JP6978371B2 - Curable resin composition and laminate - Google Patents

Description

The present invention relates to a curable resin composition capable of obtaining a cured product having excellent heat resistance, mechanical strength, and dielectric properties. The present invention also relates to a laminate made of the curable resin composition.

Curable resins such as epoxy resins, which have low shrinkage and are excellent in adhesiveness, insulation, and chemical resistance, are used in many industrial products. In particular, in electronic equipment applications, curable resin compositions that give good results in a solder reflow test for short-time heat resistance and a cold-heat cycle test for repeated heat resistance are often used.

Further, the curable resin composition used as an interlayer insulating material for a printed wiring board or the like is required to have dielectric properties such as low dielectric constant and low dielectric loss tangent. As a curable resin composition having such excellent dielectric properties, for example, Patent Documents 1 and 2 disclose a curable resin composition containing a curable resin and a polyimide or a bismaleimide compound having a specific structure. ing. However, although these curable resin compositions are excellent in dielectric properties, the glass transition temperature of the cured product is low, so that the printed wiring board produced using these curable resin compositions is elastic at the mounting temperature. There were problems in terms of heat resistance and mechanical strength, such as a low rate and difficulty in mounting semiconductor elements.

Japanese Unexamined Patent Publication No. 2017-186551 International Publication 2016/114286

An object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent heat resistance, mechanical strength, and dielectric properties. Another object of the present invention is to provide a laminate made of the curable resin composition.

The present invention contains a curable resin and an imide compound, and the imide compound is a curable resin composition containing a polyfunctional maleimide compound having a trimertriamine residue.
The present invention will be described in detail below.

The present inventors obtain a curable resin composition capable of obtaining a cured product having excellent heat resistance, mechanical strength, and dielectric properties by using a polyfunctional maleimide compound having a specific structure as a curing agent. We have found that we can do this, and have completed the present invention.

The curable resin composition of the present invention contains an imide compound.
The imide compound includes a polyfunctional maleimide compound having a trimertriamine residue (hereinafter, also referred to as "polyfunctional maleimide compound according to the present invention").
By containing the polyfunctional maleimide compound according to the present invention, the curable resin composition of the present invention can obtain a cured product having excellent heat resistance, mechanical strength, and dielectric properties.

The polyfunctional maleimide compound according to the present invention has a trimertriamine residue. Since the polyfunctional maleimide compound according to the present invention has the trimertriamine residue, the glass transition temperature and dielectric properties of the curable resin composition of the present invention can be improved.
In the present specification, the above-mentioned "residue" means the structure of a portion other than the functional group provided for binding, and for example, the "trimertriamine residue" refers to the structure of the portion other than the amino group in the trimertriamine. means.

The trimertriamine from which the trimertriamine residue is derived can be made from the corresponding trimer acid.
As the trimer acid, for example, a trimer of an aliphatic acid having 10 or more and 30 or less carbon atoms such as oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid, and a trimer of the fatty acid are further hydrogenated. The ones that have been made are mentioned.
Examples of commercially available trimmer triamines include PRIAMINE 1071 (manufactured by Croda Japan) and the like. In the commercial product of trimertriamine, the content of trimertriamine is usually about 15 to 20% by mass, and the commercially available product may contain diamine diamine in an amount of more than 80% by mass.

The preferred upper limit of the molecular weight of the polyfunctional maleimide compound according to the present invention is 1100. When the molecular weight is 1100 or less, the cured product of the obtained curable resin composition is superior in heat resistance and mechanical strength. A more preferable upper limit of the molecular weight of the polyfunctional maleimide compound according to the present invention is 1050.
Further, although there is no particular preferable lower limit of the molecular weight of the polyfunctional maleimide compound according to the present invention, the practical lower limit is 310.
In the present specification, the above-mentioned "molecular weight" is the molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of degree of polymerization and a compound having an unspecified modification site. It may be expressed using a number average molecular weight. In the present specification, the above-mentioned "number average molecular weight" is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industry Co., Ltd.).

Specifically, as the polyfunctional maleimide compound according to the present invention, a trismaleimide compound represented by the following formula (1) is preferable.

Examples of the method for producing the polyfunctional maleimide compound according to the present invention include a method of reacting maleic anhydride, which may have a substituent, with the trimertriamine.
When the maleic anhydride has a substituent, examples of the substituent include a methyl group and the like.

Specific examples of the method for reacting the maleic anhydride with the trimertriamine are shown below.
First, the trimertriamine and a catalytic amount of tetra-n-butylammonium chloride are previously dissolved in a solvent (for example, toluene or the like) in which the maleinamic acid obtained by the reaction is soluble. The above maleic anhydride is added to the obtained solution and reacted under reflux for 2 hours to obtain a maleic anhydride solution. The polyfunctional maleimide compound according to the present invention can then be obtained by attaching a Dean-Stark trap and refluxing the mixture for 12 hours to dehydrate and cyclize the maleeamic acid.

