JP2021075664A - Low dielectric loss tangent resin composition - Google Patents

Abstract

To provide a low dielectric loss tangent resin composition which has excellent film forming ability, provides a cured product having high heat resistance and adhesion, and is low in dielectric constant and dielectric loss tangent.SOLUTION: The resin composition contains: a terminal-modified polymer compound that is a reactant of a terminal hydroxyl group of a random copolymer compound of (A) a polyphenylene ether resin having phenolic hydroxyl groups on both terminals, (B) an aliphatic polymer having alcoholic hydroxyl groups on both terminals and (C) an acid dichloride compound that is a binder, in which a mol number a of (A) the polyphenylene ether resin, a mol number b of (B) the aliphatic polymer and a mol number c of (C) the acid dichloride compound that is the binder satisfy a relation of (a+b)>c, and a substituent reactive with a hydroxyl group in (D) a compound having a substituent reactive with a hydroxyl group and an unsaturated double bond group; a modified polystyrene compound having an unsaturated double bond on the side chain; and a radical initiator.SELECTED DRAWING: None

Description

The present invention relates to a resin composition that can be easily formed into a film shape by casting a solution onto a substrate, and the cured product thereof is excellent in flexibility, heat resistance, water resistance, dielectric properties, and adhesiveness.

The phenoxy resin is a polymer compound having a very large molecular weight obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenol compound. By adding this phenoxy resin, a general epoxy resin composition or radically polymerizable composition can be formed into a film shape, and therefore, it is used in a wide range of fields as an important component of a film-like adhesive. Especially in the electric and electronic fields, it is used for an interlayer insulating layer of a printed wiring board and a copper foil with a resin. However, the cured product of the resin composition to which the phenoxy resin is added has excellent adhesiveness but low heat resistance and high dielectric constant and dielectric loss tangent (dielectric constant 3.5 and dielectric loss tangent 0.03 at a frequency of 1 GHz). The fact is that it cannot be used for electronic device applications where the signal response speed has increased in recent years. Polymer fluorine compounds (Patent Document 1) such as polytetrafluoroethylene (PTFE) and liquid crystal polymers (Patent Document 2) are generally known as resins having excellent dielectric properties such as low dielectric constant and dielectric loss tangent. , These resins have a problem that the compatibility with other resins is extremely low and the adhesiveness is low.
Patent Document 3 describes a method of mixing a rubber component in order to impart flexibility to the polyphenylene ether resin, but the epoxy resin is poor in adhesiveness only with the polyphenylene ether resin and the rubber component. Had no choice but to add. Although the epoxy resin has excellent adhesiveness, it generates a highly polar alcoholic hydroxyl group during the reaction, so that there is a problem that the dielectric property is deteriorated like the above-mentioned phenoxy resin.

Japanese Unexamined Patent Publication No. 2005-001274 Japanese Unexamined Patent Publication No. 2014-060449 JP-A-2010-222408

The present invention has been made in view of the above points, and provides a resin composition having an excellent film-forming ability, a cured product having high heat resistance and adhesiveness, and a low dielectric constant and low dielectric loss tangent. The purpose is to do.

As a result of diligent studies, the present inventors have conducted a random combination of a polyphenylene ether resin having a relatively low molecular weight having phenolic hydroxyl groups at both ends, an aliphatic polymer having alcoholic hydroxyl groups at both ends, and a binder. A resin composition containing a terminally modified polymer compound in which the end of the polymer compound is further modified with a compound having an unsaturated double bond, a modified polystyrene compound having an unsaturated double bond in the polymer chain, and a radical initiator. The present invention has been completed by finding that the above-mentioned requirements are satisfied.
That is, the present invention
[1] A terminally modified polymer compound, which is a reaction product of a random copolymer compound and a compound having a substituent (D) capable of reacting with a hydroxyl group and an unsaturated double bond group.
A resin composition containing a modified polystyrene compound having an unsaturated double bond in the side chain and a radical initiator.
The random copolymer compound
(A) Polyphenylene ether resin having phenolic hydroxyl groups at both ends,
(B) Aliphatic polymers having alcoholic hydroxyl groups at both ends,
(C) A random copolymer compound with an acid dichloride compound which is a binder, and the number of moles a of the (A) polyphenylene ether resin, the number b of the (B) aliphatic polymer, and the (C). ) A resin composition in which the number of moles c of the acid dichloride compound as a binder satisfies the relationship of (a + b)> c,
[2] The resin composition according to the preceding item [1], wherein the number of moles a of the (A) polyphenylene ether resin and the number b of the moles of the (B) aliphatic polymer satisfy the relationship of a> b.
[3] The terminal-modified polymer compound has the following formula (1).

