JP2009242737A - Thermosetting resin composition, its preparation, and copper plated laminate plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition with the excellent thermal resistance, preferable electric characteristics and the brittleness dramatically improved, and its preparation. <P>SOLUTION: The resin composition is made of a resin (A) before thermosetting having a dihydrobenzoxazine structure reprsented by general formula (IV) and a resin (B) after thermosetting. In general formula (IV), Ar<SP>1</SP>is a quadrivalent aromatic group, R<SP>1</SP>is a hydrocarbon group as a residue of diamine, and n is an integer of 2-500. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition that has excellent heat resistance and good electrical characteristics, and a method for producing the same.

As polymer insulating materials used for copper-clad laminates, the following points have been mainly desired.
(1) It has been demanded that a polymer insulating material and a copper foil bonded to the polymer insulating material cannot be peeled off at a use temperature of high temperature to low temperature.
One of the causes of copper foil peeling is that the coefficient of thermal expansion (hereinafter also referred to as “CTE”) of copper foil is different from the CTE of the insulating material and the rate of expansion of the material with respect to temperature change: 18 ppm / ° C. Was considered. When the temperature changes, the insulation material and copper extend in different amounts, and a stress corresponding to the amount of extension occurs at the interface between different materials, and when this generated stress exceeds the peel strength, the insulation material and copper foil peel off. Because it ends up. From the above, in order to prevent peeling, it has been desired that the CTE of the polymer insulating material is close to that of copper.

(2) It has been required to lower the temperature during curing.
It has been desired that the curing temperature of the thermosetting resin be 200 ° C. or less, particularly 180 ° C. or less, due to the limitation of the hot press process for curing. This is because a lower curing temperature is desirable in terms of energy efficiency, equipment construction, and cost.

(3) It has been required to reduce the dielectric constant ε and the dielectric loss tan δ.
In recent years, CPUs, computers, and computer motherboards that use digital signals with clocks within or outside 1 GHz or exceeding 1 GHz have been used. Therefore, in order to deal with digital signals, an insulating material of either or both of tan δ having a small dielectric constant ε and a small dielectric loss has been desired.

As a means for solving the above-mentioned problem, as a technique for reducing CTE, “a composition comprising an organic polymer insulating material and silica (SiO 2) can be cited (for example, see Patent Document 1).
However, the addition of silica to the organic polymer insulating material reduces the CTE, but increases the dielectric constant of the blend. This is because the dielectric constant of silica is large, that is, the dielectric constant of silica is 4.2 while the dielectric constant of the organic polymer insulating material is 2.7-3. Therefore, there has been a demand for a thermosetting resin composition, a copper-clad laminate, and a method for producing the same, which are excellent in heat resistance and electrical characteristics.
JP-A-6-321221

  An object of this invention is to provide the thermosetting resin composition excellent in heat resistance, and an electrical property, a copper clad laminated board, and its manufacturing method.

〔一般式（ＩＶ）において、Ａｒ^１は、４価の芳香族基を示し、Ｒ¹は、ジアミンの残基である炭化水素基であり、ｎは、２〜５００の整数を示す。〕
本発明の第２の特徴は、一般式（Ｉ−１）又は（Ｉ−２）で示される多官能フェノール化合物、ジアミン化合物、アルデヒド化合物を加熱して反応させて、一般式（ＩＶ）で表されるジヒドロベンゾキサジン構造を有する熱硬化前の樹脂（Ａ）を製造する工程と、

［式（Ｉ）中、Ｘは直接結合手（原子もしくは原子団が存在しない）、または炭化水素基を表わす。］

〔一般式（ＩＶ）において、Ａｒ^１は、４価の芳香族基を示し、Ｒ¹は、ジアミンの残基である炭化水素基であり、ｎは、２〜５００の整数を示す。〕
熱硬化前の樹脂（Ａ）を硬化させて熱硬化後の樹脂（Ｂ）を得る工程と、熱硬化前の樹脂（Ａ）及び熱硬化後の樹脂（Ｂ）を混合する工程と、を有する樹脂組成物の製造方法を要旨とする。 The first feature of the present invention is a resin composition comprising a resin (A) before thermosetting having a dihydrobenzoxazine structure represented by the general formula (IV) and a resin (B) after thermosetting. Is the gist.