The imide compound may contain other imide compounds in addition to the polyfunctional maleimide compound according to the present invention.
Examples of the other imide compound include a bismaleimide compound having a dimerdiamine residue.

When the imide compound contains the other imide compound, the preferable lower limit of the content of the polyfunctional maleimide compound according to the present invention in the imide compound is 5% by weight, and the preferable upper limit is 50% by weight. When the content of the polyfunctional maleimide compound according to the present invention is in this range, the cured product of the obtained curable resin composition is excellent in heat resistance, mechanical strength, and dielectric properties. A more preferable lower limit of the content of the polyfunctional maleimide compound according to the present invention is 10% by weight, and a preferable upper limit is 40% by weight.

The preferable lower limit of the content of the imide compound in 100 parts by weight of the curable resin and the imide compound is 0.1 part by weight, and the preferable upper limit is 50 parts by weight. When the content of the imide compound is in this range, the cured product of the obtained curable resin composition is excellent in heat resistance, mechanical strength, and dielectric properties. The more preferable lower limit of the content of the imide compound is 0.2 parts by weight, and the more preferable upper limit is 40 parts by weight.

The curable resin composition of the present invention may contain other curing agents in addition to the above-mentioned imide compound in order to improve processability in an uncured state, etc., as long as the object of the present invention is not impaired. good.
Examples of the other curing agents include phenol-based curing agents, thiol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, active ester-based curing agents, and the like. Of these, a phenol-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent are preferable.

When the curable resin composition of the present invention contains the other curing agent, the preferable upper limit of the content ratio of the other curing agent in the entire curing agent is 50% by weight, and the more preferable upper limit is 40% by weight.

The curable resin composition of the present invention contains a curable resin.
As the curable resin, at least one selected from the group consisting of an epoxy resin, a cyanate resin, a phenol resin, an active ester resin, a carbodiimide resin, and a benzoxazine resin is preferable. Above all, it is more preferable that the curable resin contains an epoxy resin.
Further, the curable resin is preferably in a liquid or semi-solid form at 25 ° C., and more preferably in a liquid form, in order to improve the processability when processing a film.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , Propoxy oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether Type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, Examples thereof include rubber-modified epoxy resins and glycidyl ester compounds. Of these, dicyclopentadiene novolac type epoxy resin and biphenyl novolac type epoxy resin are preferable because the glass transition temperature after curing is high and the dielectric loss tangent is low.

Examples of the cyanate resin include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized. Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin.
Examples of commercially available phenol novolac type cyanate ester resins include PT-30 and PT-60 (both manufactured by Lonza Japan Co., Ltd.).
Among the prepolymers in which the above bisphenol type cyanate ester resin is partially quantified, commercially available ones include, for example, BA-230S, BA-3000S, BTP-1000S, and BTP-6020S (all manufactured by Lonza Japan). And so on.
The cyanate resin may be used alone or in combination of two or more.

Examples of the phenol resin include a novolak type phenol resin, a biphenyl novolak type phenol resin, an aralkyl type phenol resin, and a phenol resin having an aminotriazine skeleton.
Examples of commercially available novolak-type phenolic resins include TD-2091 (manufactured by DIC Corporation) and the like.
Among the above-mentioned biphenyl novolac type phenol resins, those commercially available include, for example, MEH-7851 (manufactured by Meiwakasei Co., Ltd.) and the like.
Examples of commercially available aralkyl-type phenol compounds include MEH-7800 (manufactured by Meiwakasei Co., Ltd.) and the like.
Examples of commercially available phenolic resins having an aminotriazine skeleton include LA1356 and LA3018-50P (both manufactured by DIC Corporation).
The above-mentioned phenol resin may be used alone or in combination of two or more.

The active ester resin refers to a compound containing at least one ester bond in the structure and having aromatic rings bonded to both sides of the ester bond.
The active ester resin is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound.

Examples of the active ester resin include compounds represented by the following formula (2).

In formula (2), X ¹ and X ² each represent a group containing an aromatic ring.
Examples of the group containing the aromatic ring include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the substituent include a hydrocarbon group and the like. The hydrocarbon group preferably has 12 or less carbon atoms, more preferably 6 or less, and even more preferably 4 or less.

^{The combination of X 1} and X ² in the above formula (2) includes, for example, a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a substituent. Examples thereof include a combination of a benzene ring which may be used and a naphthalene ring which may have a substituent. Further, ^{examples of the combination of X 1} and X ² include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The active ester resin is preferably an active ester resin having two or more aromatic skeletons from the viewpoint of further enhancing thermal dimensional stability. Further, it is more preferable that the active ester resin has a naphthalene ring in the main chain skeleton from the viewpoint of lowering the dielectric loss tangent of the obtained cured product and enhancing the thermal dimensional stability.
Examples of commercially available active ester resins include HPC-8000-65T, EXB9416-70BK, EXB8100-65T, HPC-8150-60T (all manufactured by DIC Corporation) and the like. The active ester resin may be used alone or in combination of two or more.

