JP7289074B2 - Resin composition, and prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, and a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board using the same.

2. Description of the Related Art In recent years, with the increase in the amount of information processed in various electronic devices, there has been rapid progress in mounting techniques such as higher integration of semiconductor devices mounted thereon, higher wiring density, and multi-layering. Substrate materials that constitute the base material of printed wiring boards used in various electronic devices are required to have a low dielectric constant and a low dielectric loss tangent in order to increase the signal transmission speed and reduce loss during signal transmission. be done.

In response to such demands, resin compositions containing polyphenylene ether (PPE) compounds whose ends are modified with methacrylic groups or the like are used as materials that are excellent in thermal properties, electrical properties, and design properties ( For example, Patent Document 1). It has also been reported that a wiring board or the like composed of a resin composition containing a PPE compound has excellent transmission characteristics.

On the other hand, it is common practice to add a filler such as silica to a resin composition used as a substrate material for the purpose of enhancing heat resistance. It is also known to surface-treat the silica with a silane coupling agent for the purpose of improving interlayer adhesion when the substrate material is used as a laminate.

However, according to the research of the present inventors, in a resin composition containing a specific modified polyphenylene ether resin, a predetermined silane coupling agent and / or silica treated with the silane coupling agent, a varnish by mixing with an organic solvent It was found that the viscosity became too high with the lapse of time and the fluidity was poor. When the fluidity of the resin composition deteriorates, it becomes waxy or pasty, making it difficult to produce electronic materials such as prepregs and laminates using the resin composition. The handling property is also deteriorated, and the appearance of the resulting prepreg and the like is also adversely affected. In addition, even if a solvent or the like is added to the resin composition once it has deteriorated in fluidity to dilute it before use, there are problems such as a decrease in Tg due to residual solvent and a decrease in insulation reliability when used as an electronic material. Viscosity changes significantly over time, and when the viscosity increases, the change in viscosity makes it impossible to stably manufacture prepregs, resin-coated films, resin-coated metal foils, etc., which are made by coating or impregnating and drying, resulting in poor appearance. It also leads to material loss due to etc.

The present invention has been made in view of such circumstances, and provides a resin composition having excellent fluidity when formed into a varnish while maintaining properties such as heat resistance and electrical properties in a cured product of the resin composition. intended to provide Another object of the present invention is to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board using the resin composition.

Japanese translation of PCT publication No. 2004-511580

The resin composition according to one aspect of the present invention includes (A) a polyphenylene ether compound having a terminal group represented by the following formula (1);
(B) (b-1) a silane coupling agent and silica particles having a functional group containing a carbon-carbon unsaturated double bond in the molecule, and (b-2) silica surface-treated with the silane coupling agent at least one of the particles;
(C) an organic solvent,
In the component (A), a mixture obtained by mixing the component (A) and ion-exchanged water (pH = 5.0) at a weight ratio of 1:3 is ultrasonically vibrated at room temperature for 10 minutes, and then filtered. It is characterized in that the pH of the extract when extracted is 5.0 or higher.

[In Formula (1), R ₁ represents a hydrogen atom or an alkyl group. ]

FIG. 1 is a schematic cross-sectional view showing the structure of a prepreg according to one embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing the configuration of a metal-clad laminate according to one embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing the configuration of a wiring board according to one embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing the configuration of a resin-coated metal foil according to one embodiment of the present invention. FIG. 5 is a schematic cross-sectional view showing the configuration of a resin film according to one embodiment of the present invention.

The present inventors, as described above, a specific modified polyphenylene ether resin (having a group represented by the formula (1) at the end), a predetermined silane coupling agent and / or treated with the silane coupling agent Extensive research has been carried out on the deterioration of fluidity in a resin composition containing silica. As a result, it has been found that the pH of the resin composition containing the polyphenylene ether compound fluctuates due to impurities (in particular, acidic impurities) contained in the polyphenylene ether compound. This is considered to be caused by the presence of the methacrylic acid compound contained as an impurity in the polyphenylene ether compound and the hydrolysis of the silane coupling agent. As a result, the pH becomes acidic, and the silane coupling agent and silica particles form a pseudo-crosslinked body due to hydrogen bonding, which is presumed to reduce the fluidity of the resin composition.

Therefore, the resin composition according to the embodiment of the present invention includes (A) a polyphenylene ether compound having a terminal group represented by the following formula (1), and (B) (b-1) a carbon-carbon unsaturated di A silane coupling agent having a functional group containing a double bond in the molecule, silica particles, (b-2) at least one of the silica particles surface-treated with the silane coupling agent, and (C) an organic solvent. Then, in the component (A), after ultrasonically vibrating a mixed liquid obtained by mixing the component (A) and ion-exchanged water (pH = 5.0) at a weight ratio of 1:3 at room temperature for 10 minutes , the pH of the extract is 5.0 or more when filtered and extracted.

[In Formula (1), R ₁ represents a hydrogen atom or an alkyl group. ]
With such a configuration, it is possible to control the pH of the resin composition while maintaining properties such as heat resistance and electrical properties in the cured product, and to ensure fluidity.

That is, according to the present invention, it is possible to provide a resin composition having excellent fluidity when formed into a varnish while maintaining properties such as heat resistance in a cured product of the resin composition. Furthermore, according to the present invention, by using the resin composition, it is possible to provide prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards having excellent performance and appearance.

Each component of the resin composition according to the present embodiment will be specifically described below.

((A) polyphenylene ether (PPE) compound)
The resin composition of the present embodiment contains (A) a polyphenylene ether compound as a resin component.

The polyphenylene ether compound used in the present embodiment has a group represented by the above formula (1) at the molecular end, and the polyphenylene ether compound and ion-exchanged water (pH = 5.0) are mixed at a ratio of 1:3. There is no particular limitation as long as it is a polyphenylene ether compound that shows a pH of 5.0 or more in the extract when the mixture is subjected to ultrasonic vibration at room temperature for 10 minutes and then filtered and extracted. By using such a polyphenylene ether compound, it is possible to provide a resin composition having excellent fluidity when formed into a varnish while maintaining properties such as heat resistance in a cured product of the resin composition.

The pH of the extract is not particularly limited as long as it is 5.0 or higher, but since the hydrolysis and condensation reaction rate of the silane coupling agent increases when the pH exceeds 7, the silane coupling agent is hydrolyzed while hydrolyzing. From the viewpoint of suppressing the condensation reaction between them as much as possible, it is preferably 7.0 or less. If the pH is 5.0 or more, it is considered that the fluidity of the resin composition is improved.

In addition, the pH can be measured by the method described in Examples to be described later.

In formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 10 carbon atoms, and may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group and the like. is mentioned. Among these, a hydrogen atom is preferable.

In particular, the resin composition of the present embodiment may contain a polyphenylene ether compound having a structure represented by the following formula (2) as the component (A) from the viewpoint of obtaining the above effects more reliably. preferable.

In formula (2) above, R ₂ to R ₉ are each independent. That is, R ₂ to R ₉ may each be the same group or different groups. R ₂ to R ₉ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

Specific examples of the above-mentioned functional groups for R ₂ to R ₉ include the following.

Although the alkyl group is not particularly limited, for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.

Although the alkenyl group is not particularly limited, for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples include vinyl groups, allyl groups, and 3-butenyl groups.

Although the alkynyl group is not particularly limited, for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. . Specific examples include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, cyclohexylcarbonyl group and the like.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specific examples include an acryloyl group, a methacryloyl group, and a crotonoyl group.

The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specific examples thereof include a propioloyl group and the like.

Further, in the above formula (2), A is a structure represented by the following formula (3), and B is a structure represented by the following formula (4):

In formulas (3) and (4), m and n, which are repeating units, each represent an integer of 1 to 50.

R ₁₀ to R ₁₇ are each independent. That is, R ₁₀ to R ₁₇ may each be the same group or different groups. Also, in this embodiment, R ₁₀ to R ₁₇ are hydrogen atoms or alkyl groups.