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group which is a residue of diamine, and n represents an integer of 2 to 500. ]
The second feature of the present invention is that the polyfunctional phenol compound, diamine compound, and aldehyde compound represented by the general formula (I-1) or (I-2) are heated and reacted, and represented by the general formula (IV). Producing a resin (A) before thermosetting having a dihydrobenzoxazine structure,

[In the formula (I), X represents a direct bond (no atom or atomic group is present) or a hydrocarbon group. ]

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group which is a residue of diamine, and n represents an integer of 2 to 500. ]
A step of curing the resin (A) before thermosetting to obtain a resin (B) after thermosetting, and a step of mixing the resin (A) before thermosetting and the resin (B) after thermosetting. The gist of the method for producing the resin composition is as follows.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in heat resistance and a thermosetting resin composition with a favorable electrical property, a copper clad laminated board, and its manufacturing method are provided.

  Hereinafter, the present invention will be described with reference to embodiments, but the present invention is not limited to the following embodiments.

  As a result of intensive studies, the present inventor achieved the above object with a composition of a heat-cured benzoxazine resin and an uncured benzoxazine resin from the viewpoint of improving heat resistance, lowering the curing temperature, and reducing CTE. Obtained knowledge of obtaining. The present invention is based on such knowledge. That is, the configuration of the present invention is as follows. Hereinafter, the “benzoxazine resin” refers to a resin having the above-mentioned dihydrobenzoxazine ring structure.

［式（Ｉ）中、Ｘは直接結合手（原子もしくは原子団が存在しない）、または炭化水素基を表わす。］

〔一般式（ＩＶ）において、Ａｒ^１は、４価の芳香族基を示し、Ｒ¹は、ジアミンの残基である炭化水素基であり、ｎは、２〜５００の整数を示す。〕
（ロ）熱硬化前の樹脂（Ａ）を硬化させて熱硬化後の樹脂（Ｂ）を得る工程と、
（ハ）熱硬化前の樹脂（Ａ）及び熱硬化後の樹脂（Ｂ）を混合する工程と、を有する。以下各成分等について詳細に説明する。 [Method for producing thermosetting resin]
The method for producing a thermosetting resin according to the embodiment is as follows.
(A) Dihydrobenzoxazine represented by the general formula (IV) by heating and reacting the polyfunctional phenol compound, diamine compound or aldehyde compound represented by the general formula (I-1) or (I-2) A step of producing a resin (A) before thermosetting having a structure;

[In the formula (I), X represents a direct bond (no atom or atomic group is present) or a hydrocarbon group. ]

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group which is a residue of diamine, and n represents an integer of 2 to 500. ]
(B) curing the resin (A) before thermosetting to obtain the resin (B) after thermosetting;
(C) mixing the resin (A) before thermosetting and the resin (B) after thermosetting. Hereinafter, each component will be described in detail.

(A) Polyfunctional phenol compound The polyfunctional phenol compound represented by the general formula (I) is not particularly limited as long as it is a bifunctional or higher polyfunctional phenol. These bifunctional or higher polyfunctional phenols are used alone or in combination of two or more.

  In the polyfunctional phenol compound, X in the general formula (I) is an organic group having 6 or more carbon atoms, preferably 8 or more carbon atoms, more preferably 12 to 21 carbon atoms, including an aromatic ring. X may have N, O, or F as a hetero atom.

  X is bonded to the OH groups of the benzene rings on both sides, particularly in terms of reactivity during synthesis of the thermosetting resin, heat resistance of the cured body, mechanical properties, and electrical properties, and It is preferable that the structure is any one or any of the following.

〔各式中、*印は前記構造（I）における芳香環への結合部位を示す。〕 Further, X is preferably a structure represented by the following X1 to X5 from the viewpoints of reactivity at the time of thermosetting resin synthesis, heat resistance of a cured product, mechanical properties, and electrical properties.