The carbodiimide resin is a compound having a structural unit represented by the following formula (3).

In the formula (3), * is a bonding site with another group, X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, and the like. It represents an arylene group or a group in which a substituent is bonded to an arylene group, and p represents an integer of 1 or more and 5 or less. When there are a plurality of X's, the plurality of X's may be the same or different.

In the above formula (3), when p is an integer of 2 or more and 5 or less, at least one X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, or a substituent to a cycloalkylene group. Is preferably a bonded group.

Examples of commercially available carbodiimide resins include carbodiimide resins manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide resins manufactured by Rheinchemy, and the like.
Examples of the carbodiimide resin manufactured by Nisshinbo Chemical Co., Ltd. include carbodilite V-02B, carbodilite V-03, carbodilite V-04K, carbodilite V-07, carbodilite V-09, carbodilite 10M-SP, and carbodilite 10M-SP (revised). And so on.
Examples of the carbodiimide resin manufactured by Rheinchemy include Stavaxol P, Stavaxol P400, and Hycadil 510.
The carbodiimide resin may be used alone or in combination of two or more.

Examples of the benzoxazine resin include P-d type benzoxazine and Fa type benzoxazine.
Examples of commercially available benzoxazine resins include P-d type (manufactured by Shikoku Chemicals Corporation).

The curable resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned curing accelerator, the curing time can be shortened and the productivity can be improved.

Examples of the curing accelerator include an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, a phosphine-based curing accelerator, a photobase generator, a sulfonium salt-based curing accelerator, and a radical curing accelerator. .. Of these, imidazole-based curing accelerators and radical curing accelerators are preferable from the viewpoint of storage stability and curability.
The curing accelerator may be used alone or in combination of two or more.

Examples of the imidazole-based curing accelerator include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. , 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino- 6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazole-(1')]-ethyl-s-triazine, 2 , 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazole- (1') ] -Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Examples thereof include 5-dihydroxymethylimidazole.

Examples of the radical curing accelerator include peroxides and the like.
Examples of commercially available peroxides include dicumyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and perhexyl 25B (manufactured by NOF CORPORATION).

The content of the curing accelerator is preferably 0.1% by weight with respect to the total weight of the curable resin, the imide compound and the curing accelerator. When the content of the curing accelerator is 0.1% by weight or more, the effect of shortening the curing time is more excellent. A more preferable lower limit of the content of the curing accelerator is 0.5% by weight.
Further, from the viewpoint of adhesiveness and the like, the preferable upper limit of the content of the curing accelerator is 20% by weight, and the more preferable upper limit is 10% by weight.

The curable resin composition of the present invention preferably contains inorganic particles.
By containing the above-mentioned inorganic particles, the curable resin composition of the present invention has a lower heat ray expansion rate, dielectric constant, and dielectric loss tangent of the cured product, and is more excellent as an interlayer insulating material or the like.

Examples of the inorganic particles include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride. Of these, silica is preferable.
The inorganic particles may be used alone or in combination of two or more.

The preferable lower limit of the average particle size of the inorganic particles is 10 nm. When the average particle diameter of the inorganic particles is 10 nm or more, an increase in melt viscosity is suppressed, and when the curable resin composition of the present invention is used as an interlayer insulating material or the like, the embedding followability of the insulating film is further improved. become. A more preferable lower limit of the average particle size of the inorganic particles is 30 nm, and a further preferable lower limit is 50 nm.
The preferable upper limit of the average particle size of the inorganic particles is 20 μm. When the average particle diameter of the inorganic particles is 20 μm or less, the flatness of the surface of the insulating film becomes even better when the curable resin composition of the present invention is used as an interlayer insulating material or the like. A more preferable upper limit of the average particle size of the inorganic particles is 10 μm, a further preferable upper limit is 5 μm, and a particularly preferable upper limit is 2 μm. Further, from the viewpoint of further improving the embedding followability of the insulating film in the pattern and the flatness of the surface of the insulating layer, the average particle size of the inorganic particles is preferably 1 μm or less.
In the present specification, the average particle diameter of the inorganic particles adopts a value of a median diameter of 50%, and is obtained by measuring using a laser diffraction type particle size distribution measuring device. As the laser diffraction type particle size distribution measuring device, Master Sizar 2000 (manufactured by Malvern) or the like can be used.