In the formula (1), RA is (A) a divalent linking group obtained by removing two hydrogen atoms from the phenolic hydroxyl groups at both ends of a polyphenylene ether resin having phenolic hydroxyl groups at both ends, and RB is (B). A divalent linking group obtained by removing two hydrogen atoms from the alcoholic hydroxyl groups at both ends of an aliphatic polymer having alcoholic hydroxyl groups at both ends is represented by the following formula (2).

(In the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups from the acid dichloride compound which is the binder (C)), and Z represents a divalent linking group. The following formula (3)

(In the formula (3), RD represents a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule.) The substituents represented by d and e are represented by d and e. Is the average value of the number of repeating units and independently represents a real number in the range of 1 to 100. The resin composition according to the preceding item [2], which contains the compound represented by).
[4] RA is the following formula (4)

(In formula (4), X is a divalent linking group excluding two phenolic hydroxyl groups of a compound having two phenolic hydroxyl groups, and R is independently a methyl group, an ethyl group, a propyl group, an allyl group or an allyl group. The phenyl group, g and h are the average values of the number of repeating units, each independently representing a real number in the range of 1 to 100, and y each independently represents an integer of 1 to 4). The resin composition according to the preceding item [3], which is a linking group of
[5] The resin composition according to the preceding item [4], wherein X is a divalent linking group obtained by removing two phenolic hydroxyl groups from bisphenol A, tetramethylbisphenol A, bisphenol F or 4,4'-biphenol.
[6] Any one of the above items [3] to [5], wherein RB is a divalent linking group obtained by removing two hydrogen atoms from the alcoholic hydroxyl groups at both ends of a polybutadiene rubber having alcoholic hydroxyl groups at both ends. The resin composition according to the section,
[7] A modified polystyrene compound having an unsaturated double bond in the side chain is represented by the following formula (9).

(In the formula, G represents a hydrogen atom or an alkyl group, and when a plurality of Gs are present, the respective Gs may be the same or different from each other. Q is a compound having a radically polymerizable double bond and a carboxy group. Represents a residue obtained by removing a hydrogen atom from a carboxy group, and when a plurality of Qs are present, the Qs may be the same or different from each other. M and n are the average values of the number of repeating units and are independent of each other. A compound having a repeating unit in the range of 1 to 2,000 and having a repeating unit represented by the relation of 0.01 ≦ n / (n + m) ≦ 0.05). 6] The resin composition according to any one of the items.
[8] The resin composition according to the preceding item [7], wherein Q is a residue obtained by independently removing a hydrogen atom from the carboxy group of methacrylic acid, acrylic acid, pentene acid or vinylbenzoic acid.
[9] A film-like adhesive comprising the resin composition according to any one of the preceding items [1] to [8], and [10] a resin according to any one of the preceding items [1] to [8]. The composition, or the cured product of the film-like adhesive according to the preceding item [9],
Regarding.

According to the present invention, a resin composition which can be easily formed into a film shape by a casting method and whose cured product is excellent in properties such as flexibility, heat resistance, water resistance, dielectric properties and adhesiveness is provided. Can be done.