[In each formula, * indicates the binding site to the aromatic ring in the structure (I). ]

〔式中、ａは０〜１０の整数を示す。〕

[In formula, a shows the integer of 0-10. ]

〔式中、ｂは０〜１０の整数を示す。〕

[Wherein, b represents an integer of 0 to 10. ]

〔式中、ｃは０〜１０の整数を示す。〕

[In formula, c shows the integer of 0-10. ]

  In X1 to X4, hydrogen in each aromatic ring may be substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group.

  Specific examples of such polyfunctional phenolic compounds include 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 2,6-bis ((2-hydroxyphenyl ) Methyl) phenol, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals Co., Ltd .: bisphenol P), 4,4 ′-[1,3-phenylenebis (1- Methyl-ethylidene)] bisphenol (Mitsui Chemicals: Bisphenol M), biphenyl novolac type phenolic resin (Maywa Kasei: MEH7851), xylylene novolac type phenolic resin (Maywa Kasei: MEH7800), dicyclopentadiene modified phenolic resin (new) Nippon Petroleum: Nisseki special phenol resin DPP series) It is. These polyfunctional phenol compounds are used alone or in combination of two or more.

(B) Diamine compound As the diamine compound, it is preferable to use a linear aliphatic diamine having 12 or less carbon atoms.
The diamine compound is preferably a diamine represented by any one of the following formulas (II-1), (II-2), and (II-3).

〔式中、Ｙは炭素数５以上の有機基であり、ヘテロ原子として、Ｎ、Ｏ、Ｆを有していてもよい。ただし、Ｙの両側のベンゼン環はＹ中の異なる原子に結合する。〕 The diamine compound is preferably a diamine represented by the general formula (II-3).

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

Y in the general formula (II-3) is preferably a group represented by the following formula (Y1), particularly in terms of solubility during thermosetting resin synthesis, mechanical properties of the cured product, and electrical properties. Is more preferably bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene rings on both sides thereof.

  Further, Y preferably contains one benzene ring from the viewpoint of heat resistance, mechanical properties and electrical properties of the cured product.

Y in the general formula (II-3) is preferably one or more groups selected from the groups Y2 and Y3 in the following formula, and Y is a meta-position or a para-group with respect to NH ₂ groups of the benzene rings on both sides thereof. More preferably, it is bonded to the position.

  Specific examples of such a diamine compound include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) neopentane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 4,4′-bis [(3-aminophenoxy) phenyl] biphenyl, 4,4′-bis [(4-aminophenoxy) phenyl] biphenyl, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- ( - aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, and the like. These diamine compounds are used singly or in combination.

(C) Aldehyde compound Although it does not specifically limit as an aldehyde compound, Formaldehyde is preferable, As this formaldehyde, it uses in forms, such as paraformaldehyde which is the polymer, and formalin which is the form of aqueous solution. Is possible. The reaction proceeds more slowly when paraformaldehyde is used. As other aldehyde compounds, acetaldehyde, propionaldehyde, butyraldehyde and the like can also be used.

  In the resin production method according to the embodiment, for example, the components (a), (b), and (c) may be heated and reacted in an appropriate solvent.

  The solvent used in the method for producing a resin according to the embodiment is not particularly limited, but those having better solubility of the raw material phenol compound, diamine compound and polymer as a product have a higher degree of polymerization. Things are easy to get. Examples of such a solvent include aromatic solvents such as toluene and xylene, halogen solvents such as chloroform and dichloromethane, ether solvents such as THF and dioxane, and the like.

  Although the reaction temperature and reaction time are not particularly limited, the reaction may usually be performed at a temperature of about room temperature to 120 ° C. for about 10 minutes to 24 hours. In particular, it is preferable to react at 30 to 110 ° C. for 20 minutes to 9 hours, because the reaction proceeds to a polymer that can exhibit the function as the thermosetting resin according to the embodiment. It is desirable to lower the reaction temperature or shorten the reaction time from the point that a resin having a higher molecular weight or a three-dimensionally crosslinked polymer is formed in a reaction at a high temperature and for a long time, and the reaction time is reduced. In this reaction, it is desirable to increase the reaction time or the reaction temperature in that a sufficiently large molecular weight resin suitable for coating cannot be synthesized.