The inorganic particles are preferably spherical, more preferably spherical silica. When the inorganic particles are spherical, the surface roughness of the surface of the cured product is effectively reduced, and when the curable resin composition of the present invention is used as an interlayer insulating material or the like, the insulating layer and the metal layer are combined. The adhesive strength is effectively increased.
When the inorganic particles are spherical, the preferable upper limit of the aspect ratio of the inorganic particles is 2, and the more preferable upper limit is 1.5.

The inorganic particles are preferably surface-treated, and more preferably surface-treated with a coupling agent. By surface-treating the inorganic particles, the surface roughness of the surface of the cured product becomes even smaller, and when the curable resin composition of the present invention is used as an interlayer insulating material or the like, the cured product and the metal layer The adhesive strength is further increased, finer wiring is formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability are imparted to the cured product.

Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and the like. Of these, a silane coupling agent is preferable.
Examples of the silane coupling agent include aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

The content of the inorganic particles is preferably 5 parts by weight and a preferable upper limit of 900 parts by weight with respect to 100 parts by weight of the total of the curable resin and the imide compound. When the content of the inorganic particles is in this range, the coefficient of linear thermal expansion, the dielectric constant, and the dielectric loss tangent of the cured product of the obtained curable resin composition become lower, and it is more excellent as an interlayer insulating material or the like. Become. The more preferable lower limit of the content of the inorganic particles is 10 parts by weight, and the more preferable upper limit is 850 parts by weight.

The curable resin composition of the present invention may contain organic particles for the purpose of stress relaxation, toughness imparting and the like.
Examples of the organic particles include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide-imide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Of these, polyamide particles, polyamide-imide particles, and polyimide particles are preferable.
The organic particles may be used alone or in combination of two or more.

The content of the organic particles is preferably 300 parts by weight with respect to 100 parts by weight of the total of the curable resin and the imide compound. When the content of the organic particles is in this range, the cured product of the obtained curable resin composition becomes more excellent in toughness and the like while maintaining excellent adhesiveness and the like. A more preferable upper limit of the content of the organic particles is 200 parts by weight.

The curable resin composition of the present invention may contain a flame retardant.
Examples of the flame retardant include metal hydrates such as boehmite type aluminum hydroxide, aluminum hydroxide and magnesium hydroxide, halogen compounds, phosphorus compounds, nitrogen compounds and the like. Of these, boehmite-type aluminum hydroxide is preferable.
The flame retardant may be used alone or in combination of two or more.

The content of the flame retardant is preferably 5 parts by weight and a preferable upper limit of 200 parts by weight with respect to 100 parts by weight of the total of the curable resin and the imide compound. When the content of the flame retardant is in this range, the obtained curable resin composition has excellent flame retardancy while maintaining excellent adhesiveness and the like. The more preferable lower limit of the content of the flame retardant is 10 parts by weight, and the more preferable upper limit is 150 parts by weight.

The curable resin composition of the present invention may contain a polymer compound as long as the object of the present invention is not impaired. The polymer compound plays a role as a film-forming component.

The polymer compound may have a reactive functional group.
Examples of the reactive functional group include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group and the like.

Further, the polymer compound may or may not form a phase-separated structure in the cured product. When the polymer compound does not form a phase-separated structure in the cured product, the polymer compound is excellent in mechanical strength at high temperature, long-term heat resistance, and moisture resistance, and therefore, as the reactive functional group. Polymer compounds having an epoxy group are preferred.

The curable resin composition of the present invention may contain a solvent from the viewpoint of coatability and the like.
As the solvent, a non-polar solvent having a boiling point of 160 ° C. or lower or an aprotic polar solvent having a boiling point of 160 ° C. or lower is preferable from the viewpoint of coatability, storage stability and the like.
Examples of the non-polar solvent having a boiling point of 160 ° C. or lower or the aprotonic polar solvent having a boiling point of 160 ° C. or lower include a ketone solvent, an ester solvent, a hydrocarbon solvent, a halogen solvent, an ether solvent, and a nitrogen-containing solvent. Examples include system solvents.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
Examples of the ester solvent include methyl acetate, ethyl acetate, isobutyl acetate and the like.
Examples of the hydrocarbon solvent include benzene, toluene, normal hexane, isohexane, cyclohexane, methylcyclohexane, normal heptane and the like.
Examples of the halogen-based solvent include dichloromethane, chloroform, trichlorethylene and the like.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, anisole and the like.
Examples of the nitrogen-containing solvent include acetonitrile and the like.
Among them, from the viewpoint of handleability and solubility of imide compounds, a group consisting of a ketone solvent having a boiling point of 60 ° C. or higher, an ester solvent having a boiling point of 60 ° C. or higher, and an ether solvent having a boiling point of 60 ° C. or higher. At least one selected from the above is preferable. Examples of such a solvent include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like.
The above "boiling point" means a value measured under the condition of 101 kPa or a value converted to 101 kPa in a boiling point conversion chart or the like.