Hereinafter, embodiments of the present invention will be described.
The resin composition of the present invention contains a terminally modified polymer compound, a modified polystyrene compound having an unsaturated double bond in the side chain (hereinafter, also simply referred to as “modified polystyrene compound”), and a radical initiator as essential components. ..
First, a random copolymer compound which is an intermediate raw material of the terminal-modified polymer compound will be described.
The random copolymer compound has (A) a phenolic hydroxyl group having phenolic hydroxyl groups at both ends and (B) an aliphatic polymer having alcoholic hydroxyl groups at both ends. The alcoholic hydroxyl group is a compound in which the acid dichloride compound, which is the (C) binder, is copolymerized with the acid chloride group (-COCl group) having two in its structure.

(A) A polyphenylene ether resin having phenolic hydroxyl groups at both ends (hereinafter, also simply referred to as “component (A)”) generally has a structure represented by the following formula (6).

In formula (6), X represents a divalent linking group excluding two phenolic hydroxyl groups of a compound having two phenolic hydroxyl groups. Specific examples of the compound having two phenolic hydroxyl groups here include bisphenol A, tetramethylbisphenol A, bisphenol F, 4,4'-biphenol and the like.
In formula (6), R represents a methyl group, an ethyl group, a propyl group, an allyl group or a phenyl group.
In equation (6), y represents an integer of 1 to 4.
In formula (6), g and h are average values of the number of repeating units, and each independently represents a real number in the range of 1 to 100.

As the component (A), those having a number average molecular weight of several thousand to several hundred thousand are usually available as commercial products, but those having a number average molecular weight of 10,000 or less are preferable as the raw material of the random copolymer compound. As a specific example of a commercially available component (A), Noril SA90 (number average molecular weight 1,700) manufactured by SABIC LLC can be used, but the present invention is not limited thereto.
The molecular weight in the present specification means a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography (GPC).

(B) Specific examples of the aliphatic polymer having alcoholic hydroxyl groups at both ends (hereinafter, also simply referred to as “component (B)”) include a butadiene copolymer having alcoholic hydroxyl groups at both ends and both ends. Examples thereof include a hydride copolymer having an alcoholic hydroxyl group. The number average molecular weight of these components (B) is usually 500 to 10,000, preferably 750 to 7,000.

The amount of the component (A) and the component (B) used in producing the random copolymer compound is not particularly limited, and even if the component (B) having an excessive number of moles with respect to the component (A) is used, ( A component (A) having an excessive number of moles with respect to the component (B) may be used, or an equimolar component (A) and a component (B) may be used, but the amount of the component (B) is excessive with respect to the component (B). It is preferable to use the number of moles of the component (A), that is, the number of moles a of the component (A) and the number of moles b of the component (B) satisfy the relationship of a> b. When the amounts of the component (A) and the component (B) used satisfy the above-mentioned preferable relationship, a random copolymer compound having excellent heat resistance and solvent solubility can be obtained.

The acid dichloride compound (hereinafter, also simply referred to as “component (C)”) as the binder (C) is not particularly limited as long as it is an acid dichloride compound, and specific examples thereof include phthalic acid dichloride, glutalyl chloride, and isophthalic acid. Acid dichloride, terephthalic acid dichloride, oxalyl chloride, malonyl chloride, adipoil chloride, azela oil chloride, sebacoil chloride, azobenzene-4,4'-dicarbonyldichloride, 4,4'-biphenyldicarbonyl chloride, itaconic acid Examples thereof include chloride, hexahydroterephthalic acid dichloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-oxydibenzoyl chloride, 2,5-furandicarbonyldichloride and diglycolyl chloride.

