JP2014070087A - Resin dispersion, resin composition, resin composition composite, and laminate sheet - Google Patents

Abstract

An excellent performance of polyphenylene ether resin, that is, a dielectric dispersion, a glass transition temperature (Tg), and a heat resistance, which can be well-balanced and easily produced, and obtained using the resin dispersion A resin composition composite and a laminate are provided.
A functionalized polyphenylene ether comprising a functionalized polyphenylene ether resin (A) and an organic solvent (B), wherein the functionalized polyphenylene ether resin (A) has a number average molecular weight (Mn) of 5000 to 40000. 30 to 90% by mass of the total amount of the resin (A) is present as particles in the organic solvent (B), and the functionalized polyphenylene ether resin (A) has a hydroxyl group at the terminal of the polyphenylene ether. A resin dispersion having a structure functionalized with a functional group in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the polyphenylene ether resin (A).
[Selection figure] None

Description

  The present invention provides a resin dispersion containing polyphenylene ether (hereinafter, also referred to as PPE) resin particles suitable as an electronic substrate material, and a resin composition produced using a varnish containing the resin dispersion and a substrate. The present invention relates to a product composite, and a laminate for electrical and electronic parts formed using the resin composition composite.

  A laminate used in a high frequency region such as satellite communication is required to have excellent dielectric properties. Polyphenylene ether is attracting attention as a material having a stable dielectric constant and dielectric loss tangent in a wide frequency range, temperature range and humidity range, and a low dielectric loss tangent.

  As a manufacturing method of a laminated board, there exists a method of impregnating a base material with the solution obtained by melt | dissolving polyphenylene ether in the non-halogen solvent heated and hold | maintained. However, this method requires complicated equipment and has problems in terms of handleability, work safety, environmental problems, and the like, and a manufacturing method that does not hold by heating is required.

  Thus, for example, Patent Document 1 and Patent Document 2 provide a method for obtaining an opaque resin liquid in which a resin component is dispersed by once heating and then cooling a resin liquid containing polyphenylene ether. Patent Document 1 describes a resin liquid containing a resin containing polyphenylene ether and an epoxy resin. Patent Document 2 describes that in order to obtain a laminate having excellent dielectric properties, a resin liquid is obtained using a polyphenylene ether resin having a Mn of 1000 to 3000 as a main component. Patent Document 3 describes a method in which a polyphenylene ether resin is stably dispersed in an aqueous solvent using a surfactant, and the particle size of the polyphenylene ether particles is 106 μm or less.

Japanese Patent Laid-Open No. 9-104094 JP 2008-50526 A JP 2003-34731 A

  However, although the above-described conventional technique can obtain a dispersion having coating properties at room temperature, for example, in Patent Documents 1 and 2, the heat resistance inherent in polyphenylene ether is sufficiently expressed. In addition, in Patent Document 3, the adhesiveness of the resin / cloth was not sufficient in the produced prepreg, and it was necessary to further improve these characteristics. In other words, the prior art uses a resin composition composite (for example, prepreg) that is suitable for an electronic substrate and has good adhesion between the resin and the base material, and has excellent heat resistance using the resin composition composite. It is not possible to provide a polyphenylene ether resin dispersion for obtaining a laminate having the same.

  Therefore, the problem to be solved by the present invention is a resin dispersion excellent in room temperature flow stability, which can be easily produced using a polyphenylene ether resin as a raw material, and is excellent in resin composition composite (for example, prepreg) and a substrate. Resin dispersion capable of producing a resin composition that gives excellent adhesiveness and a cured resin composition excellent in heat resistance, and a resin composition composite (for example, prepreg) and laminate obtained using the resin dispersion It is to provide a board.

In order to solve the above problems, the present inventors have intensively studied and repeated experiments, and as a result, unexpectedly include a functionalized polyphenylene ether resin in which the hydroxyl group at the terminal of the polyphenylene ether resin is functionalized as a raw material. The present inventors have found that the above problems can be solved by using a resin dispersion, and have completed the present invention.
That is, the present invention is as follows.

[1] containing a functionalized polyphenylene ether resin (A) and an organic solvent (B),
The functionalized polyphenylene ether resin (A) has a number average molecular weight (Mn) of 5000 to 40000,
30 to 90% by mass of the total amount of the functionalized polyphenylene ether resin (A) is present as particles in the organic solvent (B),
In the functionalized polyphenylene ether resin (A), the hydroxyl group at the terminal of the polyphenylene ether is functionalized with a functional group in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the functionalized polyphenylene ether resin (A). A resin dispersion having a structure.
[2] The resin dispersion according to [1], wherein in the functionalized polyphenylene ether resin (A), a terminal hydroxyl group of the polyphenylene ether is functionalized with an acid anhydride.
[3] The resin dispersion according to [2], wherein the acid anhydride is maleic anhydride.
[4] The resin dispersion according to any one of [1] to [3], wherein 60% or more of the total number of the particles has a major axis of 3 μm or more and 30 μm or less.
[5] The resin dispersion according to any one of [1] to [4], further including a crosslinkable curable component (C) and an initiator (D).
[6] A varnish containing the resin dispersion according to any one of [1] to [5].
[7] A resin composition obtained by removing the solvent from the varnish described in [6].
[8] A resin composition obtained by applying a varnish containing the resin dispersion liquid according to any one of [1] to [5] to a substrate, and then removing the solvent from the substrate to which the varnish is applied. Compound complex.
[9] A laminate comprising a layer obtained from the resin composition according to [7] or a layer obtained from the resin composition composite according to [8].

  According to the present invention, it is possible to obtain a resin dispersion that can be applied at room temperature for producing a resin composition composite (for example, prepreg) having excellent adhesion between the resin and the substrate, and further the resin composition. A laminate produced using the composite can exhibit the excellent heat resistance of the polyphenylene ether resin.