The preferable lower limit of the content of the solvent in the curable resin composition of the present invention is 20% by weight, and the preferable upper limit is 90% by weight. When the content of the solvent is in this range, the curable resin composition of the present invention is excellent in coatability and the like. The more preferable lower limit of the content of the solvent is 30% by weight, and the more preferable upper limit is 80% by weight.

The curable resin composition of the present invention may contain a reactive diluent as long as the object of the present invention is not impaired.
As the reactive diluent, a reactive diluent having two or more reactive functional groups in one molecule is preferable from the viewpoint of adhesive reliability.

The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, an antibleeding agent, a flux agent, and a leveling agent.

As a method for producing the curable resin composition of the present invention, for example, a curable resin, an imide compound, and an imide compound are added as necessary using a mixer such as a homodisper, a universal mixer, a Banbury mixer, and a kneader. Examples thereof include a method of mixing with a solvent and the like.

In the curable resin composition of the present invention, the preferable lower limit of the glass transition temperature before curing is −20 ° C., and the preferred upper limit is 80 ° C. When the glass transition temperature before curing is in this range, the curable resin composition of the present invention is more excellent in processability. The more preferable lower limit of the glass transition temperature before curing is −10 ° C., and the more preferable upper limit is 60 ° C.
In the present specification, the above-mentioned "glass transition temperature before curing" is from the inflection point of the heat absorption peak accompanying the glass transition when measured at a temperature rise rate of 10 ° C./min using a differential scanning calorimeter. This is the required value.
Examples of the differential scanning calorimeter include a differential scanning calorimeter measuring machine DSC7000 series (manufactured by Hitachi High-Tech Science Corporation).
Further, the measurement of the glass transition temperature before curing is performed on a curable resin composition film having a thickness of 400 μm, which will be described later.

In the curable resin composition of the present invention, the preferable lower limit of the glass transition temperature of the cured product is 100 ° C., and the preferable upper limit is 240 ° C. When the glass transition temperature before curing is in this range, the cured resin composition of the present invention is superior in mechanical strength and heat resistance. The more preferable lower limit of the glass transition temperature of the cured product is 120 ° C., and the more preferable upper limit is 220 ° C.
In the present specification, the above-mentioned "glass transition temperature of the cured product" is from −0 ° C. to 300 ° C. at a temperature rise rate of 10 ° C./min, a frequency of 10 Hz, and a chuck-to-chuck distance of 24 mm using a dynamic viscoelasticity measuring device. It is a value obtained as the peak temperature of the tan δ curve obtained when measured under the temperature rising condition. Examples of the dynamic viscoelasticity measuring device include a Leovibron dynamic viscoelasticity automatic measuring device DDV-GP series (manufactured by A & D Co., Ltd.).
Further, the cured product for measuring the "glass transition temperature of the cured product" can be obtained by heating a curable resin composition film having a thickness of 400 μm, which will be described later, at 190 ° C. for 1 hour.

By applying the curable resin composition of the present invention on a base film and drying it, a curable resin composition film composed of the curable resin composition of the present invention can be obtained, and the curable resin composition can be obtained. A cured product can be obtained by curing the material film.

Specific examples of the method for obtaining the curable resin composition film include the following methods.
That is, an extrusion molding method in which the curable resin composition of the present invention is melt-kneaded and extruded using an extruder and then molded into a film by a T-die, a circular die or the like, or the curable resin composition of the present invention. Examples thereof include a casting molding method in which the resin is dissolved or dispersed in a solvent such as an organic solvent and then cast to form a film. Of these, the extrusion molding method or the casting molding method is preferable because it can be made thinner.
The "film" includes a "sheet".

After obtaining the curable resin composition film, a semi-cured product can be obtained by heating and drying at 90 to 200 ° C. for 1 to 180 minutes to the extent that curing by heat does not proceed too much.
Hereinafter, the semi-cured product obtained by the drying step as described above is referred to as a B stage film. The B stage film is not completely cured and can be further cured.

The B stage film is preferably not a prepreg. When the B stage film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the B stage film is laminated or pre-cured, unevenness due to the glass cloth does not occur on the surface. Further, by using the curable resin composition of the present invention as a B-stage film which is not a prepreg, the dimensional change due to the heat of the cured product is reduced, the shape retention is improved, and the suitability for the semi-additive process is improved.

The curable resin composition of the present invention is suitably used for forming a laminated film including a base material and the B stage film laminated on one surface of the base material.
A laminate having a substrate and a cured product of the curable resin composition of the present invention laminated on the substrate is also one of the present inventions.

Examples of the base material include polyester resin films, olefin resin films, polyimide resin films, metal foils, and the like.
Examples of the polyester resin film include polyethylene terephthalate film and polybutylene terephthalate film.
Examples of the olefin resin film include polyethylene films and polypropylene films.
Examples of the metal foil include copper foil and aluminum foil.
The surface of the base material may be mold-released, if necessary.