From the viewpoint of sufficient crosslinking and high heat resistance, the firing temperature of the resin (B) after thermosetting is preferably 240 ° C. or higher and 300 ° C. or lower. Similarly, from the viewpoint of sufficient crosslinking and high heat resistance, the resin (B) after thermosetting has a peak at 58 ± 2 ppm as measured by ¹³ C NMR, and the half width of the peak is 4 to 4%. It is preferably in the range of 10 ppm. Furthermore, the resin (B) after thermosetting is classified, and the ratio of the powder having a long side of 5 μm or more is 1% by mass or less from the viewpoint of forming a fine line and space by etching the resin. preferable.

  Further, removing water generated during the reaction out of the system is also an effective technique for promoting the reaction. For example, a polymer can be precipitated by adding a large amount of poor solvent such as methanol to the solution after the reaction, and the desired polymer can be obtained by separating and drying the polymer.

  In addition, a monofunctional amine compound, a trifunctional amine compound, and another diamine compound can also be used in the range which does not impair the characteristic of the thermosetting resin which concerns on embodiment. When a monofunctional amine is used, the degree of polymerization can be adjusted, and when a trifunctional amine is used, a branched polymer is obtained. Moreover, physical properties can be adjusted by the combined use of other diamine compounds. These can be used at the same time as the diamine compound essential to the present invention, but can be added to the reaction system and reacted later in consideration of the order of the reaction.

〔一般式（ＩＶ）において、Ａｒ^１は、４価の芳香族基を示し、Ｒ¹は、ジアミンの残基である炭化水素基であり、ｎは、２〜５００の整数を示す。〕 [Thermosetting resin composition]
The thermosetting resin composition according to the embodiment includes a resin (A) before thermosetting and a resin (B) after thermosetting having a dihydrobenzoxazine structure represented by the general formula (IV).

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group which is a residue of diamine, and n represents an integer of 2 to 500. ]

The thermosetting resin which concerns on embodiment can be obtained with the manufacturing method of the thermosetting resin mentioned above.
The heat-cured benzoxazine resin may be obtained by baking the synthesized benzoxazine resin at 200 ° C. or more and 300 ° C. or less for 10 minutes to 1 hour in an oven or the like. About the hardening body after baking, it grind | pulverizes with a jet mill. For pulverization, any of a jet mill, a dry bead mill, and a wet bead mill may be used. It is desirable to use a wet bead mill in terms of handling the powder after grinding. About the hardening body after grind | pulverizing, it classifies using a wet classifier. A dry classifier may be used.
The pulverized benzoxazine resin after thermosetting and the non-thermosetting benzoxazine resin should be made into a composition by methods such as mixing in a solid layer, dispersion in a solvent, and dissolution and dispersion in a solvent. Can do.

  The thermosetting resin composition according to the embodiment has particularly excellent heat resistance and good electrical characteristics.

  The thermosetting composition according to the embodiment preferably contains the thermosetting resin as a main component, for example, the thermosetting resin as a main component, and another thermosetting as a subcomponent. It may also contain a functional resin.

Examples of other thermosetting resins as accessory components include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, melamine resins, urea resins, allyl resins, phenol resins, and unsaturated resins. Examples include polyester resins, bismaleimide resins, alkyd resins, furan resins, polyurethane resins, aniline resins, and the like. Among these, an epoxy resin, a phenol resin, and a thermosetting polyimide resin are more preferable from the viewpoint of further improving the heat resistance of a molded body formed from the composition. These other thermosetting resins may be used alone or in combination of two or more.
In the thermosetting composition according to the embodiment, it is preferable to use a compound having at least one, preferably two dihydrobenzoxazine rings in the molecule described in the publicly known literature as a subcomponent. Only one type of compound having at least one dihydrobenzoxazine ring in the molecule may be used, or two or more types may be used in combination.