  Hereinafter, although the embodiment of the present invention is described in detail, it is not intended that the present invention be limited to these embodiments.

<Resin dispersion>
This embodiment
Including a functionalized polyphenylene ether resin (A) and an organic solvent (B),
The functionalized polyphenylene ether resin (A) has a number average molecular weight (Mn) of 5000 to 40000,
30 to 90% by mass of the total amount of the functionalized polyphenylene ether resin (A) is present as particles in the organic solvent (B),
In the functionalized polyphenylene ether resin (A), the hydroxyl group at the terminal of the polyphenylene ether is functionalized with a functional group in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the functionalized polyphenylene ether resin (A). There is provided a resin dispersion having a structure.

[Functionalized polyphenylene ether resin (A)]
In the functionalized polyphenylene ether resin (A), the hydroxyl group at the end of the polyphenylene ether is functionalized, so that the crystal precipitation temperature from the solution can be lowered compared to the unmodified polyphenylene ether, As a result, it is possible to suppress excessive crystal particle growth in the room temperature region when the resin dispersion is produced by heating and then cooling the resin liquid. By using functionalized polyphenylene ether, it is possible to easily adjust the precipitation amount and particle size of the resin particles in the resin dispersion in a normal temperature range, so that fluidity is good even at normal temperature, varnish stability and A resin dispersion excellent in coating uniformity can be obtained. In addition, the ability to suppress crystal precipitation in the room temperature range enables a large amount of dissolved polyphenylene ether to be preserved at the same time. Dissolved polyphenylene ether has high wettability with the base material and can reduce the viscosity of the resin composition during heat molding. The cured body produced from the resin composition composite also has excellent heat resistance.

（式中、Ｒ₁〜Ｒ₈は、各々独立して、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよいアミノ基、ニトロ基又はカルボキシル基を表し、Ｒ₉は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよいアミノ基、ニトロ基又はカルボキシル基である）
で表される構造を含む。すなわちＲ₉は官能化によって導入された官能基である。官能基化ポリフェニレンエーテル樹脂（Ａ）は、官能化された構造（例えば上記式（１）で表される構造）に加え、未変性構造（例えば上記式中のＲ₉の部位が水素原子である構造）を有してもよい。官能基化ポリフェニレンエーテル樹脂（Ａ）は、ポリフェニレンエーテル骨格を有する２種以上の樹脂の混合物であってもよく、官能基化ポリフェニレンエーテル樹脂（Ａ）全体として本発明所定の特性を満足すればよい。例えば、官能基化ポリフェニレンエーテル樹脂（Ａ）は、本発明の効果を損なわない範囲で、未変性ポリフェニレン分子を含んでもよい。 The functionalized polyphenylene ether resin (A) has a polyphenylene ether skeleton, and typically has the following formula (1):

(In the formula, R _{1 to} R ₈ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. Represents an aryl group which may have a substituent, an amino group which may have a substituent, a nitro group or a carboxyl group, and R ₉ may have a halogen atom, an alkyl group which may have a substituent, or a substituent. An alkoxy group, an aryl group which may have a substituent, an amino group which may have a substituent, a nitro group or a carboxyl group)
The structure represented by is included. That is, R ₉ is a functional group introduced by functionalization. The functionalized polyphenylene ether resin (A) has a functionalized structure (for example, a structure represented by the above formula (1)) and an unmodified structure (for example, the R ₉ site in the above formula is a hydrogen atom). Structure). The functionalized polyphenylene ether resin (A) may be a mixture of two or more resins having a polyphenylene ether skeleton, and the functionalized polyphenylene ether resin (A) as a whole should satisfy the predetermined characteristics of the present invention. . For example, the functionalized polyphenylene ether resin (A) may contain unmodified polyphenylene molecules as long as the effects of the present invention are not impaired.

Specific examples of the structure before functionalization of the functionalized polyphenylene ether resin (A) (referred to as polyphenylene ether in the present disclosure), for example, a structure in which R ₉ is a hydrogen atom in the general formula (1) include, for example, Poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether) ), Poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol, 2-methyl-6- And polypheny obtained by coupling 2,6-dimethylphenol and biphenols or bisphenols. N'eteru copolymer, and the like. In view of availability, poly (2,6-dimethyl-1,4-phenylene ether) is a preferred example.

  The number average molecular weight Mn of the functionalized polyphenylene ether resin (A) is 5000 or more and 40000 or less, preferably 8500 or more and 30000 or less, and more preferably 9000 or more and 25000 or less. When Mn is 5000 or more, a resin dispersion capable of forming a cured product excellent in Tg and solder heat resistance is obtained, and when it is 40000 or less, a resin dispersion having excellent substrate moldability is obtained because the melt viscosity is appropriate. Is obtained.

  Examples of the functional group added by functionalization include benzyl group, vinylbenzyl group, allyl group, propargyl group, glycidyl group, methacryl group, cyano group, maleic acid group, and the like. You may combine.

  In a preferred embodiment, the hydroxyl group of the polyphenylene ether is functionalized with an acid anhydride. Examples of the acid anhydride include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. Maleic anhydride is preferred because crystallization during cooling of the resin liquid is suppressed and the fluidity of the resin dispersion can be easily secured without precipitation of excess particles.

  The functionalization reaction is performed, for example, by heating polyphenylene ether and acid anhydride in a temperature range of 100 ° C to 390 ° C. At this time, a radical initiator may coexist. Both the solution method and the melt mixing method can be used, but the melt mixing method using an extruder or the like is more preferable in that it is simple.