The random copolymer compound has a structure in which the component (A) and the component (B) are randomly copolymerized via the component (C). Copolymerization occurs between the components (A), the components (B), and between the components (A) and the component (B) via the component (C). The obtained copolymer has a structure in which these components are bonded by an ester bond.
Further, the random copolymer compound is a compound having a phenolic hydroxyl group and / or an alcoholic hydroxyl group at both ends, that is, the number of moles a of the component (A), the number b of the component (B) and the component (C). The number of moles c is a copolymer of the components (A), (B) and (C) satisfying the relationship of (a + b)> c. By using phenolic hydroxyl groups and / or alcoholic hydroxyl groups at both ends of the random copolymer compound, substituents and unsaturated double-bonding groups that can react with the hydroxyl group (D) described later by utilizing these terminal hydroxyl groups. It is possible to obtain a terminal-modified polymer compound in which the terminal structure is further modified by the compound having and.

The terminal-modified polymer compound contained in the resin composition of the present invention is not a substituent capable of reacting the phenolic hydroxyl group and / or alcoholic hydroxyl group having the terminal of the above-mentioned random copolymer compound with the (D) hydroxyl group. It is a compound modified with a compound having a saturated double bond group (hereinafter, also simply referred to as “component (D)”). The modification is brought about by the reaction between the hydroxyl group of the random copolymer compound at the end and the hydroxyl group of the component (D) that can react with the hydroxyl group, and even if both ends of the random copolymer compound are modified, one of them is modified. Although only the ends may be modified, a terminal-modified polymer compound in which both ends are knitted is preferable.

The component (D) is not particularly limited as long as it is a compound having a substituent capable of reacting with a hydroxyl group and an unsaturated double bond group in one molecule, but is not particularly limited as long as it is an acid chloride group and an unsaturated double bond group in one molecule. A compound having a heavy bonding group is preferable.
The "unsaturated double bond group" in the present specification is not particularly limited as long as it is a substituent containing a carbon-carbon double bond, but for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, etc. Examples thereof include a pentenyl group, a hexenyl group, a cyclohexenyl group and a heptenyl group, and a vinyl group or an allyl group is preferable.

Specific examples of the compound having an acid chloride group and an unsaturated double bond group in one molecule include methacrylic acid chloride and acrylic acid chloride.

As the terminal-modified polymer compound contained in the resin composition of the present invention, a compound represented by the following formula (1) is preferable.

In the formula (1), RA is a divalent linking group obtained by removing two hydrogen atoms from the phenolic hydroxyl groups at both ends of the component (A), and RB is a hydrogen atom from the alcoholic hydroxyl groups at both ends of the component (B). The divalent linking group excluding two, L is the divalent linking group represented by the following formula (2), Z is the substituent represented by the following formula (3), and d and e are repeated. It is the average value of the number of units and represents a real number in the range of 1 to 100 independently.

In the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups (-COCl groups) from the acid dichloride compound which is the binder (C).

In formula (3), RD represents a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule.

As the terminal-modified polymer compound contained in the resin composition of the present invention, a compound in which RA in the above formula (1) is a divalent linking group represented by the following formula (4) is more preferable.

In formula (4), X is a divalent linking group excluding two phenolic hydroxyl groups of a compound having two phenolic hydroxyl groups, and R is an independently methyl group, ethyl group, propyl group, allyl group or phenyl. As for the group, g and h are the average values of the number of repeating units, and each of them independently represents a real number in the range of 1 to 100, and y represents an integer of 1 to 4, respectively.

Further, as the terminal-modified polymer compound contained in the resin composition of the present invention, X in the above formula (4) is bisphenol A, tetramethylbisphenol A, bisphenol F or 4,4'-biphenol excluding two hydroxyl groups. A compound that is a divalent linking group is more preferable.

Further, as the terminal-modified polymer compound used in the present invention, the RB in the above formula (1) is a polybutadiene rubber having alcoholic hydroxyl groups at both ends, and two hydrogen atoms are removed from the alcoholic hydroxyl groups at both ends. Compounds that are valence linking groups are more preferred.