The curable resin composition of the present invention can be suitably used for forming an insulating layer of a printed wiring board because the cured product has a low dielectric constant and a low dielectric loss tangent and is excellent in dielectric properties.

When the curable resin composition of the present invention is used to form the insulating layer, the thickness of the layer formed by the curable resin composition of the present invention is equal to or greater than the thickness of the conductor layer forming the circuit. Is preferable. The preferable lower limit of the thickness of the layer formed by the curable resin composition of the present invention is 5 μm, and the preferable upper limit is 200 μm.

The printed wiring board can be obtained, for example, by heat-press molding the B-stage film using the B-stage film formed of the curable resin composition of the present invention.

In the printed wiring board, a metal foil can be laminated on one side or both sides of the B stage film.
Examples of the method of laminating the metal foil on one side or both sides of the B stage film include a method of pressurizing with or without heating using a device such as a parallel flat plate press or a roll laminator.

Further, the curable resin composition of the present invention is suitably used for obtaining a copper-clad laminate. Examples of the copper-clad laminate include a copper-clad laminate having a copper foil and the B-stage film laminated on one surface of the copper foil. That is, the B-stage film of the copper-clad laminate is suitably formed by the curable resin composition of the present invention.

The thickness of the copper foil is preferably in the range of 1 μm or more and 50 μm or less. Further, in order to increase the adhesive strength between the cured product layer obtained by curing the curable resin composition of the present invention and the copper foil, it is preferable that the copper foil has fine irregularities on the surface.
Examples of the method for forming the unevenness include a method for forming the unevenness by a treatment using a known chemical solution.

Further, the curable resin composition of the present invention is suitably used for obtaining a multilayer substrate.
An example of the multilayer board is a multilayer board including a circuit board and a cured product layer laminated on the surface of the circuit board. That is, the cured product layer of this multilayer substrate is suitably formed by curing the curable resin composition of the present invention. In this case, the cured product layer is preferably laminated on the surface on which the circuit of the circuit board is provided. It is preferable that a part of the cured product layer is embedded between the circuits.

In the multilayer board, it is preferable that the surface of the cured product layer opposite to the surface on which the circuit board is laminated is roughened.

As the roughening treatment, a conventionally known roughening treatment method can be used.
The surface of the cured product layer may be swelled before the roughening treatment.

It is preferable that the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the cured product layer.

As another example of the multilayer board, the circuit board, the cured product layer laminated on the surface of the circuit board, and the cured product layer laminated on the surface opposite to the surface on which the circuit board is laminated are laminated. Examples thereof include a multilayer substrate provided with a copper foil. In this case, the cured product layer and the copper foil are cured by curing the B stage film using a copper-clad laminate having the copper foil and the B stage film laminated on one surface of the copper foil. It is preferably formed. Further, the copper foil is etched and preferably a copper circuit.

Yet another example of the multilayer board is a multilayer board including a circuit board and a plurality of cured product layers laminated on the surface of the circuit board. In this case, at least one of the plurality of cured product layers is formed by curing the curable resin composition of the present invention. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the cured product layer formed by curing the curable resin composition of the present invention.

FIG. 1 is a partially cutaway front sectional view schematically showing a multilayer substrate using the curable resin composition of the present invention.
In the multilayer board 11 shown in FIG. 1, a plurality of cured product layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The cured product layers 13 to 16 are insulating layers. A metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12. Of the plurality of cured product layers 13 to 16, the cured product layers 13 to 15 other than the cured product layer 16 located on the outer surface opposite to the circuit board 12 side have a metal layer 17 in a part of the upper surface. Is formed. The metal layer 17 is wiring. The metal layer 17 is arranged between the circuit board 12 and the cured product layer 13 and between the layers of the laminated cured product layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

In the multilayer substrate 11, the cured product layers 13 to 16 are formed by curing the curable resin composition of the present invention. The surface of the cured product layers 13 to 16 has been roughened, and fine pores (not shown) are formed on the surface of the cured product layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine pores. Further, in the multilayer board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer which are not connected by via hole connection and through hole connection (not shown).

The curable resin composition of the present invention is preferably used to obtain a cured product to be roughened. The cured product also includes a pre-cured product that can be further cured.

In order to form fine irregularities on the surface of the pre-cured product obtained by pre-curing the curable resin composition of the present invention, it is preferable that the pre-cured product is roughened. Prior to the roughening treatment, the pre-cured product is preferably swelled.
It is preferable that the cured product is swelled and further cured after the roughening treatment after the pre-curing and before the roughening treatment. However, the pre-cured product does not necessarily have to be swelled.