  In this embodiment, the addition amount of the functional group by the acid anhydride etc. to a hydroxyl group is 0.1 mass part or more as a ratio with respect to 100 mass parts of functionalized polyphenylene ether resin (A). The added amount is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less. Further, as described above, the functionalized polyphenylene ether resin (A) does not need to be functionalized in all the polyphenylene ethers contained therein, and may contain unfunctionalized (ie, unmodified) polyphenylene ether. . Since the above ratio is functionalized per 100 parts by mass of the whole polyphenylene ether resin contained in the resin dispersion, an effect of preventing excessive precipitation of particles at room temperature is brought about. Thereby, not only fluidity | liquidity can be ensured but the resin dispersion liquid which can manufacture the resin composition composite excellent in the adhesiveness of resin and a base material can be obtained easily. For example, when the functionalized polyphenylene ether resin (A) in the resin dispersion is functionalized with an acid anhydride, the functional group addition amount can be measured by neutralization titration of a general carboxylic acid. For example, a base such as sodium hydroxide is added to the solution containing the functionalized polyphenylene ether resin (A) until the solution is neutralized, and the functionalized polyphenylene ether resin (A ) Can be calculated. For example, when an acid anhydride is used, the functionalized polyphenylene ether resin (A) having the above addition amount is obtained by controlling the equivalent amount of the acid anhydride and the radical initiator with respect to the polyphenylene ether resin before functionalization. For example, when a benzyl group is introduced, it can be obtained by blending the equivalent of benzyl chloride or benzyl bromide and the base with the equivalent of the hydroxyl group of the polyphenylene ether resin before functionalization.

  In the present embodiment, a part of the functionalized polyphenylene ether resin (A) in the resin dispersion is present as particles in the organic solvent, and the remainder is dissolved in the organic solvent. The proportion of the particles is 30% by mass or more and 90% by mass or less, preferably 30% by mass or more and 80% by mass or less, more preferably 30% by mass or more, with respect to 100% by mass of the total amount of the functionalized polyphenylene ether resin (A). 75% by mass or less. When the ratio of the particles is 30% by mass or more, an appropriate resin dispersion having a viscosity excellent in dispersion stability at room temperature can be obtained. In addition, when the ratio of the particles is 90% by mass or less, the prepreg having excellent adhesion between the base material and the resin is obtained using the resin dispersion (this is a resin composition composite according to one embodiment of the present invention). As a result, the laminated board manufactured using the prepreg has excellent heat resistance.

Here, the ratio of the functionalized polyphenylene ether resin (A) existing as particles to the total amount of 100 mass% of the functionalized polyphenylene ether resin (A) contained in the resin dispersion (hereinafter referred to as functionalized polyphenylene ether particles). (Also called ratio) can be determined by the following measurement. First, particles are precipitated from the resin dispersion by a method such as a centrifugal separation method to obtain a supernatant containing no particles. This supernatant is collected in a unit amount (for example, 1 g), the solvent is completely removed by a method such as heat drying, and the mass of the resulting residue is measured to obtain dissolved components per unit amount of the supernatant (for example, 1 g). The amount is measured to obtain the dissolved component mass ratio of the supernatant. On the other hand, by collecting a predetermined amount of the original resin dispersion containing particles (hereinafter referred to as a resin dispersion sample) and recovering the solvent from the resin dispersion sample by a method such as heat drying, the resin dispersion sample contains Measure the solid mass (c) and the amount of solvent. From this amount of solvent and the previous dissolved component mass ratio, the mass (b) of the dissolved component in the resin dispersion sample can be calculated. Also, the mass (a) of the particles present in the resin dispersion sample can be calculated by subtracting the mass (b) of the dissolved component from the total solid content (c) after drying the resin dispersion sample. it can. Finally, the following formula (1):
(Particle ratio) = (Particle mass (a)) ÷ (Total solids mass (c)) (1)
Thus, the ratio of particles when the total solid content in the resin dispersion sample is 100% by mass can be obtained.

When there is no resin other than the functionalized polyphenylene ether resin (A) in the resin dispersion, the particle ratio calculated by the above formula (1) is directly used as the functionalized polyphenylene ether particle ratio. On the other hand, when a component other than the functionalized polyphenylene ether resin (A) is present in the resin dispersion, for example, the functionalized polyphenylene ether resin (A) contained in the resin dispersion by the following method: The ratio of the functionalized polyphenylene ether particles can be derived by determining the ratio with other components.
The solvent is dried and removed from the resin dispersion at a temperature not higher than the boiling point of the solvent so that the solvent content is 1% by mass or less. Then, 20 g of a mixed solvent of toluene and methanol having a mass ratio of 95: 5 at 23 ° C. ± 3 ° C. is added to 1.5 g of the dispersion from which the solvent has been removed by drying. Allow 1 hour to elapse while shaking vigorously every 5 minutes in a constant temperature room at 23 ° C. ± 2 ° C. Next, it is allowed to stand for 24 hours in the same constant temperature room. Next, the supernatant is removed, 5 g of a mixed solvent of toluene and methanol with a mass ratio of 95: 5 is added, shaken vigorously, and then allowed to stand in the same constant temperature room for 24 hours. Next, the supernatant is removed, and 5 g of a mixed solvent of toluene and methanol having a mass ratio of 95: 5 is added. Next, after removing the solvent by drying, it is developed in chloroform, and insolubles are removed by filtration to obtain an extract (hereinafter, this extract is also referred to as “extract (A)”). On the other hand, particles are settled from the resin dispersion by a method such as a centrifugal separation method to obtain a supernatant containing no particles. The solvent is completely removed from the supernatant by a method such as heat drying to obtain a residue. This residue is developed in chloroform, and insolubles are removed by filtration to obtain an extract (hereinafter, this extract is also referred to as extract (B)). The amount of each polyphenylene ether in the extract (A) and the extract (B) is quantified by carbon nuclear magnetic resonance spectroscopy, and the ratio (P _A ) of the polyphenylene ether in the extract ( _A ) and the extract The ratio (P _B ) (based on mass) of the polyphenylene ether in ( _B ) is obtained. Using these values, the following formula (2):
(Functionalized polyphenylene ether particle ratio) = (particle mass (a) × ratio (P _A )) ÷ (particle mass (a) × ratio (P _A ) + dissolved component mass (b) × ratio (P _B )) (2)
Thus, the functionalized polyphenylene ether particle ratio can be calculated.