Next, a method for producing the terminal-modified polymer compound contained in the resin composition of the present invention will be described.
In the terminal-modified polymer compound, the component (A) and the component (B) are uniformly dissolved in a solvent, then the component (C) is added and reacted under heating, and then the component (D) is further added and reacted under heating. It can be obtained by letting it. It is preferable that the number of moles of the component (A) is larger than the number of moles of the component (B). Examples of the solvent include toluene, xylene, methyl isobutyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like, and a mixed solvent thereof may be used, but the solvent is particularly low in boiling point and dried. Easy toluene is preferred. The reaction temperature is usually 50 to 150 ° C., preferably 60 to 140 ° C. for both the reaction of adding the component (C) and the reaction of adding the component (D). The reaction time is preferably 5 to 60 hours.

A catalyst can also be used in combination to promote the reaction. As the catalyst, organic base compounds such as triethylamine, tripropenylamine and pyridine are preferable. When an organic base catalyst is used, the hydrochloric acid generated by the reaction and the organic base form a salt, so that the reaction can be safely carried out without the hydrochloric acid corroding the reaction apparatus. The produced salt can be easily removed by filtration after the reaction is completed. Further, the organic base catalyst acts as a catalyst not only when the component (D) is an acid chloride compound but also when an isocyanate compound or a dimethylchlorosilane compound is used. The amount of the catalyst used is usually 0.1 to 200% by mass, preferably 0.5 to 100% by mass, based on the total amount of the reactants.

The molecular weight range of the terminally modified polymer compound thus obtained is preferably 10,000 to 200,000, more preferably 15,000 to 150,000 in terms of polystyrene-equivalent weight average molecular weight in GPC. If the molecular weight is smaller than the above range, the film forming ability may be insufficient, and if it is large, the viscosity may be high and coating or the like may be difficult.

Next, the modified polystyrene compound contained in the resin composition of the present invention will be described.
The modified polystyrene compound used in the present invention includes (E) styrene (hereinafter, simply referred to as “(E) component”) and (F) a polymerizable monomer having an oxazoline group (hereinafter, simply referred to as “(F) component”). A copolymer of (described), which is obtained by a copolymerization reaction of the component (E) and the component (F) having a specific mass ratio and has a specific number average molecular weight, and (G). ) A reaction product with a compound having a compound having a radically polymerizable double bond and a carboxy group (hereinafter, simply referred to as "component (G)").

Specific examples of the component (F) include 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-vinyl-5,6-dihydro-4H-1,3-oxazoline and 2-propenyl-5. , 6-Dihydro-4H-1,3-oxazoline and the like, with 2-isopropenyl-2-oxazoline being preferred.

When synthesizing a copolymer of the component (E) and the component (F), the component (F) of 1% by mass or more and less than 5% by mass is used with respect to the total mass of the component (E) and the component (F). By setting the amount of the unit derived from the component (F) in the copolymer to the range of the previous term, the resin composition of the present invention containing the modified polystyrene compound obtained by reacting the component (G) with the copolymer , Excellent dielectric properties and high adhesiveness to low-roughness copper foil.

The copolymerization reaction of the component (E) and the component (F) may be carried out according to a general polystyrene synthesis method such as radical polymerization or anionic polymerization.

The number average molecular weight of the copolymer of the component (E) and the component (F) is usually 20,000 to 300,000, preferably 30,000 to 200,000. The number average molecular weight in the present invention means a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography (GPC).

As the copolymer of the component (E) and the component (F), a copolymer having a repeating unit represented by the following formula (7) is preferable.

In formula (7), G represents a hydrogen atom or an alkyl group, and when a plurality of Gs are present, each G may be the same or different from each other. m and n are average values of the number of repeating units, and represent real numbers that are independently in the range of 1 to 2,000 and satisfy the relationship of 0.01 ≦ n / (n + m) ≦ 0.05. The formula (7) is expressed using the average value of the number of repeating units, and the copolymer used as an intermediate raw material of the modified polystyrene compound has a structure in which the components (E) and (F) are randomly copolymerized. It has.