In formula (2) above, X is a group represented by formula (1) above.

Furthermore, in the above formula (2), Y may be a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms. More specifically, it is a structure represented by the following formula (5):

In formula (5), R ₁₈ and R ₁₉ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Examples of the group represented by formula (5) include methylene group, methylmethylene group, and dimethylmethylene group.

In the present embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited, but is preferably 1,000 to 5,000, more preferably 1,000 to 4,000. Here, the weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically includes a value measured using gel permeation chromatography (GPC). In addition, when the polyphenylene ether compound has repeating units (m, n) in the molecule, these repeating units are numerical values such that the weight average molecular weight of the polyphenylene ether compound is within such a range. is preferred.

When the weight average molecular weight of the polyphenylene ether compound is within such a range, it has excellent low dielectric properties possessed by the polyphenylene ether skeleton, and not only is the cured product excellent in heat resistance, but also excellent in moldability. Become. This is believed to be due to the following. Compared with ordinary polyphenylene ether, if the weight-average molecular weight is within the above-mentioned range, the weight-average molecular weight is relatively low, so that the heat resistance of the cured product tends to decrease. In this respect, the polyphenylene ether compound according to the present embodiment has a structure represented by the above formula (1) at the end, so it has high reactivity, and it is thought that a cured product with sufficiently high heat resistance can be obtained. be done. In addition, when the weight average molecular weight of the polyphenylene ether compound is within such a range, it has a high molecular weight compared to styrene and divinylbenzene, but has a relatively low molecular weight than general polyphenylene ether, so it can be molded. It is considered to be superior in terms of sex. Therefore, it is considered that by using such a polyphenylene ether compound, a cured product having not only excellent heat resistance but also excellent moldability can be obtained.

In addition, the average number of X substituents (the number of terminal functional groups) at the molecular end per molecule of modified polyphenylene ether in the polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal functional groups is too large, the reactivity becomes too high, and problems such as deterioration in the storage stability of the resin composition and deterioration in fluidity of the resin composition may occur. . That is, when such a modified polyphenylene ether is used, molding defects such as voids occur during multi-layer molding due to insufficient fluidity, etc., and it is difficult to obtain a highly reliable printed wiring board. Problems could arise.

The terminal functional group number of the polyphenylene ether compound includes, for example, a numerical value representing the average value of the substituents per molecule of all polyphenylene ether compounds present in 1 mol of the polyphenylene ether compound. The number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained polyphenylene ether compound and calculating the amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. Then, the method for measuring the number of hydroxyl groups remaining in the polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to the solution of the polyphenylene ether compound, and measure the UV absorbance of the mixed solution. can be obtained by

Moreover, the intrinsic viscosity of the polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl/g, preferably 0.04 to 0.11 dl/g, more preferably 0.06 to 0.095 dl/g. . If the intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as a low dielectric constant and a low dielectric loss tangent. On the other hand, when the intrinsic viscosity is too high, the viscosity tends to be too high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to deteriorate. Therefore, if the intrinsic viscosity of the polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

In addition, the intrinsic viscosity here is the intrinsic viscosity measured in methylene chloride at 25 ° C. More specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) , etc. Examples of this viscometer include AVS500 Visco System manufactured by Schott.

Further, in the resin composition of the present embodiment, the amount of methacrylic acid dimer and its hydrolyzate contained as impurities in the component (A) is preferably 200 μg/g or less. As a result, it is considered that the effects as described above can be obtained more reliably.

The resin composition of the present embodiment may contain a thermosetting resin other than the polyphenylene ether compound as described above. Other usable thermosetting resins include, for example, epoxy resins, phenol resins, amine resins, unsaturated polyester resins, and thermosetting polyimide resins.

Further, a method for synthesizing a polyphenylene ether compound preferably used in the present embodiment is a modified polyphenylene ether whose terminal is modified with the substituent X as described above and the pH of the extract under the predetermined conditions is 5.0 or more. The method is not particularly limited as long as it can synthesize a compound. Specifically, the polyphenylene ether compound can be produced, for example, by the method described in International Publication 2010/503754.

The raw polyphenylene ether is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether. Specifically, polyphenylene ether such as poly(2,6-dimethyl-1,4-phenylene oxide) and polyphenylene ether composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol. and the like as a main component. Bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like. A trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.

As an example of a method for synthesizing a polyphenylene ether compound, for example, in the case of a polyphenylene ether compound represented by the above formula (2), specifically, 4 By reacting in the presence of -(N,N-dimethylamino)pyridine, the modified polyphenylene ether represented by the above formula (2) of the present embodiment can be obtained.

After the reaction is completed, the acid anhydride remaining as a residue is removed by washing with an aqueous solution containing about 0.0001 to about 1 normal sodium hydroxide. On the other hand, for example, by washing with hydrochloric acid as a washing liquid, the basic impurities present as residues can be removed, and the pH can be adjusted to a specified value. In order to further adjust the pH, the washing may be performed multiple times.

(Other resin components)
The resin component in the resin composition of the present embodiment preferably contains a cross-linking curing agent in addition to the polyphenylene ether compound (A).

The crosslinkable curing agent that can be used in the present embodiment is particularly limited as long as it has a carbon-carbon unsaturated double bond in the molecule or can be cured by reacting with the (A) polyphenylene ether compound. not. That is, the crosslinkable curing agent may be one that can be cured by forming crosslinks by reacting with the modified polyphenylene ether compound. The cross-linking curing agent is a compound having two or more carbon-carbon unsaturated double bonds in the molecule or a compound having at least one functional group in the molecule that contributes to the reaction with the (A) polyphenylene ether compound. Preferably.

The weight average molecular weight of the crosslinking curing agent used in this embodiment is preferably 100 to 5,000, more preferably 100 to 4,000, even more preferably 100 to 3,000. If the weight-average molecular weight of the cross-linking curing agent is too low, the cross-linking curing agent may easily volatilize from the component system of the resin composition. On the other hand, if the weight average molecular weight of the crosslinkable curing agent is too high, the viscosity of the varnish of the resin composition and the melt viscosity during heat molding may become too high. Therefore, when the weight-average molecular weight of the crosslinkable curing agent is within such a range, a cured resin composition having excellent heat resistance can be obtained. It is considered that this is because the reaction with the modified polyphenylene ether compound can favorably form crosslinks. Here, the weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically includes a value measured using gel permeation chromatography (GPC).

In addition, the cross-linking curing agent used in the present embodiment has an average number of carbon-carbon unsaturated double bonds (number of terminal double bonds) per molecule of the cross-linking curing agent, or the compound (A) and The average number (number of functional groups) per molecule of the cross-linking curing agent of the functional groups contributing to the reaction of (1) varies depending on the weight-average molecular weight of the cross-linking curing agent. ~18 is more preferred. If the number of terminal double bonds and the number of functional groups are too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, when the number of terminal double bonds and the number of functional groups are too large, the reactivity becomes too high, and problems such as deterioration of the storage stability of the resin composition and deterioration of the fluidity of the resin composition occur. It may occur.

As for the number of terminal double bonds and the number of functional groups of the cross-linking curing agent, the weight-average molecular weight of the cross-linking curing agent is less than 500 (for example, 100 or more and less than 500). is preferably 1 to 4. The number of terminal double bonds and the number of functional groups of the crosslinkable curing agent are preferably 3 to 20 when the weight average molecular weight of the crosslinkable curing agent is 500 or more (for example, 500 or more and 5000 or less). In each case, if the number of terminal double bonds and the number of functional groups are less than the lower limit of the above range, the reactivity of the cross-linking curing agent is lowered, the cross-linking density of the cured product of the resin composition is lowered, and heat resistance is reduced. It may become impossible to sufficiently improve the properties and Tg. On the other hand, when the number of terminal double bonds and the number of functional groups are more than the upper limit of the above range, the resin composition may easily gel.