  Quantification of polyphenylene ether using carbon nuclear magnetic resonance spectroscopy can be performed by the following method. Tetramethylsilane is used as a standard for chemical shift, and its peak is 0 ppm. As the peak of PPE, the intensities of peaks near 16.8, 114.4, 132.5, 145.4, and 154.7 ppm are totaled, and the ratio to the peak intensity of tetramethylsilane is X. If this value for the standard substance is X1, and the value for the extract (ie extract (A) or (B)) is X2, the value in the extract is calculated by calculating the value of (X2 / X1) × 100. The PPE content (based on mass) can be measured. Here, the signal derived from the PPE may be used at the same position as the standard material, and is not limited to the above. For quantitative determination, the ratio of peak intensities obtained from the same measurement sample amount using poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight of 15,000 to 25,000 as a standard substance. Find using. As poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight of 15,000 to 25,000, for example, S202A grade manufactured by Asahi Kasei Chemicals Corporation can be used.

  The particle diameter of the particle component of the functionalized polyphenylene ether resin (A) can be measured as follows. Particles are precipitated from the resin dispersion by a method such as centrifugation, and the supernatant is removed therefrom. Then, 5 g of a mixed solvent of toluene and methanol with a mass ratio of 95: 5 is added and shaken vigorously. Let stand for hours. Next, the supernatant is removed, and 5 g of a mixed solvent of toluene and methanol having a mass ratio of 95: 5 is added. After dropping this extract on a sample stage and volatilizing the solvent, SEM-EDX observation was performed, and particles having a total of 95% or more of carbon, oxygen, and hydrogen as functionalized polyphenylene ether resin (A) particles, The major axis of the primary particle is measured. A straight line is drawn so as to pass through the inside of the primary particle, and the length when the straight line becomes the longest is defined as the major axis of the primary particle. Randomly measure the major axis of 400 or more primary particles.

  In the present embodiment, the total number of particle components (total number of particles) of the functionalized polyphenylene ether resin (A) from the viewpoint of ensuring good fluidity within a range in which dispersion stability is maintained in the resin dispersion. Is preferably 60% or more, more preferably 70% or more and 100% or less, still more preferably 80% or more and 100% or less, and the major axis is preferably 3 μm or more and 30 μm or less, and the major axis is 5 μm or more and 25 μm or less. It is more preferable that the length is 5 μm or more and 20 μm or less.

  The ratio of the functionalized polyphenylene ether resin (A) to the total solid content of the resin dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass from the viewpoint of obtaining good dielectric properties. % Or more. The above ratio may be 100% by mass, but from the viewpoint of obtaining the effect of other components described later well, that is, for the purpose of imparting heat resistance and flame retardancy of the laminate, further use of other resins and the like is further used. From the viewpoint, the upper limit is at most 90% by mass.

[Organic solvent (B)]
Examples of the organic solvent (B) contained in the resin dispersion include aromatic organic solvents such as benzene, toluene and xylene, ketones such as cyclohexanone, methyl ethyl ketone and methyl isobutyl ketone, and alcohols such as methanol, ethanol and butanol. The organic solvent (B) to be used may be a solvent composed of one of these or a mixed solvent of two or more.

  The amount of the organic solvent (B) is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, from the viewpoint of ensuring the stability of the resin dispersion with respect to 100 parts by mass of the functionalized polyphenylene ether resin (A). More preferably, it is 140 parts by mass or more, and preferably 900 parts by mass or less, more preferably 700 parts by mass or less, and still more preferably 500 parts by mass, from the viewpoint of securing a viscosity suitable for using the resin dispersion for varnish and the like. It is below mass parts.

[Additional ingredients]
The resin dispersion liquid of this embodiment may contain an additional component in addition to the functionalized polyphenylene ether resin (A) and the organic solvent (B). For example, the resin dispersion can further contain a crosslinkable curable component (C) and an initiator (D). In a preferred embodiment, the resin dispersion may further contain a flame retardant, other resins, various additives, and the like. The resin dispersion can be used alone or in combination with other substances as a varnish. On the other hand, the resin dispersion of this embodiment can be composed of a functionalized polyphenylene ether resin (A) and an organic solvent (B). In this case, the resin dispersion can be used as a varnish alone or in combination with additional components (such as those described above).

  As the crosslinkable curable component (C), a monomer having two or more unsaturated groups in the molecule is preferable. The resin dispersion is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 100 parts by mass of the functionalized polyphenylene ether resin (A). 10-70 mass parts, More preferably, it contains 20-70 mass parts. When the amount of the crosslinkable curable component (C) is 5 parts by mass or more, since the melt viscosity of the resin in the resin dispersion can be reduced satisfactorily, the substrate moldability is good. Moreover, when it is 95 mass parts or less, the outstanding dielectric constant and dielectric loss tangent which polyphenylene ether has can be expressed.

  Monomers having two or more unsaturated groups in the molecule include triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethallyl cyanurate, trimethylolpropane trimethacrylate, divinylbenzene, divinylnaphthalene, diallyl. Examples thereof include phthalate and diallyl cyanurate, among which TAIC having good compatibility with polyphenylene ether is preferable.

  As the initiator (D), any initiator having the ability to promote a polymerization reaction of a vinyl monomer can be used. For example, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-di Hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t- Butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxy Benzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5- Examples thereof include peroxides such as dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilyl peroxide. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator. Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne is preferred from the viewpoint that it can provide a cured product having excellent heat resistance and mechanical properties and having a lower dielectric constant and dielectric loss tangent. 3, α, α′-bis (t-butylperoxy-m-isopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are preferred.