  There are no particular restrictions on the epoxy resin, and specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, biphenyl type epoxy resin, and substituted bisphenol A type epoxy resin. , Cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol / biphenylene type epoxy resin, phenoxy resin, glycidyl ether type epoxy resin, 3,4-epoxycyclohexylmethyl Cyclic aliphatic epoxy resins such as -3 ', 4'-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate, adipic acid diglycidyl ester type, phthalic acid diglycol Glycidyl ester type epoxy resins such as glycidyl ester type, diglycidyl aniline type, aminophenol type, aliphatic amine type, hydantoin type glycidyl amine type epoxy resin, hydroxybenzoic acid type ester type, α-methylstilbene type liquid crystal Examples thereof include epoxy resins, epoxy resins having functions such as photosensitivity and decomposability, triglycidyl isocyanurate, and thiirane-modified epoxy resins. Among these, it is preferable to use a phenol / biphenylene type epoxy resin (for example, NC3000 series manufactured by Nippon Kayaku Co., Ltd.) from the viewpoint of flexibility and heat resistance.

  In addition, the thermosetting composition according to the embodiment includes a flame retardant, a nucleating agent, an antioxidant (anti-aging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, if necessary. Various additives such as an auxiliary agent, an antistatic agent, an antifogging agent, a filler, a layered silicate, a softener, a plasticizer, and a colorant may be contained. These may be used alone or in combination of two or more. Moreover, when preparing the thermosetting composition which concerns on embodiment, a reactive or non-reactive solvent can also be used.

  Further, when curing is performed, an appropriate curing accelerator may be added. As the curing accelerator, any curing accelerator generally used in ring-opening polymerization of a dihydrobenzoxazine compound can be used. For example, polyfunctional phenols such as catechol and bisphenol A, p- Sulfonic acids such as toluenesulfonic acid and p-phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid and adipic acid, cobalt (II) acetylacetonate, aluminum (III) acetylacetonate, zirconium (IV) acetyl Metal complexes such as acetonate, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide, iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diazabicycloundecene, diazabicyclononene, and These salts, triphenylphosphine, triphenylphosphine Examples thereof include phosphorus compounds such as tin / benzoquinone derivatives, triphenylphosphine / triphenylboron salts, tetraphenylphosphonium / tetraphenylborate and derivatives thereof. These may be used alone or in combination of two or more.

  The addition amount of the curing accelerator is not particularly limited. However, if the addition amount is excessive, the dielectric constant and dielectric loss tangent of the molded body may be increased to deteriorate the dielectric properties or adversely affect the mechanical properties. Therefore, in general, it is desirable to use the curing accelerator at a ratio of preferably 5 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the thermosetting resin.

  When an inorganic filler is used as the filler, the material of the inorganic filler is such that when the cured molded body of the thermosetting resin composition is roughened, the surface roughness of the cured molded body is small, and copper plating and curing are performed. Various inorganic fillers can be used without particular limitation as long as the adhesive strength with the molded body is increased. For example, powders such as silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, fosterite, steatite, spinel, mullite, titania, Or the beads, glass fiber, etc. which made these spherical are mentioned, These may be used independently or may be used in combination of 2 or more type. Of these, silica is preferable. This is because, in addition to the surface roughness, the number and shape of the holes contribute to the improvement in peel strength. Specifically, the product name “Admuffin” manufactured by Admatechs can be used. The blending amount of the inorganic filler subjected to the silane coupling treatment (excluding the solvent weight) is preferably 10 to 40 parts by weight, and 20 parts by weight when the total weight of the thermosetting resin composition is 100 parts by weight. 30 parts by weight is more preferable.

As the layered silicate (= clay), various types can be used without particular limitation. For example, natural or synthetic Na-type tetralithic fluorine mica, Li-type tetrasilicic fluorine mica, Na-type fluorine teniolite, or swellable mica-group clay minerals such as Li-type fluorine teniolite, vermiculite, smectite, saponite, stevensite, viterite , Smectite group clay minerals such as montmorillonite, nontronite, or bentonite, or substitutions, derivatives or mixtures thereof. In addition, in the substituted body, a part of Na ⁺ or Li ⁺ ion of the interlayer ion is substituted by K ⁺ ion, or a part of Si ⁺ ion of the tetrahedral sheet is substituted by Mg ²⁺ ion. Is included.
As the layered silicate, an organically modified layered silicate obtained by organically modifying a layered silicate with a quaternary ammonium salt type cationic surfactant or the like may be used. Specifically, synthetic smectite (Lucentite STN manufactured by Co-op Chemical Co., Ltd.) that has been subjected to organic treatment with dimethyldioctadecyl ammonium salt can be used. The amount of layered silicate is preferably 0.1 to 5 parts by weight, more preferably 2 to 3 parts by weight, when the total weight of the thermosetting resin is 100 parts by weight.