The number of terminal double bonds and the number of functional groups here can be found from the product standard values of the cross-linking curing agent to be used. Specifically, the number of terminal double bonds and the number of functional groups herein are, for example, the number of double bonds and the number of functional groups per molecule of all cross-linking curing agents present in 1 mol of the cross-linking curing agent. Numerical values representing average values and the like are included.

Further, the cross-linking curing agent used in the present embodiment specifically includes, for example, styrene, a styrene derivative, a compound having an acryloyl group in the molecule, a compound having a methacryloyl group in the molecule, and a vinyl group in the molecule. compounds having an allyl group in the molecule, compounds having a maleimide group in the molecule, modified maleimide compounds, compounds having an acenaphthylene structure in the molecule, and isocyanurate compounds having an isocyanurate group in the molecule. . It is believed that the use of these compounds will result in more favorable formation of crosslinks through the curing reaction, and the heat resistance of the cured product of the resin composition used in the present embodiment can be further enhanced.

Examples of the styrene derivative include bromostyrene and dibromostyrene.

A compound having an acryloyl group in the molecule is an acrylate compound. Examples of the acrylate compound include monofunctional acrylate compounds having one acryloyl group in the molecule and polyfunctional acrylate compounds having two or more acryloyl groups in the molecule. Examples of the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the polyfunctional acrylate compound include tricyclodecanedimethanol diacrylate.

A compound having a methacryloyl group in the molecule is a methacrylate compound. Examples of the methacrylate compounds include monofunctional methacrylate compounds having one methacryloyl group in the molecule and polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule. Examples of the monofunctional methacrylate compounds include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the polyfunctional methacrylate compound include tricyclodecanedimethanol dimethacrylate.

A compound having a vinyl group in the molecule is a vinyl compound. Examples of the vinyl compound include monofunctional vinyl compounds (monovinyl compounds) having one vinyl group in the molecule and polyfunctional vinyl compounds having two or more vinyl groups in the molecule. Examples of the polyfunctional vinyl compound include a polyfunctional aromatic vinyl compound, a polyfunctional aliphatic vinyl compound, a polymer or copolymer containing a structure derived from a polyfunctional aromatic vinyl compound, and a structure derived from a polyfunctional aliphatic vinyl compound. Examples thereof include divinylbenzene, divinylbenzene copolymers, polybutadiene, butadiene copolymers, and the like.

A compound having an allyl group in the molecule is an allyl compound. Examples of the allyl compound include monofunctional allyl compounds having one allyl group in the molecule and polyfunctional allyl compounds having two or more allyl groups in the molecule. Examples of the polyfunctional allyl compound include diallyl phthalate (DAP).

A compound having a maleimide group in the molecule is a maleimide compound. Examples of the maleimide compound include monofunctional maleimide compounds having one maleimide group in the molecule and polyfunctional maleimide compounds having two or more maleimide groups in the molecule. Examples of the modified maleimide compound include modified maleimide compounds partially modified with an amine compound, modified maleimide compounds partially modified with a silicone compound, and partially amine compounds. and modified maleimide compounds modified with silicone compounds.

A compound having an acenaphthylene structure in the molecule is an acenaphthylene compound. Examples of the acenaphthylene compounds include acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes. Examples of the alkylacenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, and 3-ethylacenaphthylene. phthalene, 4-ethylacenaphthylene, 5-ethylacenaphthylene and the like. Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, and 3-bromoacenaphthylene. rene, 4-bromoacenaphthylene, 5-bromoacenaphthylene and the like. Examples of the phenylacenaphthylenes include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene and the like. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule. .

A compound having an isocyanurate group in the molecule is an isocyanurate compound. Examples of the isocyanurate compounds include compounds further having an alkenyl group in the molecule (alkenyl isocyanurate compounds), and examples thereof include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC).

Among the above, the cross-linking curing agent includes, for example, a polyfunctional acrylate compound having two or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule, and a vinyl group in the molecule. Polyfunctional vinyl compounds having two or more, styrene derivatives, allyl compounds having an allyl group in the molecule, maleimide compounds having a maleimide group in the molecule, acenaphthylene compounds having an acenaphthylene structure in the molecule, and isocyanurate groups in the molecule isocyanurate compounds with

The cross-linking curing agent may be used alone or in combination of two or more. In addition, as the cross-linking curing agent, a compound having two or more carbon-carbon unsaturated double bonds in the molecule and a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination. good.

(Content of resin component)
In the resin composition of the present embodiment, the content of the modified polyphenylene ether compound is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, based on the total resin composition.

Further, the content of the modified polyphenylene ether compound is preferably 30 to 90 parts by mass, preferably 50 to 90 parts by mass, with respect to a total of 100 parts by mass of the resin component (the polyphenylene ether compound and the crosslinkable curing agent). Parts by mass are more preferred.

Further, when the resin composition of the present embodiment contains the crosslinkable curing agent, the content of the crosslinkable curing agent is It is preferably 10 to 70 parts by mass, more preferably 10 to 50 parts by mass. That is, the content ratio of the modified polyphenylene ether compound and the crosslinkable curing agent is preferably from 90:10 to 30:70, more preferably from 90:10 to 50:50. If the respective contents of the modified polyphenylene ether compound and the cross-linkable curing agent satisfy the above ratio, the cured resin composition will be more excellent in heat resistance and flame retardancy. It is considered that this is because the curing reaction between the modified polyphenylene ether compound and the crosslinkable curing agent proceeds favorably.

((B) Silane coupling agent and silica particles or surface-treated silica particles)
The resin composition of the present embodiment includes (b-1) a silane coupling agent and silica particles having a functional group containing a carbon-carbon unsaturated double bond in the molecule, or (b-2) the silane coupling It contains at least one of silica particles surface-treated with an agent.

(Silane coupling agent)
The silane coupling agent used in the present embodiment is not particularly limited as long as it has a functional group containing a carbon-carbon unsaturated double bond in its molecule. By containing such a silane coupling agent and/or by containing silica particles surface-treated with such a silane coupling agent, the resin composition of the present embodiment has superior heat resistance and adhesion. properties (interlayer adhesion).

Specific examples of the functional group containing a carbon-carbon unsaturated double bond include at least one selected from the group consisting of a methacryloxy group, a styryl group, a vinyl group, and an acryloxy group. That is, the silane coupling agent has at least one of a methacryloxy group, a styryl group, a vinyl group, and an acryloxy group as a reactive functional group, and further includes a compound having a hydrolyzable group. . Examples of the silane coupling agent having a methacryloxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxypropylethyldiethoxysilane, and the like. Examples of the silane coupling agent having a styryl group include p-styryltrimethoxysilane and p-styryltriethoxysilane. Examples of the silane coupling agent having a vinyl group include vinyltriethoxysilane and vinyltrimethoxysilane. Examples of the silane coupling agent having an acryloxy group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.

Moreover, the hydrolyzable group of the silane coupling agent of the present embodiment includes a methoxy group and an ethoxy group, preferably a methoxy group.

Examples of the silane coupling agent include a silane coupling agent contained in the resin composition and a silane coupling agent contained in silica particles surface-treated with the silane coupling agent. The silane coupling agent contained in the resin composition and the silane coupling agent contained in the silica particles surface-treated with the silane coupling agent each have a carbon-carbon unsaturated double bond in the molecule. The silane coupling agent may be the same silane coupling agent, or may be different silane coupling agents.

(silica particles)
The silica particles used in the present embodiment are not particularly limited, and may be surface-treated silica particles or non-surface-treated silica particles. Moreover, as said silica particle, what is called spherical silica etc. are mentioned. Examples of the surface treatment include treatment with a silane coupling agent. The surface-treated silica particles may be silica particles surface-treated with the silane coupling agent. That is, the resin composition contains either the silica particles or the silica particles surface-treated with the silane coupling agent.

By including such silica particles, the resin composition of the present embodiment is excellent in heat resistance and thermal conductivity.