  Although the usage-amount of an initiator (D) can be set suitably, generally from a viewpoint of accelerating | stimulating a polymerization reaction favorably with respect to 100 mass parts of crosslinkable curable components (C), Preferably it is 1.0 mass. Part or more, more preferably 3.0 parts by weight or more, still more preferably 5.0 parts by weight or more, and preferably 25 parts by weight or less from the viewpoint that the dielectric constant and dielectric loss tangent of the cured product can be kept low. Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less.

  The flame retardant is not particularly limited as long as it has a function of inhibiting the combustion mechanism. Inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, decabromodiphenyl Examples include ethane, aromatic bromine compounds such as 4,4-dibromobiphenyl and ethylenebistetrabromophthalimide, and phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate. Of these, decabromodiphenylethane and the like are preferable from the viewpoint of keeping the dielectric constant and dielectric loss tangent of the obtained cured product low.

  The amount of the flame retardant used varies depending on the flame retardant used, and is not particularly limited. From the viewpoint of maintaining flame retardancy at the UL standard 94V-0 level, the functionalized polyphenylene ether resin (A) and cross-linkable curing are used. Preferably it is 5 mass parts or more with respect to a total of 100 mass parts with a sex component (C), More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more. Moreover, from the viewpoint that the dielectric constant and dielectric loss tangent of the obtained cured product can be kept small, the amount used is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

  Examples of other resins include thermoplastic resins and curable resins. Thermoplastic resins include ethylene, propylene, butadiene, isoprene, styrene, divinylbenzene, methacrylic acid, acrylic acid, methacrylic ester, acrylic ester, vinyl chloride, acrylonitrile, maleic anhydride, vinyl acetate, ethylene tetrafluoride, etc. Examples thereof include homopolymers of vinyl compounds and copolymers of two or more vinyl compounds, and polyamides, polyimides, polycarbonates, polyesters, polyacetals, polyphenylene sulfides, polyethylene glycols, and the like. Among these, a styrene homopolymer, a styrene-butadiene copolymer, and a styrene-ethylene-butadiene copolymer can be preferably used from the viewpoints of solubility of the curable resin composition in a solvent and moldability. Examples of the curable resin include phenol resins, epoxy resins, and cyanate esters. The thermoplastic resin and curable resin may be modified with a functional compound such as an acid anhydride, an epoxy compound, or an amine.

  The amount of the other resin used is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, further with respect to 100 parts by mass in total of the functionalized polyphenylene ether resin (A) and the curable component (C). The amount is preferably 20 parts by mass or more, and preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less, from the viewpoint of developing the excellent dielectric properties and heat resistance of the polyphenylene ether resin. .

  Other various additives include flame retardants, heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, fillers, polymer additives, and the like. The amount of these additives used is appropriately set by those skilled in the art as desired.

  Using the resin dispersion according to the present invention, a laminate in which a cured product composite containing a cured product of a resin composition obtained from the resin dispersion and a substrate and a metal foil are laminated can be formed. The laminate is preferably one in which the cured product composite and the metal foil are in close contact with each other, and is suitably used as a material for an electronic substrate. As the metal foil, for example, an aluminum foil and a copper foil can be used, and among them, the copper foil is preferable because of its low electric resistance. The cured product composite to be combined with the metal foil may be one sheet or a plurality of sheets, and the metal foil is overlapped on one side or both sides of the composite to be processed into a laminate according to the use. As a method for producing a laminate, for example, a resin composition composite (for example, the above-mentioned prepreg) having a resin composition obtained by removing a solvent from a varnish containing a resin dispersion and a substrate is formed. The method of obtaining the laminated board on which the hardened | cured material composite body and the metal foil are laminated | stacked is mentioned by hardening a resin composition after lapping with metal foil. One particularly preferred application of the laminate is a printed wiring board.

<Manufacture of resin dispersion>
As a method for producing the resin dispersion of the present embodiment, for example, a method of adding polyphenylene ether to a non-halogen solvent, heating and dissolving the polyphenylene ether, and then lowering the temperature (hereinafter referred to as “crystal dispersion method”) Also called). In a method of adding polyphenylene ether to a non-halogen solvent, heating and dissolving it, and then lowering the temperature to obtain polyphenylene ether crystal particles, a resin solution containing 70% by mass or more of polyphenylene ether in solid content is used. It is better to obtain particles by lowering the temperature. The number of particles having a major axis of 3 μm or more and 30 μm or less is preferably 60% or more of the total number of particles from the viewpoint of obtaining a viscosity suitable for coating.

  In the PPE solution, it is preferable that the ratio of PPE to all dissolved components is high because the PPE concentration in the PPE particles can be increased and PPE particles satisfying the requirements of the present invention can be easily obtained. Further, the PPE solution includes, in addition to PPE, a polystyrene resin, a polymer block A mainly composed of one kind of vinyl aromatic compound, and a polymer block B mainly composed of at least one kind of conjugated diene compound. An additive such as a hydrogenated block copolymer obtained by hydrogenating the block copolymer obtained may be included. Moreover, it is preferable that a PPE solution does not contain a component having a melting point of 30 ° C. or higher. In this case, a PPE crystal dispersion having stable and reproducible fluidity can be obtained.

<Resin composition composite and laminate>
Another aspect of the present invention provides a varnish containing the above-described resin dispersion of the present invention.
Another aspect of the present invention provides a resin composition obtained by removing a solvent from the varnish.
Another aspect of the present invention is a resin composition composite obtained by applying a varnish containing the above-described resin dispersion of the present invention to a substrate and then removing the solvent from the substrate coated with the varnish. provide. The resin composition composite can be, for example, a prepreg.
Another aspect of the present invention is a resin composition composite comprising a step of applying a varnish containing the above-described resin dispersion of the present invention to a substrate, and a step of removing the solvent from the substrate coated with the varnish. A method for producing a body (eg, prepreg) is provided.
Another aspect of the present invention provides a laminate comprising a layer obtained from the above-described resin composition of the present invention or a layer obtained from the above-described resin composition composite (eg, prepreg) of the present invention.
In another aspect of the present invention, the step of laminating the above-described resin composition or resin composition composite (for example, prepreg) of the present invention on a substrate, and the resin composition or the resin composition composite Provided is a method for producing a laminated board including a step of heat-pressing a laminated substrate.