As the method for the swelling treatment, for example, a method for treating the pre-cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component, an organic solvent dispersion solution, or the like is used.
The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is carried out by treating the pre-cured product at a treatment temperature of 30 ° C. to 85 ° C. for 1 to 30 minutes using a 40 wt% ethylene glycol aqueous solution or the like. The temperature of the swelling treatment is preferably in the range of 50 ° C to 85 ° C. If the temperature of the swelling treatment is too low, the swelling treatment takes a long time, and the adhesive strength between the cured product and the metal layer tends to be low.

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric acid compound is used as the roughening liquid. The chemical oxidizing agent is used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added.
The roughening solution generally contains an alkali as a pH adjuster or the like. The roughening solution preferably contains sodium hydroxide.

Examples of the manganese compound include potassium permanganate and sodium permanganate.
Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate.
Examples of the persulfate compound include sodium persulfate, potassium persulfate, ammonium persulfate and the like.

As the roughening treatment method, specifically, for example, 30 to 90 g / L permanganate or permanganate solution and 30 to 90 g / L sodium hydroxide solution are used, and the treatment temperature is 30 ° C. to 85 ° C. A method of treating the pre-cured product once or twice under the conditions of 1 to 30 minutes is preferable. The temperature of the roughening treatment is preferably in the range of 50 ° C to 85 ° C.

When the swelling treatment is performed using the swelling liquid and then the roughening treatment is performed using the roughening liquid, the arithmetic average roughness Ra of the surface of the roughened cured product is preferably 50 nm or more and 350 nm or less. .. In this case, the adhesive strength between the cured product and the metal layer or the wiring is increased, and further finer wiring can be formed on the surface of the cured product layer.

Through holes may be formed in the pre-cured product or the cured product obtained by pre-curing the curable resin composition of the present invention. In the multilayer board or the like, vias or through holes are formed as through holes. For example, vias can be formed by irradiation with a laser such as _{a CO 2 laser.} The diameter of the via is not particularly limited, but is about 60 to 80 μm. Due to the formation of the through holes, smear, which is a residue of the resin derived from the resin component contained in the cured product layer, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product layer is preferably desmear-treated. The desmear treatment may also serve as the roughening treatment.

In the desmear treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric compound is used as the desmear treatment liquid in the same manner as in the roughening treatment. The chemical oxidizing agent is used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added.
The desmear treatment liquid generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

As the method of desmear treatment, for example, 30 to 90 g / L permanganate or permanganate solution and 30 to 90 g / L sodium hydroxide solution are used, and the treatment temperature is 30 ° C. to 85 ° C. and 1 to 30 minutes. The method of treating the pre-cured product or the cured product once or twice under the above conditions is preferable. The temperature of the desmear treatment is preferably in the range of 50 ° C to 85 ° C.

By using the curable resin composition of the present invention, the surface roughness of the surface of the desmear-treated cured product is sufficiently reduced.

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product having excellent heat resistance, mechanical strength, and dielectric properties. Further, according to the present invention, it is possible to provide a laminate made of the curable resin composition.

FIG. 1 is a partially cutaway front sectional view schematically showing a multilayer substrate using the curable resin composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1 (Preparation of Maleimide Composition A))
It was dissolved in 140 parts by weight of a mixture of diamine diamine and trimer triamine ("PRIAMINE 1071" manufactured by Croda Japan), 5 parts by weight of tetra-n-butylammonium chloride, and 800 parts by weight of toluene (manufactured by Wako Pure Chemical Industries, Ltd.). .. The mixture of the diamine diamine and the trimer triamine is a mixture of the diamine diamine represented by the following formula (4) and the trimer triamine represented by the following formula (5), and the diamine diamine: trimer triamine = 80: 20 (weight ratio). It is a mixture contained in the ratio of.
58.8 parts by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred under reflux for 2 hours to react to obtain a maleic anhydride solution. Then, a Dean-Stark trap was attached, and the obtained maleaemia acid solution was stirred and reacted under reflux for 12 hours to dehydrate and cyclize the maleein amid acid. The maleimide composition A was obtained by cooling to room temperature, performing extraction washing with 1000 parts by weight of pure water three times, drying with 100 parts by weight of magnesium sulfate, and then removing toluene under reduced pressure.
The ^{maleimide composition A obtained by 1} H-NMR, GPC, GC-MS and FT-IR analysis is a trismaleimide compound represented by the above formula (1) as the polyfunctional maleimide compound according to the present invention. Was confirmed to contain 20% by weight, and 80% by weight of the bismaleimide compound represented by the following formula (6) was confirmed as another imide compound.