Further, the total content of the silica particles and the silica particles surface-treated with the silane coupling agent is 50 to 250 parts by mass with respect to 100 parts by mass of the resin component as described above, and 100 to 250 parts by mass. , more preferably 120 to 230 parts by mass, and even more preferably 150 to 200 mass %. Note that the total content here does not include the silica particles, and when silica particles surface-treated with the silane coupling agent are included, the content of the silica particles surface-treated with the silane coupling agent. Yes, and when it does not contain the silica particles surface-treated with the silane coupling agent but contains the silica particles, it is the content of the silica particles. If the total content is too small, the thermal conductivity of the metal-clad laminate tends to be insufficiently increased. On the other hand, if the total content is too large, it is difficult to obtain excellent low dielectric properties, and heat resistance tends to decrease. Therefore, by setting the total content within the above range, it is possible to increase the thermal conductivity and decrease the thermal expansion coefficient while maintaining excellent low dielectric properties and heat resistance.

Further, the content of the silane coupling agent is preferably 0.3 to 5 parts by mass with respect to a total of 100 parts by mass of the silica particles and the silica particles surface-treated with the silane coupling agent. , more preferably 0.4 to 4 parts by mass. The content of the silane coupling agent here is the content of the silane coupling agent contained in the resin composition and the content of the silane coupling agent contained in the silica particles surface-treated with the silane coupling agent. It is the total content. That is, the content of the silane coupling agent here is the silane coupling agent when the silica particles and the silane coupling agent are added by an integral blend method, and the surface treatment with the silane coupling agent. It is the total content with the silane coupling agent contained in the silica particles. If the content of the silane coupling agent is too small, the heat resistance, interlayer adhesive strength, metal foil adhesive strength, etc. tend to decrease. On the other hand, when the content of the silane coupling agent is too large, it is difficult to obtain excellent low dielectric properties, and the heat resistance tends to decrease. Therefore, by setting the content of the silane coupling agent within the above range, the inclusion of silica particles increases the thermal conductivity, and even if the coefficient of thermal expansion is reduced, excellent low dielectric properties, heat resistance, adhesiveness, etc. characteristics can be maintained.

Further, when producing the resin composition, the silica particles previously surface-treated with the silane coupling agent may be added, or the silica particles and the silane coupling agent are integrally blended. may be added.

((C) organic solvent)
The organic solvent used in this embodiment is not particularly limited as long as it does not inhibit the curing reaction of the (A) polyphenylene ether compound. Examples include toluene, methyl ethyl ketone (MEK), cyclohexanone and propylene glycol monomethyl ether acetate. These may be used alone or in combination of two or more.

The content of the organic solvent in the resin composition of the present embodiment is preferably 30 to 50% by mass of the entire composition in the varnish state of the resin mixture. It is more preferably 30 to 40% by mass.

The amount of volatile matter contained in the resin layer of the prepreg or resin-coated film or the resin layer of the resin-coated metal foil, which will be described later, is 100% by mass of the resin layer of the prepreg or resin-coated film or the resin layer of the resin-coated metal foil. is preferably 4% by mass or less, more preferably 3.5% by mass or less, and even more preferably 3.0% by mass or less. The amount of volatile matter here means the weight loss before and after the heat treatment of the sample at 200 ° C. for 10 minutes by the GC / MS method, and the total weight loss under this condition. is the volatile content, and the obtained weight reduction amount is converted to mass%.
<Analysis conditions>
Apparatus: TurboMatrix650/Clarus 600T/Clarus600 (manufactured by PerkinElmer)
Column: SPB-1 (60 m × 0.25 mm × 0.25 μm)
Column heating conditions: 35°C/5 min-(10°C/min)-100°C-(20°C/min)-290°C/19 min
Sample heating conditions: 200°C/10 min
Carrier gas: helium (1 mL/min)
Injection volume: 4.5%
Measurement mode: Scan (m/z = 24-500)

Furthermore, the amount of organic solvent contained in the resin layer of the prepreg or the resin-coated film or the resin layer of the resin-coated metal foil is 100% by mass of the resin layer of the prepreg or resin-coated film or the resin layer of the resin-coated metal foil. is preferably 2% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.6% by mass or less. The amount of the organic solvent is the value obtained by converting the amount of weight reduction corresponding to the organic solvent among the components qualitatively and quantified after the analysis under the same method and under the same conditions as described above, into % by mass.

If the amount of volatile matter is low in this way, there are advantages such as ensuring the heat resistance of the cured product by reducing the amount of generated gas and reducing the risk of curing inhibition due to the generated gas. In addition, the low amount of the organic solvent also has the advantage of reducing the risk of curing inhibition, and reducing the risk of lowering the Tg and reliability of the cured product, including heat resistance, due to the curing inhibition.

(other ingredients)
Moreover, the resin composition according to the present embodiment may further contain other components in addition to the components described above.

For example, the resin composition of the present embodiment may contain a flame retardant, and examples of the flame retardant include halogen-based flame retardants such as brominated flame retardants and phosphorus-based flame retardants. Specific examples of halogen flame retardants include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane, and chlorine flame retardants such as chlorinated paraffin. etc. Specific examples of phosphorus flame retardants include phosphoric acid esters such as condensed phosphoric acid esters and cyclic phosphoric acid esters, phosphazene compounds such as cyclic phosphazene compounds, and phosphinate metal salts such as aluminum dialkylphosphinates. Examples thereof include phosphinate-based flame retardants, melamine-based flame retardants such as melamine phosphate and melamine polyphosphate, and phosphine oxide compounds having a diphenylphosphine oxide group. As the flame retardant, each of the exemplified flame retardants may be used alone, or two or more thereof may be used in combination.

When a flame retardant is contained, the content thereof is preferably 5 to 50 parts by mass, preferably 10 to 3 parts by mass, with respect to the total 100 parts by mass of the resin component containing the (A) polyphenylene ether compound. is more preferred.

Moreover, the resin composition may contain a filler other than the silica particles. Examples of the filler include those added to improve the heat resistance and flame retardancy of the cured product of the curable composition and to improve the dimensional stability during heating, and are not particularly limited. That is, by containing a filler, heat resistance and flame retardancy can be enhanced, and dimensional stability during heating can be enhanced. Specific examples of the filler include metal oxides such as alumina, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. etc.

Moreover, the resin composition according to the present embodiment may further contain a reaction initiator. The curing reaction can proceed even with the component (A) and the above-mentioned cross-linking curing agent alone. may be added. The reaction initiator is not particularly limited as long as it can accelerate the curing reaction of the resin component of the present embodiment. Specifically, for example, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, peroxide Benzoyl oxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyl Oxidizing agents such as lonitrile can be mentioned. Moreover, carboxylic acid metal salt etc. can be used together as needed. By doing so, the curing reaction can be further accelerated. Among these, α,α'-bis(t-butylperoxy-m-isopropyl)benzene is preferably used. Since α,α'-bis(t-butylperoxy-m-isopropyl)benzene has a relatively high reaction initiation temperature, it suppresses the acceleration of the curing reaction at a time when curing is not necessary, such as when the prepreg is dried. It is possible to suppress the deterioration of the storage stability of the resin composition. Furthermore, since α,α'-bis(t-butylperoxy-m-isopropyl)benzene has low volatility, prepregs, films, etc. do not volatilize during drying or storage, and have good stability. Moreover, the reaction initiator may be used alone or in combination of two or more. The content of the reaction initiator is preferably 0.1 to 2 parts by mass per 100 parts by mass of the resin component containing the (A) polyphenylene ether compound.

Furthermore, the resin composition according to the present embodiment may contain various additives other than those described above. Examples of additives include antifoaming agents such as silicone antifoaming agents and acrylic acid ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, dispersants such as wetting and dispersing agents. agents and the like.

The resin composition according to the present embodiment is a varnish-like resin composition because it contains the resin component, the inorganic component, and the organic solvent described above. The resin composition (resin varnish) of the present embodiment is prepared, for example, as follows.