  A preferred example of the laminated board is a printed wiring board including a cured body obtained by curing the resin composition of the resin composition composite of the present invention described above and a base material. A printed wiring board can typically be formed by pressure heating molding using the prepreg described above. Examples of the substrate include those described below. Since the printed wiring board is formed using the resin dispersion liquid as described above, it can have excellent insulation reliability and mechanical characteristics.

  As the base material, various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; wholly aromatic polyamide fiber, wholly aromatic polyester fiber Woven or non-woven fabrics obtained from liquid crystal fibers such as polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen cloth and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed yarn, etc. Natural cellulose base materials; polytetrafluoroethylene porous films; etc. can be used alone or in combination of two or more.

  The resin content in the resin composition composite (that is, the total content of the functionalized polyphenylene ether resin (A), the crosslinkable curable component (C) and any other resin) is determined by the thickness of the substrate and the prepreg. For example, when glass cloth is used as the base material, the dielectric constant of the glass cloth is higher than the dielectric constant of the resin. Therefore, it is better to increase the resin content. This is advantageous. In general, the resin content is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more from the viewpoint of improving dielectric properties and improving moldability. From the viewpoint of improving the rigidity of the cured product obtained by curing the resin composition composite, it is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

  As a method for producing a resin composition composite according to the present embodiment, the above-mentioned base material is impregnated with a varnish comprising a resin dispersion in which particle components are dispersed or made of the resin dispersion, and the solvent is removed by drying. The method of doing is mentioned. In the drying step, for example, the solvent can be removed by heating the prepreg at 50 ° C. to 150 ° C. and 1 minute to 30 minutes. In the resin composition composite, the solid content contained in the resin dispersion is impregnated in the base material. The solid content may form a layer on the surface of the resin composition composite.

  The prepreg is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the functionalized polyphenylene ether resin (A). 70 mass parts, More preferably, it contains 20-70 mass parts. When the amount of the crosslinkable curable component (C) is 5 parts by mass or more, the resin is satisfactorily impregnated in the base material when forming a laminate by forming a substrate using a prepreg and insulation reliability. Can be obtained. Moreover, when it is 95 mass parts or less, the laminated board excellent in mechanical characteristics, such as an elasticity modulus, and a dielectric characteristic is obtained.

  In the laminate according to this embodiment, typically, one or a plurality of the above-described prepregs are stacked on a substrate such as a copper foil, and then an insulating layer is formed by curing a resin component by heat and pressure molding. Can be manufactured.

The conditions for heat and pressure molding depend on the thickness of the laminate to be produced and the resin content of the prepreg, but for example, the temperature is 180 to 220 ° C, the pressure is 5 to 60 kg / cm ² , and the time is 30 to 150 minutes. I can do it.

  Each parameter described above in the present disclosure is a value measured by a method described in the following examples or a method understood by those skilled in the art to be equivalent thereto.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to the following examples. The physical properties in the following examples and comparative examples were measured by the following methods. In the following, parts and% are based on mass unless otherwise specified.

1) Number average molecular weight of functionalized polyphenylene ether resin Using gel permeation chromatography analysis (GPC), the number average molecular weight was determined by comparison with the elution time of standard polystyrene with a known molecular weight.
HLC-8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, column: Shodex GPC K-806L × 3 (manufactured by Showa Denko KK), eluent: chloroform at 50 ° C., detector: RI, column temperature 40 ° C. The measurement was performed under the following conditions.

2) Particle size distribution of particles in the resin dispersion The particles are precipitated by centrifuging the resin dispersion, the supernatant liquid is removed, 5 g of a mixed solvent of toluene and methanol with a mass ratio of 95: 5 is added, and the mixture is vigorously shaken. After that, it was allowed to stand for 24 hours in the same constant temperature room. Next, the supernatant was removed, and 5 g of a mixed solvent of toluene and methanol having a mass ratio of 95: 5 was added. After dropping this extract on a sample stage and volatilizing the solvent, SEM-EDX observation is performed, and particles having a total of 95% or more of carbon, oxygen, and hydrogen are defined as PPE particles (A), and the major axis of the primary particles. Was measured. The particle size distribution was measured by randomly extracting 400 or more particles and measuring the long diameter of these particles. The number average particle diameter was calculated, and the particle distribution range occupying 90% by number and 60% by number was measured.