The thermosetting resin composition according to the embodiment may be dissolved in an organic solvent and cast, and the solvent may be dried to form a film.
About the thermosetting resin composition concerning this invention, the one where the solubility in organic solvents, such as toluene, is larger is preferable. This makes it possible to reduce the amount of solvent when casting into a solution to form a film. Further, if the solvent content is low, the energy for solvent evaporation is small, the drying time is short, and rapid drying is possible. This is because there is a secondary effect that there is no blistering caused.

The benzoxazine resin after thermosetting in the embodiment is a product obtained by thermosetting the benzoxazine resin of the synthesis example. At the time of thermosetting, 240 ° C. or higher, preferably 250 ° C. or higher from the viewpoint of sufficiently proceeding with ring-opening polymerization, and 300 ° C. or lower, preferably 290 ° C. or lower, from the viewpoint of thermal degradation. The curing time is 10 minutes to 24 hours, preferably 15 minutes to 4 hours.
From the viewpoint that the thermosetting has sufficiently progressed, as shown in WO JP / 2007129640NMR, it is desirable that a peak is observed at 58 ppm ± 2 ppm when NMR is measured.
As the resin composition according to the embodiment, since the thermosetting resin composition described above has moldability before curing, the dimensions and shape thereof are not particularly limited, and for example, a sheet shape (plate shape) In addition, a block shape and the like may be mentioned, and another part (for example, an adhesive layer) may be provided. Moreover, the sheet-like thing may be formed on the support film.

  When used for a copper-clad laminate, it is desirable to use a resin having a sufficiently small particle size as the resin (B) after thermosetting in terms of laser drilling workability and surface smoothness. Specifically, the proportion of the splits having a long side of 5 μm or more is 1% by mass or less. In practice, after pulverization, a conventionally known method such as a filtration operation or a separation operation using a cyclone may be performed.

[Copper laminate]
The resin composition may be made into a solution and then cast on a copper foil to evaporate the solvent to form a copper-clad laminate. You may heat-press at the temperature which does not complete | finish an effect. 80 to 120 ° C is desirable.

[Cured laminate after curing]
The cured copper-clad laminate according to the embodiment is obtained by applying heat to a copper-clad laminate composed of a thermosetting resin composition having a thermosetting property and a copper foil, and curing. As the curing method, any conventionally known curing method can be used. Generally, it may be heated at about 120 to 300 ° C. for several hours, but if the heating temperature is lower or the heating time is insufficient, In some cases, curing may be insufficient and mechanical strength may be insufficient. In addition, if the heating temperature is too high or the heating time is too long, side reactions such as decomposition may occur in some cases, and the mechanical strength may be disadvantageously reduced. Therefore, it is desirable to select appropriate conditions according to the characteristics of the thermosetting compound to be used. In particular, 200 degrees or less, more desirably 180 degrees C or less is desirable in terms of productivity.

  As described above, the copper-clad laminate according to the embodiment made of the thermosetting composition thus obtained has a benzoxazine resin that is uncured and has been cured in the composition, and thus can be cured at a low temperature. In addition, heat resistance and excellent dielectric properties can be realized.

The cured body according to the embodiment can be suitably used for applications such as electronic parts / electronic devices and materials thereof, multilayer boards, copper-clad laminates, sealants, adhesives and the like that particularly require excellent dielectric properties. .
Here, the electronic component includes a substrate or an IC element having a terminal for electrical connection such as a flexible substrate, an electric conductor layer on the surface of the cured body according to the embodiment, a resistor, a capacitor, a coil, Refers to the board on which is mounted.