First, (A) a polyphenylene ether compound, and each component that can be dissolved in an organic solvent, such as a cross-linking curing agent and other additives, are put into (C) an organic solvent and dissolved. At this time, it may be heated as necessary. After that, a component that does not dissolve in an organic solvent, the (B) inorganic component material (silica particles and/or silica particles surface-treated with a silane coupling agent), etc. are added, and ball mills, bead mills, planetary mixers, and roll mills are added. A varnish-like resin composition is prepared by dispersing until a predetermined dispersed state is achieved using a varnish-like resin composition.

Since the varnish-like resin composition of the present embodiment is excellent in fluidity, it has advantages of good film flexibility, good film-forming property, and good impregnation property into a fibrous base material, and is easy to handle. Moreover, by using the resin composition of the present embodiment, it is possible to provide prepregs, metal-clad laminates, and the like that are excellent in appearance.

(Prepregs, films with resin, metal-clad laminates, circuit boards, and metal foils with resin)
Next, a prepreg, a metal-clad laminate, a wiring board, and a resin-coated metal foil using the resin composition of the present embodiment will be described. Reference numerals in the drawings described below are: 1 prepreg, 2 resin composition or semi-cured resin composition, 3 fibrous base material, 11 metal-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring. , 21 wiring substrate, 31 resin-coated metal foil, 32 and 42 resin layers, 41 resin-coated film, and 43 support film (substrate), respectively.

FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the invention.

A prepreg 1 according to the present embodiment includes the resin composition or a semi-cured material 2 of the resin composition, and a fibrous base material 3, as shown in FIG. Examples of the prepreg 1 include those in which a fibrous base material 3 is present in the resin composition or semi-cured material 2 thereof. That is, this prepreg 1 comprises the resin composition or its semi-cured material, and the fibrous base material 3 present in the resin composition or its semi-cured material 2 .

In the present embodiment, the term "semi-cured product" refers to a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a semi-cured resin composition (B-staged). For example, when a resin composition is heated, the viscosity of the resin composition first gradually decreases, and thereafter, curing starts and the viscosity gradually increases. In such a case, semi-curing includes the state between when the viscosity starts to rise and before it is completely cured.

The prepreg obtained using the resin composition according to the present embodiment may include a semi-cured product of the resin composition as described above, or may be the uncured resin composition. It may be provided with the same. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition in the B stage) and a fibrous base material, or the resin composition before curing (the resin composition in the A stage). and a fibrous base material. Specifically, for example, the resin composition may include a fibrous base material. The resin composition or its semi-cured material may be obtained by drying or heat-drying the resin composition.

As a method for producing the prepreg 1 of the present embodiment using the varnish-like resin composition of the present embodiment, for example, the fibrous base material 3 is impregnated with the resin varnish-like resin composition 2, and then dried. method.

Specific examples of fibrous base materials used for producing prepreg include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven fabric, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. When glass cloth is used, a laminate having excellent mechanical strength can be obtained, and flattened glass cloth is particularly preferable. The glass cloth used in this embodiment is not particularly limited, but examples thereof include low dielectric constant glass cloth such as E glass, S glass, NE glass, and L glass. Specifically, the flattening process can be carried out, for example, by continuously pressurizing the glass cloth with press rolls at an appropriate pressure to flatten the yarn. As for the thickness of the fibrous base material, for example, one with a thickness of 0.01 to 0.3 mm can be generally used.

Impregnation of the fibrous base material 3 with the resin varnish (resin composition 2) is performed by dipping, coating, or the like. This impregnation can be repeated multiple times if desired. In this case, it is also possible to repeat the impregnation using a plurality of resin varnishes having different compositions and concentrations to finally adjust the desired composition (content ratio) and resin amount.

The fibrous base material 3 impregnated with the resin varnish (resin composition 2) is heated under desired heating conditions, for example, at 80° C. or higher and 180° C. or lower for 1 minute or longer and 10 minutes or shorter. By heating, the solvent is volatilized from the varnish and the solvent is reduced or removed to obtain the pre-cured (A stage) or semi-cured (B stage) prepreg 1 .

Further, as shown in FIG. 4, the resin-coated metal foil 31 of the present embodiment has a configuration in which a metal foil 13 and a resin layer 32 containing the above-described resin composition or a semi-cured material of the resin composition are laminated. have That is, the resin-coated metal foil of the present embodiment may be a resin-coated metal foil comprising a resin layer containing the resin composition before curing (the resin composition in the A stage) and a metal foil, It may be a resin-coated metal foil comprising a resin layer containing a semi-cured product of the resin composition (the B-stage resin composition) and a metal foil.

As a method of manufacturing such a resin-coated metal foil 31, for example, there is a method of coating the surface of the metal foil 13 such as a copper foil with the above-described resin composition in the form of a resin varnish, followed by drying. Examples of the coating method include a bar coater, a comma coater, a die coater, a roll coater, and a gravure coater.

As the metal foil 13, metal foils used in metal-clad laminates, wiring boards, and the like can be used without limitation, and examples thereof include copper foil and aluminum foil.

Furthermore, as shown in FIG. 5, the resin-coated film 41 of the present embodiment is formed by laminating a resin layer 42 containing the above-described resin composition or a semi-cured product of the resin composition and a film supporting substrate 43. have a configuration. That is, the resin-coated film of the present embodiment may be a resin-coated film comprising the resin composition before curing (the resin composition in the A stage) and a film supporting substrate, or the resin composition (B-stage resin composition) and a film supporting substrate.

As a method for producing such a resin-coated film 41, for example, after applying a resin varnish-like resin composition as described above to the surface of the film supporting substrate 43, the solvent is volatilized from the varnish to reduce the solvent. or removing the solvent, it is possible to obtain a resin-coated film before curing (A stage) or in a semi-cured state (B stage).

Examples of the film supporting substrate include electrically insulating films such as polyimide film, PET (polyethylene terephthalate) film, polyester film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polycarbonate film, and polyarylate film. etc.

In the resin-coated film and resin-coated metal foil of the present embodiment, the resin composition or its semi-cured material may be obtained by drying or heat-drying the resin composition, similarly to the prepreg described above.

The thickness and the like of the metal foil 13 and the film supporting substrate 43 can be appropriately set according to the desired purpose. For example, the metal foil 13 may have a thickness of about 0.2 to 70 μm. When the thickness of the metal foil is, for example, 10 μm or less, it may be a copper foil with a carrier provided with a release layer and a carrier for improved handling. The application of the resin varnish to the metal foil 13 and the film supporting substrate 43 is performed by coating or the like, and this can be repeated multiple times as necessary. In this case, it is also possible to repeatedly apply a plurality of resin varnishes having different compositions and densities to finally adjust the desired composition (content ratio) and resin amount.

Drying or heat-drying conditions in the manufacturing method of the resin-coated metal foil 31 and the resin film 41 are not particularly limited, but after the resin composition in the form of a resin varnish is applied to the metal foil 13 or the film supporting substrate 43, a desired amount of heat is applied. heating conditions, for example, heating at 80 ~ 170 ° C. for about 1 ~ 10 minutes to volatilize the solvent from the varnish, reduce the solvent, or remove the solvent, before curing (A stage) or semi-curing The metal foil 31 with resin and the resin film 41 in the state (B stage) are obtained.

The resin-coated metal foil 31 and the resin film 41 may be provided with a cover film or the like, if necessary. By providing the cover film, it is possible to prevent foreign matter from entering. The cover film is not particularly limited as long as it can be peeled off without damaging the form of the resin composition. Films formed by providing layers, papers obtained by laminating these films on paper substrates, and the like can be used.

As shown in FIG. 2, the metal-clad laminate 11 of the present embodiment is characterized by having an insulating layer 12 containing a cured product of the above-described resin composition or a cured product of the above-described prepreg, and a metal foil 13. do. As the metal foil 13 used in the metal-clad laminate 11, the same metal foil 13 as described above can be used.

The metal-clad laminate 13 of the present embodiment can also be produced using the metal foil 31 with resin or the resin film 41 described above.