(Synthesis Example 2 (Preparation of Maleimide Composition B))
Synthesis Example 1 except that 136 parts by weight of dimerdiamine (“PRIAMINE 1074” manufactured by Croda Japan) represented by the above formula (4) was used instead of 140 parts by weight of the mixture of dimerdiamine and trimertriamine. The maleimide composition B was obtained in the same manner as above.
The ^{maleimide composition B obtained by 1} H-NMR, GPC, GC-MS and FT-IR analysis does not contain the polyfunctional maleimide compound according to the present invention and is represented by the above formula (6). It was confirmed that the vismaleimide compound was contained in an amount of 99% by weight.

(Examples 1 and 2, Comparative Examples 1 and 2)
Each material was stirred and mixed according to the compounding ratio shown in Table 1 to prepare each curable resin composition of Examples 1 and 2 and Comparative Examples 1 and 2.
Each of the obtained curable resin compositions was coated on a base material PET film so as to have a thickness of about 20 μm, and dried to obtain a curable resin composition film.

<Evaluation>
The following evaluations were performed on each curable resin composition and each curable resin composition film obtained in Examples and Comparative Examples. The results are shown in Table 1.

(Glass transition temperature of cured product)
The base material PET film was peeled off from each of the curable resin composition films obtained in Examples and Comparative Examples, laminated using a laminator, and then cured by heating at 190 ° C. for 1 hour to cure to a thickness of 400 μm. I made a thing. The obtained cured product was used at a temperature rise rate of 10 ° C./min, a frequency of 10 Hz, and a chuck distance of 24 mm at 0 ° C. using a dynamic viscoelasticity measuring device (“Leovibron DDV-25GP” manufactured by A & D Co., Ltd.). The peak temperature of the tan δ curve obtained when the temperature was raised to 300 ° C. was determined as the glass transition temperature.
When the glass transition temperature was 120 ° C. or higher, it was rated as “◯”, when it was lower than 120 ° C. and 100 ° C. or higher, it was rated as “Δ”, and when it was lower than 100 ° C., it was rated as “x”.

(Heat-decomposable (1% weight loss temperature))
The base material PET film was peeled off from each of the curable resin composition films obtained in Examples and Comparative Examples, and cured by heating at 190 ° C. for 1 hour to prepare a cured product.
The weight of the obtained cured product is reduced by 1% in a temperature range of 30 ° C to 500 ° C and a temperature rise condition of 10 ° C / min using a thermogravimetric measuring device (“TG / DTA6200” manufactured by Hitachi High-Tech Science Co., Ltd.). The temperature was measured.
The case where the 1% weight loss temperature was 390 ° C. or higher was designated as "◯", the case where the temperature was lower than 390 ° C. and higher than 370 ° C. was "Δ", and the case where the temperature was lower than 370 ° C. was "x".

(Dissipation factor)
The base material PET film was peeled off from each of the curable resin composition films obtained in Examples and Comparative Examples, cut into a size of 2 mm in width and 80 mm in length, laminated using a laminator, and then laminated at 190 ° C. 1 It was cured by heating for an hour to prepare a cured product having a thickness of 400 μm. For the obtained cured product, at 25 ° C, a dielectric constant measuring device (Kanto Denshi Applied Development Co., Ltd., "Cavity Resonant Permittivity Measuring Device CP521" and a network analyzer (KeySight Technology Co., Ltd., "Network Analyzer N5224A PNA"" ) Was used to measure the dielectric positive contact under the condition of 5.8 GHz by the cavity resonance method.
The case where the dielectric loss tangent was less than 0.0035 was designated as “◯”, the case where it was 0.0035 or more and less than 0.0040 was designated as “Δ”, and the case where it was 0.0040 or more was designated as “x”.

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product having excellent heat resistance, mechanical strength, and dielectric properties. Further, according to the present invention, it is possible to provide a laminate made of the curable resin composition.

11 Multilayer board 12 Circuit board 12a Top surface 13 to 16 Hardened material layer 17 Metal layer (wiring)

Claims (6)

Contains curable resin and imide compound,
The curable resin composition is characterized in that the imide compound contains a polyfunctional maleimide compound having a trimertriamine residue. The curable resin composition according to claim 1, wherein the content of the polyfunctional maleimide compound having the trimertriamine residue in the imide compound is 5% by weight or more and 50% by weight or less. The curable resin composition according to claim 1 or 2, wherein the content of the imide compound in a total of 100 parts by weight of the curable resin and the imide compound is 0.1 parts by weight or more and 50 parts by weight or less. The curability according to claim 1, 2 or 3, wherein the curable resin contains at least one selected from the group consisting of an epoxy resin, a cyanate resin, a phenol resin, an active ester resin, a carbodiimide resin, and a benzoxazine resin. Resin composition. The curable resin composition according to claim 1, 2, 3 or 4, which contains inorganic particles. A laminate having a substrate and a cured product of the curable resin composition according to claim 1, 2, 3, 4 or 5 laminated on the substrate.

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