Although the typical Example in this invention is shown below, this invention is not limited at all by this.
[Synthesis Example of Thermosetting Resin Having Dihydrobenzoxazine Ring of Formula (IV) (hereinafter referred to as BO1)]
In chloroform, bisphenol M (Mitsui Chemicals, 99.5%) 27.86 g (0.08 mol), bisaniline M (Mitsui Chemicals, 99.98%) 27.57 g (0.08 mol), paraformaldehyde (Japanese) 1003) 10.73 g (0.34 mol) was added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 31.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. In the molecular weight measurement of the obtained resin by GPC, the weight average molecular weight was 16,600.

[Preparation of resin (B) after thermosetting]
The BO1 benzoxazine resin was heated in an oven at 260 ° C. for 30 minutes. After this, Nissin Engineering Co., Ltd., BM-15 and CJ-10, pulverized, sieved to 25 μm, further dispersed in toluene, filtered through a membrane filter with a pore size of 5 μ to remove large particles of 5 μm or larger did.
[Preparation of benzoxazine resin before thermosetting]
In chloroform, bisphenol M (Mitsui Chemicals, 99.5%) 27.86 g (0.08 mol), bisaniline M (Mitsui Chemicals, 99.98%) 20.68 g (0.06 mol), 1,12- Diaminododecane (manufactured by Ogura Kasei Kogyo Co., Ltd.) 4.00 g paraformaldehyde (manufactured by Wako Pure Chemicals, 94%) 10.73 g (0.34 mol) was added, and the reaction was carried out for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 31.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure. In the molecular weight measurement of the obtained resin by GPC, the weight average molecular weight was 12,200. (Abbreviated as BO2)

[Production of resin composition and resin composition film]
0.10 g of the cured BO1 benzoxazine resin and 0.90 g of the uncured BO2 benzoxazine resin were stirred in a shaker for 1 hour using 1.50 g of toluene as a solvent, and the solid content was 40%. A dispersion was prepared. After defoaming the produced resin composition dispersion, coating was performed on release-treated PET using a coating machine in which an applicator was set to obtain a film containing a solvent. The film was dried at 60 ° C. to 100 ° C. and then held at 160 ° C. for 30 minutes and at 180 ° C. for 2 hours to obtain a cured film. The cured film was 60 μm thick.
Further, the obtained film was finely cut and evaluated for 5% weight loss temperature (Td5) in an air atmosphere at a temperature rising rate of 10 ° C./min using TG / DTA6200 manufactured by SII. It was.
The dielectric constant and dielectric loss tangent were 2.7 GHz and dielectric loss tangent were 0.0045 as measured using HP 8510 and a cavity resonator cell.

"Comparative example"
When producing the resin composition film, the same procedure was followed except that 1.00 g of an uncured body of BO2 was used instead of 0.10 g of the cured body of BO1 and 0.90 g of the uncured resin of BO2. A cured product of the resin composition film was prepared.
Further, the obtained film was finely cut and evaluated for 5% weight loss temperature (Td5) in an air atmosphere at a heating rate of 10 ° C./min using SII TG / DTA6200. It was.
The dielectric constant and dielectric loss tangent were 2.7 GHz and dielectric loss tangent were 0.0045 as measured using HP 8510 and a cavity resonator cell.

Claims (29)

A resin composition comprising a resin (A) before thermosetting having a dihydrobenzoxazine structure represented by the general formula (IV) and a resin (B) after thermosetting.

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group which is a residue of diamine, and n represents an integer of 2 to 500. ] The resin composition according to claim ^1, wherein Ar ¹ is represented by the following formula.

[In formula (iii), X represents a direct bond (no atom or atomic group is present) or a hydrocarbon group. ] The resin composition according to claim 2, wherein X is a group selected from the following group A.

[In each formula, * indicates the binding site to the aromatic ring in the structure (IV). ] The resin composition according to claim 2, wherein X is represented by the following formula.

[In formula, a shows the integer of 0-10. ] The resin composition according to claim 2, wherein X is represented by the following formula.

[Wherein, b represents an integer of 0 to 10. ] The resin composition according to claim 2, wherein X is represented by the following formula.