As a method of producing a metal-clad laminate using the prepreg 1, the resin-coated metal foil 31, and the resin film 41 obtained as described above, the prepreg 1, the resin-coated metal foil 31, and the resin film 41 are prepared one by one or A double-side or single-side metal-foil-clad laminate is obtained by stacking a plurality of sheets, stacking a metal foil 13 such as copper foil on both sides or one side of the stack, and laminating and integrating them by heating and pressurizing them. It is something that can be made. The heating and pressurizing conditions can be appropriately set depending on the thickness of the laminated plate to be produced, the type of the resin composition, etc. It can be ˜150 minutes.

Alternatively, the metal-clad laminate 11 may be produced by forming a film-like resin composition on the metal foil 13 without using the prepreg 1 or the like, followed by heating and pressing.

Then, as shown in FIG. 3, the wiring board 21 of the present embodiment has an insulating layer 12 containing a cured product of the resin composition described above or a cured product of the prepreg described above, and wiring 14 .

As a method for manufacturing such a wiring board 21, for example, the metal foil 13 on the surface of the metal-clad laminate 13 obtained above is etched to form a circuit (wiring), thereby forming a circuit (wiring) on the surface of the laminate. The wiring board 21 provided with the conductor pattern (wiring 14) as a circuit can be obtained. In addition to the methods described above, examples of methods for forming a circuit include forming a circuit by a semi-additive process (SAP: Semi-Additive Process) or a modified semi-additive process (MSAP: Modified Semi-Additive Process).

The prepreg, resin-coated film, and resin-coated metal foil obtained using the resin composition of the present embodiment have low dielectric properties, heat resistance, adhesiveness, etc. in the cured product, and are therefore very useful in industrial applications. Useful. In addition, the metal-clad laminate and wiring board containing them also have low dielectric properties, excellent heat resistance, adhesiveness, and the like. Furthermore, since the resin composition of the present embodiment has excellent fluidity, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards obtained using the resin composition have excellent appearance.

As described above, this specification discloses technologies of various aspects, and the main technologies thereof are summarized below.

The resin composition according to one aspect of the present invention includes (A) a polyphenylene ether compound having a terminal group represented by the following formula (1), and (B) (b-1) a carbon-carbon unsaturated double bond. A silane coupling agent and silica particles having a functional group containing in the molecule, and (b-2) at least one of the silica particles surface-treated with the silane coupling agent, and (C) an organic solvent, In the component (A), a mixture obtained by mixing the component (A) and ion-exchanged water (pH = 5.0) at a weight ratio of 1:3 is ultrasonically vibrated at room temperature for 10 minutes, and then filtered. It is characterized in that the pH of the extract when extracted is 5.0 or higher.

[In Formula (1), R ₁ represents a hydrogen atom or an alkyl group. ]
With such a configuration, it is possible to provide a resin composition having excellent fluidity when formed into a varnish while maintaining properties such as heat resistance and electrical properties in a cured product of the resin composition.

Further, in the resin composition, the total content of the silica particles and the silica particles surface-treated with the silane coupling agent is 50 parts by mass to 250 parts by mass with respect to 100 parts by mass of the resin component containing the polyphenylene ether compound. Parts by mass are preferred. Thereby, in the cured product of the resin composition, it is possible to increase the thermal conductivity and decrease the thermal expansion coefficient while maintaining excellent low dielectric properties and heat resistance.

Furthermore, the functional group containing a carbon-carbon unsaturated double bond preferably has at least one functional group selected from the group consisting of methacryloxy, styryl, vinyl and acryloxy groups. As a result, it is considered that the effects as described above can be obtained more reliably.

Furthermore, in the resin composition, it is preferable that the silane coupling agent further has a methoxy group. It is considered that the effect of the present invention can be more exhibited thereby.

Further, in the resin composition, the amount of methacrylic acid dimer and its hydrolyzate as impurities contained in the component (A) is preferably 200 μg/g or less. As a result, it is considered that the effects as described above can be obtained more reliably.

Moreover, it is preferable that the resin composition further contains a cross-linking curing agent. As a result, the curing reaction is thought to form crosslinks more favorably, and the heat resistance of the cured product of the resin composition can be further enhanced.

A prepreg according to still another aspect of the present invention is characterized by comprising the above resin composition or a semi-cured product of the resin composition and a fibrous base material.

A resin-coated film according to still another aspect of the present invention is characterized by having a resin layer containing the above resin composition or a semi-cured product of the resin composition and a support film.

A resin-coated metal foil according to still another aspect of the present invention comprises a metal foil and a resin layer containing the above resin composition or a semi-cured product of the resin composition.

A metal-clad laminate according to still another aspect of the present invention is characterized by comprising an insulating layer containing a cured product of the above-described resin composition or a cured product of the above-described prepreg, and a metal foil.

A wiring board according to still another aspect of the present invention is characterized by comprising an insulating layer containing a cured product of the above-described resin composition or a cured product of the above-described prepreg, and wiring.

According to the configuration as described above, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, which can obtain a substrate having properties such as heat resistance and low dielectric properties and having an excellent appearance, A wiring board or the like can be provided.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these.

First, the components used in preparing the resin composition in this example will be described.

<A component: Polyphenylene ether compound>
· Polyphenylene ether compound 1 (pH = 5.0)
A polyphenylene ether compound 1 was obtained by reacting a polyphenylene ether resin having an intrinsic viscosity of 0.09 dL/g with methacrylic anhydride.

Specifically, by reacting polyphenylene ether and methacrylic anhydride in the presence of 4-(N,N-dimethylamino)pyridine as a catalyst, the modification represented by the above formula (2) of the present embodiment A polyphenylene ether compound A was obtained.

Next, the resulting modified polyphenylene ether compound A was washed with an acid aqueous solution (pH) and a base aqueous solution (pH) while adjusting the pH to 5.0 to obtain a polyphenylene ether compound 1. .

· Polyphenylene ether compound 2 (pH = 6.0)
Polyphenylene ether compound 2 was obtained by adjusting the pH of polyphenylene ether compound A to 6.0 while appropriately adjusting washing with an aqueous solution (pH) and an aqueous base solution (pH).

· Polyphenylene ether compound 3 (pH = 4.0)
Polyphenylene ether compound 3 was obtained by adjusting the pH of polyphenylene ether compound A to 4.0 while appropriately adjusting washing with an aqueous solution (pH) and an aqueous base solution (pH).

· Polyphenylene ether compound 4 (pH = 4.7)
Polyphenylene ether compound 4 was obtained by adjusting the pH of polyphenylene ether compound A to 4.7 while appropriately adjusting washing with an aqueous solution (pH) and an aqueous base solution (pH).

<Other resins>
・ Cresol novolac type epoxy resin “N690” (manufactured by DIC Corporation)
・ Novolak type phenolic resin “TD2131” (manufactured by DIC Corporation)
・ Dicyclopentadiene type epoxy resin “HP-7200H” (manufactured by DIC Corporation)
・Unmodified polyphenylene ether compound “SA90” (manufactured by SABIC Innovative Plastics)
・ Cyanate ester resin “BADCy” (manufactured by Lonza Japan Co., Ltd.)

<Crosslinking type curing agent>
・ TAIC: triallyl isocyanurate, (manufactured by Nippon Kasei Co., Ltd.)
・DVB810: Divinylbenzene (Nippon Steel & Sumikin Chemical Co., Ltd.)

<Reaction initiator>
Peroxide: 1,3-bis(butylperoxyisopropyl)benzene (Perbutyl P manufactured by NOF Corporation)
<Reaction catalyst>
・ Imidazole curing agent “2E4MZ” (manufactured by Shikoku Kasei Co., Ltd.)
・Metal soap “Zinc octanoate (OCT-Zn) (manufactured by DIC Corporation)

<B component: silane coupling agent>
Epoxysilane: a silane coupling agent having an epoxy group in the molecule (3-glycidoxypropyltrimethoxysilane, "KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.)
Aminosilane: a silane coupling agent having an amino group in the molecule (3-aminopropyltrimethoxysilane, "KBM-903" manufactured by Shin-Etsu Silicone Co., Ltd.)
- Vinylsilane: a silane coupling agent having a vinyl group in the molecule (vinyltrimethoxysilane, "KBM-1003" manufactured by Shin-Etsu Silicone Co., Ltd.)
- Methacrylsilane: a silane coupling agent having a methacryl group in the molecule (3-methacryloxypropyltrimethoxysilane, "KBM-503" manufactured by Shin-Etsu Silicone Co., Ltd.)