3) Particle component ratio of functionalized polyphenylene ether resin (A) First, particles were precipitated from the resin dispersion by centrifugation, and the supernatant was obtained as a functionalized polyphenylene ether solution. 1 g of this solution was sampled, the solvent was completely removed by heating and drying, the mass of the obtained solid content was measured, and the mass ratio of dissolved components per 1 g of the solution was measured. On the other hand, by collecting a predetermined amount of the original resin dispersion containing particles (hereinafter referred to as a resin dispersion sample) and recovering the solvent from the resin dispersion sample by heat drying, the total solid content in the resin dispersion sample is recovered. The mass (c) and the amount of solvent were measured. The mass (b) of the dissolved component in the resin dispersion sample was calculated from the amount of the solvent and the previous dissolved component mass ratio. Moreover, the mass (a) of the particles present in the resin dispersion sample was calculated by subtracting the mass of the dissolved component from the total solid content (c) after drying of the resin dispersion sample. Finally, the following formula (1):
(Particle ratio) = (Particle mass (a)) ÷ (Total solids mass (c)) (1)
Thus, the ratio of particles when the total solid content in the resin dispersion sample was 100% by mass was obtained.
On the other hand, for the extract obtained in the same manner as in 2) above, the extracted particles were dissolved in chloroform, and the insoluble matter was removed by filtration to obtain an extract (A). On the other hand, particles were sedimented from the resin dispersion by centrifugation to obtain a supernatant containing no particles. The solvent was completely removed from the supernatant by heat drying to obtain a residue. This residue was dissolved in chloroform, and insoluble matters were removed by filtration to obtain an extract (B).
The ratio (P _A ) of polyphenylene ether in the extract ( _A ) and the ratio (P _B ) of polyphenylene ether in the extract ( _B ) (each based on mass) were measured by carbon nuclear magnetic resonance spectroscopy. Tetramethylsilane was used as a standard for chemical shift, and its peak was 0 ppm. The polyphenylene ether content ratio (mass basis) was calculated from the peaks in the vicinity of 16.8, 114.4, 132.5, 145.4, and 154.7 ppm, which are unique to the polyphenylene ether resin. Following formula (2):
(Functionalized polyphenylene ether particle ratio) = (particle mass (a) × ratio (P _A )) ÷ (particle mass (a) × ratio (P _A ) + dissolved component mass (b) × ratio (P _B )) (2)
Thus, the ratio of functionalized polyphenylene ether particles was calculated.

4) Viscosity measurement B-type viscometer, rotor No. 3 was used, and the viscosity was measured under the conditions of 25 ° C., 30 rpm, and 30 seconds.

5) Resin / Cross Adhesiveness It was examined and evaluated whether resin powder fall or resin peeling occurred when the prepreg was bent at 180 °. First, the prepreg was cut out to a size of 200 mm × 300 mm using a cutter blade. Next, the prepreg was bent at 180 ° so that the two long sides of the rectangle overlapped, and then returned to its original state. Next, the prepreg was bent at 180 ° so that the two sides of the short side of the rectangle overlapped, and then returned to its original state. In the above-described series of prepreg handling, resin powder falling and resin peeling were not visually observed and evaluated as “good”. On the other hand, those in which resin powder omission or resin peeling was observed visually were evaluated as “bad”.

6) Solder heat resistance Two prepreg layers are stacked on top of each other with 18μm thick copper foil (GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) and heated and pressed for 60 minutes at 200 ° C and 40kg / cm ^2. Then, a copper clad laminate having a thickness of 0.3 mm was produced. The copper foil is removed by etching, and the 50 mm × 50 mm laminated plate, which is a cured product of the prepreg, is washed with water, heated and dried at 130 ° C. for 1 hour, treated at 121 ° C. and 2 atm for 3 hours, and then 260 ° C. It was immersed in solder for 20 seconds, and the surface of the laminate was observed. The surface where swelling and whitening were not visually observed was designated as “OK”, and the surface where swelling or whitening was visually observed was designated as “NG”.

7) Dielectric loss tangent The dielectric constant and dielectric loss tangent of the laminate at 1 GHz were measured using an impedance analyzer. Using an impedance analyzer (4291B op.002 with 16453A, 16454A, manufactured by Agilent Technologies) as a measuring device, measurement is performed under the conditions of test piece thickness: about 2 mm, voltage: 100 mV, frequency: 1 mm Hz to 1.8 GHz, and 100 sweeps. It calculated | required as an average value of times.

8) Substrate Tg
Two prepregs were stacked, and 18 μm thick copper foil (GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) was layered on both sides and heat-pressed for 60 minutes under the conditions of 200 ° C. and 40 kg / cm ^2. A 3 mm copper clad laminate was produced. The substrate after removing the copper foil by etching, washing with water and air-drying was measured for viscoelasticity with RDAII (manufactured by TA Instruments) at a temperature increase rate of 2.5 ° C. and step temperature increase, and the peak of tan δ Was the glass transition temperature (Tg).

[Example 1]
As shown in Table 1, 25 parts of maleic acid-modified polyphenylene ether 1 (as a functionalized polyphenylene ether resin (A)) and 75 parts of toluene (as an organic solvent (B)) are added to polystyrene (manufactured by Asahi Kasei Chemicals, GPPS 685). ) After dissolving 1.53 parts at 80 ° C., it was cooled to 35 ° C. to prepare a dispersion. With respect to this dispersion, the particle size (major axis) distribution, particle component ratio and viscosity of the particles were measured, and the results are shown in Table 1. A viscosity of 360 mPa.s in which polyphenylene ether particles having a particle diameter of 6 to 12 μm were dispersed in 90% by number of the particles. In the dispersion liquid of s, TAIC (Nippon Kasei Co., Ltd.) (as a crosslinkable curable component (B)) 11.4 parts, Decabromodiphenylethane (Albemarle, SAYTEX8010) (as a flame retardant) 8 parts, and α, α 0.76 parts of '-bis (t-butylperoxy-m-isopropyl) benzene (manufactured by NOF Corporation, perbutyl P) (as initiator (D)) was added to obtain a resin dispersion of the present invention. In addition, although evaluation of the particles of maleic acid-modified polyphenylene ether 1 was performed with respect to the above dispersion liquid, it is considered that the presence state of the particles is the same in the resin dispersion liquid. By the above procedure, a coating varnish made of a resin dispersion was obtained. This was impregnated into 0.1 mm thick E glass cloth (manufactured by Asahi Sebel, 2116 type), and the solvent was removed to obtain a prepreg having a resin content of 59%. The resin / cloth adhesion was good and the handleability was excellent.