Commercially available products can also be used as the copolymer as an intermediate raw material of the modified polystyrene compound. For example, as a commercial product of a copolymer having a structure represented by the above formula (7), Epocross RPS-1005 (number average molecular weight 70) manufactured by Nippon Shokubai Co., Ltd. having a repeating unit represented by the following formula (8). 000, weight average molecular weight 160,000, m≈654 in formula (8), n≈19) and the like, but are not limited thereto. The proportion of the polymerizable monomer unit having an oxazoline group in Epocross RPS-1005 is 2.8% by mass. The formula (8) is expressed using the average value of the number of repeating units (indicated by m and n in the formula), and the copolymer having the repeating unit represented by the formula (8) is (E). It has a structure in which the component () and the component (F) are randomly copolymerized.

Specific examples of the component (G) include acrylic acid, methacrylic acid, pentene acid, vinyl benzoic acid and the like, and methacrylic acid or acrylic acid is preferable.

The amount of the copolymer (copolymer of (E) component and (F) component) and the component (G) used in synthesizing the modified polystyrene compound is not particularly limited, but with respect to the oxazoline group in the copolymer. It is preferable to use the equivalent amount or less of the component (G). When an excessive number of moles of the (G) component with respect to the oxazoline group in the copolymer is used, the resin composition is cured due to the influence of the unreacted (G) component remaining in the modified polystyrene compound after synthesis. The dielectric properties and heat resistance of the object may decrease. The amount of the component (G) used in synthesizing the modified polystyrene compound is preferably 0.7 to 1 equivalent, preferably 0.8 to 1 equivalent, based on the oxazoline group in the copolymer of the components (E) and (F). 1 equivalent is more preferred, and 0.9 to 1 equivalent is even more preferred.

Next, a method for synthesizing the modified polystyrene resin contained in the resin composition of the present invention (reaction between the copolymer of the component (E) and the component (F) and the component (G)) will be described.
In the modified polystyrene compound, the copolymer and the component (G) are charged into a reactor, a solvent is added to uniformly dissolve the compound, and then the temperature is raised to react the oxazoline group of the copolymer with the carboxy group of the component (G). Obtained by letting. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like, and a mixed solvent thereof may be used. However, toluene having a low boiling point and easy drying is particularly preferable. The reaction temperature is usually 50 to 150 ° C, preferably 60 to 140 ° C. The reaction time is preferably 1 to 30 hours. No catalyst needs to be added to the reaction. After the reaction, the solvent may be distilled off under heating and reduced pressure and taken out as a solid resin, or the solvent may be left as it is and used as a resin varnish.

Further, in order to prevent the polymerization reaction between the double bonds in the molecule during the reaction, it is preferable to add a small amount of the polymerization inhibitor before the reaction. Specific examples of the polymerization inhibitor include paramethoxyphenol, methylhydroquinone, dibutylhydroxytoluene and the like.

The number average molecular weight of the modified polystyrene compound thus obtained is preferably 20,000 to 300,000, more preferably 35,000 to 200,000. If the number average molecular weight is smaller than the above range, the adhesiveness to the low-roughness copper foil is low, and if it is large, the viscosity is high, which may make coating difficult.

As the modified polystyrene compound contained in the resin composition of the present invention, a compound having a repeating unit represented by the following formula (9) is preferable. In the formula, G represents a hydrogen atom or an alkyl group, and when a plurality of Gs are present, each G may be the same as or different from each other. Q represents a residue obtained by removing a hydrogen atom from the carboxy group of the component (G), and when a plurality of Qs are present, each Q may be the same as or different from each other. m and n are average values of repeating units, and represent real numbers that are independently in the range of 1 to 2,000 and satisfy the relationship of 0.01 ≦ n / (n + m) ≦ 0.05. The formula (9) is expressed using the average value of the number of repeating units, and the modified polystyrene compound used in the present invention contains oxazoline groups in the random copolymers of the components (E) and (F). It has a structure that has reacted with the component (G).