<B component: silica particles>
Silica-1: silica particles surface-treated with a silane coupling agent (silica particles surface-treated with a silane coupling agent having an epoxy group in the molecule, "SC2500-SEJ" manufactured by Admatechs)
Silica-2: silica particles surface-treated with a silane coupling agent (silica particles surface-treated with a silane coupling agent having a vinyl group in the molecule, SC-2300SVJ manufactured by Admatechs Co., Ltd.)
・ Untreated silica: silica particles that have not been surface-treated with a silane coupling agent (“SO-25R” manufactured by Admatechs)

<C component: organic solvent>
·toluene

[Test Example 1]
<Examples 1 to 12, Comparative Examples 1 to 2>
[Preparation of resin composition (varnish)]
Resin component (I) was prepared by mixing 60 parts by mass of polyphenylene ether compound 1 (pH=5.0), 40 parts by mass of cross-linking curing agent (TAIC) and 1 part by mass of reaction initiator (PBP). This resin component (I) was mixed with a silane coupling agent, silica particles and an organic solvent (toluene) in the amounts (parts by mass) shown in Tables 1 and 2. The mixture was stirred at 25° C. for 60 minutes to obtain varnish-like resin compositions (varnishes) of Examples 1-12 and Comparative Examples 1-2. In the following, the resin component (I) means a resin component containing a polyphenylene ether compound as a main component and using TAIC as a cross-linking curing agent.

<Example 13>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 1 (pH = 5.0), 40 parts by mass of cross-linking curing agent (DBV), and 1 part by mass of reaction initiator (PBP) were used as resin component (II). A varnish-like resin composition (varnish) was obtained in the same manner as in Example 1. In the following description, resin component (II) means a resin component containing a polyphenylene ether compound as a main component and using DBV as a cross-linking curing agent.

<Comparative Examples 3 to 18>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 3 (pH = 4.0), 40 parts by mass of cross-linking curing agent (TAIC), and 1 part by mass of reaction initiator (PBP) were used as resin component (I). A varnish-like resin composition (varnish) was obtained in the same manner as in Example 1.

<Comparative Example 19>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 3 (pH = 4.0), 40 parts by mass of cross-linking curing agent (DBV), and 1 part by mass of reaction initiator (PBP) were used as resin component (II). A varnish-like resin composition (varnish) was obtained in the same manner as in Example 1.

<Evaluation test>
(pH of PPE compound)
Each PPE compound and ion-exchanged water (pH=5.0) were weighed at a weight ratio of 1:3 and treated at room temperature (20 to 23° C.) for 10 minutes while applying ultrasonic vibration. After the treatment, the pH of the ion-exchanged water was measured with pH test paper.

(Impurity content in PPE compound)
First, about 11 g of pure water was added to about 0.8 g of each sample, and after applying ultrasonic waves for 10 minutes, filter filtration was performed.

Next, the contents of the methacrylic acid dimer and the hydrolyzate of the methacrylic acid dimer in each polyphenylene ether compound were measured from the obtained samples by ion chromatography (IC) analysis.

The apparatus used was "DX500" manufactured by Thermo Fisher, and the separation column used was Ionpac AS17C. Table 1 shows each measurement result (IC detection amount).

(Cup viscosity of varnish-like resin composition)
Solvent (methyl ethyl ketone) was taken in a jug, a cup viscometer ("NK-2" manufactured by Anest Iwata Co., Ltd.) was immersed in it, and the mixture was stirred for 2 to 3 minutes so that the temperature of the cup body became the same as that of the solvent. The cup body was filled with the solvent in the solvent, and the cup body was lifted out of the new solvent to start the measurement. A stopwatch was used to measure the time from the start of the measurement until the solvent dropped from the hole in the cup. The cup body was kept as horizontal as possible, and the solvent was allowed to drop smoothly through the hole in the cup. It was confirmed that the time (seconds) required from the start of measurement to the end of measurement was 6 to 7 seconds.

Next, three types of varnishes (resin compositions) were prepared as samples. varnish immediately after preparation, varnish 7 days after preparation and varnish 30 days after preparation. The storage conditions were as follows: the temperature was 20° C. and the humidity was 55% or less.

The cup body of the cup viscometer is immersed in each resin varnish (varnish immediately after preparation, varnish 7 days after preparation, and varnish 30 days after preparation), stirred for 2 to 3 minutes, and the cup body is the resin varnish. The temperature was kept the same. The cup body was filled with varnish in the resin varnish, and the cup body was lifted out of the varnish to start the measurement. A stopwatch was used to measure the time from the start of measurement until the varnish fell from the cup hole. The cup body was kept as horizontal as possible, and the varnish was smoothly dropped from the hole of the cup. The time (seconds) required from the start of the measurement to the end of the measurement was taken as the cup viscosity. This was repeated and the cup viscosity was measured twice. If the difference between the two data was within 3 seconds, it was determined that the measurement was performed correctly.

(Production of prepreg and appearance evaluation)
A prepreg was obtained by impregnating a glass cloth (manufactured by Nittobo Co., Ltd., 2116 type) with the resin varnish immediately after preparation prepared in each example and comparative example, followed by drying by heating at 130° C. for about 3 minutes. At that time, the content of the resin composition (resin content) relative to the weight of the prepreg was adjusted to about 56% by mass.

The appearance of the obtained prepreg was evaluated by visual inspection. Evaluation criteria are as follows.

○: Uniformly applied, no streaks or resin unevenness × (streaks/unevenness): There is unevenness in how the resin is applied or streaks can be seen

(Preparation of copper-clad laminate and evaluation of heat resistance)
Six sheets of the prepreg were placed on both sides of the 35 μm-thick copper foil (“3EC3” manufactured by Mitsui Kinzoku Co., Ltd.) to form ^a pressurized body. After heating and pressing for 90 minutes, a copper-clad laminate having a thickness of about 0.76 mm with copper foil adhered to both sides was obtained.

• Heat resistance The solder heat resistance of the obtained copper-clad laminate after moisture absorption was measured by the following method. First, the obtained 50 mm × 50 mm copper clad laminate was etched, each sample was subjected to a pressure cooker test (PCT) at 121 ° C. humidity 100%, 1 atm, 4 hours, and immersed in a solder bath at 288 ° C. for 20 seconds. Then, the presence or absence of measling or blistering was visually observed. A case where measling or blistering did not occur was evaluated as ◯, and a case where it did was evaluated as x.

The above results are shown in Table 1 (Example) and Table 2 (Comparative Example). In Tables 1 and 2, resin system (I) refers to a resin component using TAIC as a cross-linking curing agent, and resin system (II) refers to a resin component using DBV as a cross-linking curing agent. means In addition, resin system (I) and resin system (II) in the table mean components other than the reaction initiator (PBP) in the respective resin component (I) and resin component (II) described above.

(Discussion)
As is clear from the results shown in Table 1, the resin composition of the present invention was excellent in fluidity, and maintained excellent fluidity even after 30 days from the preparation of the varnish. In addition, the appearance of the prepreg and the heat resistance of the laminate were excellent.

On the other hand, as shown in Table 2, Comparative Examples 3-19 using a PPE compound with a low pH exhibited poor fluidity and, therefore, poor appearance of the prepreg. In addition, (b-1) a silane coupling agent and silica particles having a functional group containing a carbon-carbon unsaturated double bond in the molecule, and (b-2) silica particles surface-treated with the silane coupling agent Sufficient heat resistance could not be obtained in the laminate in Comparative Example 1-2, which had none of them.