[Example 2]
A dispersion was obtained in the same manner from 22.5 parts of maleic acid-modified polyphenylene ether 1, 77.5 parts of toluene, and 1.37 parts of polystyrene. TAIC (Nippon Kasei) 10.2 parts, Decabromodiphenylethane (Albemarle, SAYTEX8010) 7 parts, and α, α'-bis (t-butylperoxy-m-isopropyl) benzene (NOF, Perbutyl P ) 0.69 part was added to form a coating varnish, and a prepreg having a resin content of 60% was obtained in the same manner as in Example 1. The prepreg was excellent in resin / cloth adhesion.

[Example 3]
Varnishes and prepregs were obtained in the same manner as in Example 1 except that maleic acid-modified polyphenylene ether 2 was used as the functionalized polyphenylene ether resin (A). The resin content was 58%, and it was a prepreg excellent in resin / cloth adhesion.

[Example 4]
Varnishes and prepregs were obtained in the same manner as in Example 1 except that a mixture of maleic acid-modified polyphenylene ether 2 and maleic acid-modified polyphenylene ether 3 was used as the functionalized polyphenylene ether resin (A). The resin content was 59%, and the prepreg was excellent in resin / cloth adhesion.

[Example 5]
A varnish and a prepreg were prepared in the same manner as in Example 1 except that a mixture of maleic acid-modified polyphenylene ether 2 and low molecular weight benzyl group-modified polyphenylene ether 2 was used as the functionalized polyphenylene ether resin (A). 58% prepreg was obtained. Functionalization with a benzyl group, as well as maleic acid modification, produced an effect of suppressing crystal precipitation, and a prepreg excellent in resin / cloth adhesion was obtained.

[Example 6]
A varnish and a prepreg were prepared by the method described in Example 1 except that methacrylic acid-modified polyphenylene ether was used instead of maleic acid-modified polyphenylene ether as the functionalized polyphenylene ether (A), and a prepreg having a resin content of 60% was prepared. Got. Functionalization with a methacryl group, as well as maleic acid modification, produced an effect of suppressing crystal precipitation, and a prepreg excellent in resin / cloth adhesion was obtained.

[Example 7]
A varnish and a prepreg were prepared by the method described in Example 1 except that benzyl group-modified polyphenylene ether 1 was used instead of maleic acid-modified polyphenylene ether as the functionalized polyphenylene ether (A), and the resin content was 58%. A prepreg was obtained. Functionalization with a benzyl group, as well as maleic acid modification, produced an effect of suppressing crystal precipitation, and a prepreg excellent in resin / cloth adhesion was obtained.

[Comparative Example 1]
Varnishes and prepregs were produced in the same manner as in Example 1 except that unmodified polyphenylene ether was used instead of the functionalized polyphenylene ether resin (A). A prepreg having a resin content of 58% was obtained, but as a result of excessive precipitation of crystals, less polyphenylene ether was dissolved in the dispersion, so that the resin was peeled off from the cloth. Was inferior.

[Comparative Example 2]
Varnishes and prepregs were produced in the same manner as in Example 2 except that unmodified polyphenylene ether was used instead of the functionalized polyphenylene ether resin (A). A prepreg having a resin content of 60% was obtained, and the resin was inferior in handleability to peel off from the cloth.

[Comparative Example 3]
Varnishes and prepregs were prepared in the same manner as in Example 1 except that the low molecular weight benzyl group-modified polyphenylene ether 2 was used as the functionalized polyphenylene ether resin (A). Although a prepreg having a resin content of 58% was obtained and the prepreg had excellent adhesion between the resin and the cloth, the solder heat resistance after molding was poor and the Tg was low.

  From the results shown in Table 1, as a result of suppressing the excessive precipitation of crystals by using the predetermined functionalized polyphenylene ether resin of the present invention modified with maleic acid, methacrylic acid or benzyl group, the precipitated functional It was possible to obtain a resin dispersion in which the particle size and the particle component ratio of the base polyphenylene ether resin were controlled, and the prepreg obtained by impregnating this into a base material and removing the solvent was a resin component and a base component. It turns out that it was the thing excellent in adhesiveness with material. Moreover, it turns out that the laminated board manufactured using the prepreg is excellent in heat resistance. In addition to the above, in the examples, the substrate further exhibits the excellent dielectric properties and high Tg inherent to polyphenylene ether, and the present invention is a useful means for producing a polyphenylene ether substrate (for example, a printed circuit board). It showed that.

  The present invention can be suitably used as a material for a printed wiring board of an electronic device using a high frequency band.

Claims (9)

Including a functionalized polyphenylene ether resin (A) and an organic solvent (B),
The functionalized polyphenylene ether resin (A) has a number average molecular weight (Mn) of 5000 to 40000,
30 to 90% by mass of the total amount of the functionalized polyphenylene ether resin (A) is present as particles in the organic solvent (B),
In the functionalized polyphenylene ether resin (A), the hydroxyl group at the terminal of the polyphenylene ether is functionalized with a functional group in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the functionalized polyphenylene ether resin (A). A resin dispersion having a structure.   The resin dispersion liquid according to claim 1, wherein in the functionalized polyphenylene ether resin (A), a terminal hydroxyl group of the polyphenylene ether is functionalized with an acid anhydride.   The resin dispersion according to claim 2, wherein the acid anhydride is maleic anhydride.   4. The resin dispersion according to claim 1, wherein 60% or more of the total number of the particles has a major axis of 3 μm or more and 30 μm or less.   The resin dispersion according to any one of claims 1 to 4, further comprising a crosslinkable curable component (C) and an initiator (D).   A varnish containing the resin dispersion according to any one of claims 1 to 5.   The resin composition obtained by removing a solvent from the varnish of Claim 6.   The resin composition composite_body | complex obtained by apply | coating the varnish containing the resin dispersion liquid of any one of Claims 1-5 to a base material, and then removing a solvent from the base material with which this varnish was apply | coated.   A laminate comprising a layer obtained from the resin composition according to claim 7 or a layer obtained from the resin composition composite according to claim 8.