[In formula, c shows the integer of 0-10. ]   The hydrogen in each aromatic ring is substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group. The resin composition according to any one of the above.   The resin composition according to any one of claims 1 to 7, wherein the resin (A) before thermosetting is redissolvable with a solvent and can be separated from the benzoxazine resin after thermosetting.   The resin composition according to any one of claims 1 to 8, wherein a baking temperature of the resin (B) after the thermosetting is 240 ° C or higher and 300 ° C or lower. The resin (B) after the thermosetting has a peak at 58 ± 2 ppm as measured by ¹³ C NMR, and the half width of the peak is in the range of 4 to 10 ppm. The resin fired product according to any one of the above items.   The resin (B) after the thermosetting is classified, and the ratio of the powder having a long side of 5 μm or more is 1% by mass or less. Resin composition.   The resin composition according to claim 1, wherein the resin composition is used as an insulating material for a copper-clad laminate.   The copper clad laminated board obtained by thermosetting the composition of any one of Claims 1-12.   The copper-clad laminate according to claim 13, wherein the thermosetting temperature is 200 ° C. or less. A polyfunctional phenol compound represented by general formula (I-1) or (I-2), a diamine compound, and an aldehyde compound are reacted by heating to have a dihydrobenzoxazine structure represented by general formula (IV) A step of producing a resin (A) before thermosetting;

[In the formula (I), X represents a direct bond (no atom or atomic group is present) or a hydrocarbon group. ]

[In General Formula (IV), Ar ¹ represents a tetravalent aromatic group, R ¹ represents a hydrocarbon group that is a residue of the diamine, and n represents an integer of 2 to 500. ]
Curing the resin (A) before thermosetting to obtain a resin (B) after thermosetting;
Mixing the resin before thermosetting (A) and the resin after thermosetting (B);
The manufacturing method of the resin composition characterized by having. 16. The method for producing a resin composition according to claim 15, wherein X is a group selected from the following group A.

[In each formula, * indicates the binding site to the aromatic ring in the structure (I). ] The said X is shown by following Formula, The manufacturing method of the resin composition of Claim 15 characterized by the above-mentioned.

[In formula, a shows the integer of 0-10. ] The said X is shown by following Formula, The manufacturing method of the resin composition of Claim 15 characterized by the above-mentioned.

[Wherein, b represents an integer of 0 to 10. ] The said X is shown by following Formula, The manufacturing method of the resin composition of Claim 15 characterized by the above-mentioned.

[In formula, c shows the integer of 0-10. ]   20. The hydrogen of each aromatic ring is substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group. A method for producing the resin composition.   The method for producing a resin composition according to any one of claims 15 to 20, wherein the diamine compound is a linear aliphatic diamine having 12 or less carbon atoms. The method for producing a resin composition according to any one of claims 15 to 20, wherein the diamine compound is a diamine represented by any one of the following formulae.

The said diamine compound is diamine represented by general formula (II-3), The manufacturing method of the resin composition of any one of Claims 15-20 characterized by the above-mentioned.

[Wherein Y is an organic group having 5 or more carbon atoms and may have N, O, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ] The Y in the general formula (II-3) is a group represented by the following formula, and Y is bonded to a meta position or a para position with respect to NH ₂ groups of benzene rings on both sides thereof. 24. A method for producing a resin composition according to 23.

Y in the general formula (II-3) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene rings on both sides thereof. The method for producing a resin composition according to claim 23.

Y in the general formula (II-3) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta position or the para position with respect to the NH ₂ groups of the benzene rings on both sides thereof. The method for producing a resin composition according to claim 23.

  27. The method for producing a resin composition according to any one of claims 15 to 26, wherein the baking temperature of the resin (B) after thermosetting is 240 ° C. or higher and 300 ° C. or lower. The resin (B) after thermosetting has a peak at 58 ± 2 ppm as measured by ¹³ C NMR, and the half width of the peak is in the range of 4 to 10 ppm. A method for producing the resin composition according to claim 1.   29. The resin (B) after thermosetting is classified, and the proportion of powder having a long side of 5 μm or more is 1% by mass or less. A method for producing a resin composition.