[Test Example 2]
<Examples 14-15>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 2 (pH = 6.0), 40 parts by mass of cross-linking curing agent (TAIC), and 1 part by mass of reaction initiator (PBP) except that the resin component was used as the resin component. Similarly, a varnish-like resin composition (varnish) was obtained.

<Example 16>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 2 (pH = 6.0), 40 parts by mass of cross-linking curing agent (DBV), and 1 part by mass of reaction initiator (PBP) except that the resin component was used as the resin component. Similarly, a varnish-like resin composition (varnish) was obtained.

<Comparative Example 20-21>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 4 (pH = 4.7), 40 parts by mass of cross-linking curing agent (TAIC), and 1 part by mass of reaction initiator (PBP) except that the resin component was used as the resin component. Similarly, a varnish-like resin composition (varnish) was obtained.

<Comparative Example 22>
[Preparation of resin composition (varnish)]
60 parts by mass of polyphenylene ether compound 4 (pH = 4.7), 40 parts by mass of cross-linking curing agent (DBV), and 1 part by mass of reaction initiator (PBP) except that the resin component was used as the resin component. Similarly, a varnish-like resin composition (varnish) was obtained.

Using the obtained varnish-like resin composition, the pH of the PPE compound, the cup viscosity of the varnish-like resin composition, the appearance of the prepreg, and the heat resistance of the laminate were evaluated in the same manner as in Example 1. Table 3 shows the results. In Table 3, resin system (I) refers to a resin component using TAIC as a cross-linking curing agent, and resin system (II) refers to a resin component using DBV as a cross-linking curing agent. do.

(Discussion)
Even at a pH of 6.0, the resin composition of the present invention showed excellent results in terms of fluidity, prepreg appearance, and laminate heat resistance, as in Examples 1-15.

On the other hand, the resin compositions of Comparative Examples 20 to 22, which had a pH of less than 5.0, were resin systems using a cross-linking curing agent different from those of the comparative examples in Table 2, but still had fluidity and Both the appearance of the prepreg and the heat resistance of the laminate were inferior.

[Test Example 3]
Furthermore, in order to evaluate further properties (electrical properties: low dielectric properties) of the resin composition of the present invention, comparative tests with other resin systems were conducted.

<Comparative Example 23>
[Preparation of resin composition (varnish)]
Resin component (III) was prepared by mixing 70 parts by mass of norezol novolak-type epoxy resin, 30 parts by mass of novolac-type phenolic resin, and 0.05 parts by mass of reaction catalyst (2E4MZ). This resin component (III) was mixed with silica particles and an organic solvent (toluene) in the amounts shown in Table 4 (parts by mass). A varnish-like resin composition (varnish) of Comparative Example 23 was obtained by stirring the mixture at 25° C. for 60 minutes.

<Comparative Example 24>
[Preparation of resin composition (varnish)]
A resin component (IV) was prepared by mixing 50 parts by mass of a dicyclopentadiene type epoxy resin, 20 parts by mass of an unmodified polyphenylene ether compound, 30 parts by mass of a cyanate ester resin, and 0.005 parts by mass of a reaction catalyst (OCT-Zn). This resin component (IV) was mixed with silica particles and an organic solvent (toluene) in the amounts shown in Table 4 (parts by mass). By stirring the mixture at 25° C. for 60 minutes, a varnish-like resin composition (varnish) of Comparative Example 24 was obtained.

(Preparation of laminate)
Using the resin compositions of Examples 1, 2, 7 and 11 and Comparative Examples 23 and 24, prepregs were produced in the same manner as in Test Example 1 above. A copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm was placed on both sides of the six prepregs thus obtained, and the pressure was applied under vacuum conditions at a temperature of 210° C. and a pressure of 30 kgf/cm ^{2 .} A copper-clad laminate having a thickness of about 0.75 mm and having copper foil adhered to both sides was obtained by heating and pressing for 90 minutes under the conditions of .

<Evaluation test>
[Dielectric properties (relative permittivity and dielectric loss tangent)]
The dielectric constant (Dk) and dielectric loss tangent (Df) of the evaluation substrate at 1 GHz were measured using a material/impedance analyzer (HP4291A and HP16453A manufactured by Hewlett-Packard). A laminate obtained by removing the copper foil from the above copper-clad laminate was used as an evaluation substrate. The measurement was carried out by a method based on PC-TM-650 2.5.5.9.

Table 4 shows the results.

（考察）
表４に示す結果から明らかなように、本発明の樹脂組成物は、他の樹脂系（比較例２３～２４）と比べて、低誘電特性を示すことが示された。以上より、本発明の樹脂組成物は、その硬化物における耐熱性や接着性、電気特性等の特性を維持したまま、ワニス状にした際の流動性に優れる樹脂組成物であることが確認された。In Table 4 below, the resin system (I) to resin system (IV) are the reaction initiator (PBP) and the reaction catalyst (2E4MZ , OCT-Zn).

(Discussion)
As is clear from the results shown in Table 4, the resin composition of the present invention exhibited lower dielectric properties than other resin systems (Comparative Examples 23-24). From the above, it was confirmed that the resin composition of the present invention is a resin composition that has excellent fluidity when made into a varnish while maintaining properties such as heat resistance, adhesiveness, and electrical properties in the cured product. rice field.

This application is based on Japanese Patent Application No. 2018-146827 filed on August 3, 2018, the content of which is included in the present application.

In order to express the present invention, the present invention has been properly and fully described above through the embodiments with reference to specific examples, drawings, etc., but those skilled in the art may modify and/or improve the above-described embodiments. should be recognized as something that can be done easily. Therefore, to the extent that modifications or improvements made by those skilled in the art do not deviate from the scope of the claims set forth in the claims, such modifications or modifications do not fall within the scope of the claims. is interpreted to be subsumed by

INDUSTRIAL APPLICABILITY The present invention has wide industrial applicability in technical fields related to electronic materials and various devices using the same.

Claims (10)

(A) a polyphenylene ether compound having a terminal group represented by the following formula (1);
(B) (b-1) a silane coupling agent and silica particles having a functional group containing a carbon-carbon unsaturated double bond in the molecule, and (b-2) silica surface-treated with the silane coupling agent at least one of the particles;
(C) an organic solvent,
In the component (A), a mixture obtained by mixing the component (A) and ion-exchanged water (pH = 5.0) at a weight ratio of 1:3 is ultrasonically vibrated at room temperature for 10 minutes, and then filtered. The pH of the extract when extracted is 5.0 or more and 7.0 or less ,
A resin composition, wherein the amount of methacrylic acid dimer and its hydrolyzate as impurities contained in the component (A) is 200 µg/g or less.

[In Formula (1), R ₁ represents a hydrogen atom or an alkyl group. ] Claim 1, wherein the total content of the silica particles and the silica particles surface-treated with the silane coupling agent is 50 parts by mass to 250 parts by mass with respect to 100 parts by mass of the resin component containing the polyphenylene ether compound. The resin composition according to . The resin according to claim 1 or 2, wherein the functional group containing a carbon-carbon unsaturated double bond has at least one functional group selected from the group consisting of a methacryloxy group, a styryl group, a vinyl group, and an acryloxy group. Composition. The resin composition according to any one of claims 1 to 3, wherein the silane coupling agent further has a methoxy group. The resin composition according to any one of claims 1 to 4 , further comprising a cross-linking curing agent. A prepreg comprising the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition and a fibrous base material. A resin-coated film comprising a resin layer containing the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition, and a support film. A resin-coated metal foil, comprising a resin layer containing the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition, and a metal foil. A metal clad laminate comprising an insulating layer containing the cured product of the resin composition according to any one of claims 1 to 5 or the cured product of the prepreg according to claim 6 , and a metal foil. A wiring board comprising an insulating layer containing the cured product of the resin composition according to any one of claims 1 to 5 or the cured product of the prepreg according to claim 6 , and wiring.

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