022-07-28 |
| TWI724229B (en) | 2021-04-11 |
| JPWO2018043380A1 (en) | 2019-06-24 |
| TW201815919A (en) | 2018-05-01 |
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