The blending ratio of the modified polystyrene compound in the resin composition of the present invention is preferably such that the terminal-modified polymer compound: the modified polystyrene compound has a mass ratio of 5:95 to 95: 5 (mass ratio), such as 10:90 to 90:10. The amount of the compound is more preferable.

The radical initiator contained in the resin composition of the present invention is not particularly limited as long as it is a known radical initiator, but for example, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-di. Hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α-bis (t-butyl) Peroxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate , 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) ) Peroxides such as peroxide and trimethylsilyltriphenylsilyl peroxide can be mentioned.
The blending ratio of the radical initiator in the resin composition of the present invention is 0.1 to 10 parts by mass, preferably 0.1 to 8 parts by mass, based on a total of 100 parts by mass of the resin components.

An organic solvent may be used in combination with the resin composition of the present invention. Specific examples of the organic solvent that can be used in combination include aromatic solvents such as toluene and xylene, ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether. Solvents, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, lactones such as γ-butyrolactone and γ-valerolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF) , N, N-Dimethylacetamide and amide solvents such as N, N-dimethylimidazolidinone, sulphons such as tetramethylene sulphon, and the like. The content of the organic solvent in the resin composition of the present invention is usually 90% by mass or less, preferably 30 to 80% by mass in the resin composition.

A polymerization inhibitor may be used in combination with the resin composition of the present invention in order to improve storage stability. Generally known polymerization inhibitors can be used, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil, and trimethylquinone, aromatic diols, and di-t-butylhydroxytoluene.

The resin composition of the present invention may contain a radically polymerizable compound in order to improve heat resistance and the like. Specifically, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide, N-p-chlorophenyl-maleimide, N. -P-methoxyphenyl-maleimide, N-p-methylphenyl-maleimide, N-p-nitrophenyl-maleimide, Np-phenoxyphenyl-maleimide, Np-phenylaminophenyl-maleimide, N-p-phenoxy Carbonylphenyl-maleimide, 1-maleimide-4-acetoxysuccinimide-benzene, 4-maleimide-4'-acetoxysquinimide-diphenylmethane, 4-maleimide-4'-acetoxysuccinimide-diphenyl ether, 4-maleimide-4'-acetamide-diphenyl ether , 2-Maleimide-6-acetamide-pyridine, 4-maleimide-4'-acetamide-diphenylmethane and N-p-phenylcarbonylphenyl-maleimide N-ethylmaleimide, N-2.6-xylylmaleimide, N-cyclohexylmaleimide , N-2,3-xylylmaleimide, xylylmaleimide, 2,6-xylenemaleimide, 4,4'-bismaleimide diphenylmethane and combinations thereof.

The resin composition of the present invention can be used by blending an amount of a filler or an additive within a range that does not impair the original performance for the purpose of imparting desired performance according to the application. The filler may be fibrous or powdery, and examples thereof include silica, carbon black, alumina, talc, mica, glass beads, and glass hollow spheres.

A flame-retardant compound, an additive, or the like can be used in combination with the resin composition of the present invention. These are not particularly limited as long as they are generally used. For example, flame-retardant compounds include bromine compounds such as 4,4-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicon-based compounds. Can be mentioned. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoaming agents, dispersants, leveling agents, brighteners. Etc., it is also possible to use them in combination as desired.

The resin composition of the present invention can be applied or impregnated on various substrates for use. For example, a film-like adhesive obtained by applying a resin composition containing an organic solvent on a PET film and then removing the organic solvent can be used as an interlayer insulating layer of a multilayer printed circuit board. Further, the polyimide film on which the film-like adhesive is provided on the surface by the same method as described above is used as a coverlay, and the copper foil on which the film-like adhesive is provided on the surface by the same method as described above is used as a copper foil with resin. be able to. It can also be used as a prepreg for printed wiring boards and CFRP by impregnating glass cloth, glass paper, carbon fiber, various non-woven fabrics, and the like.

These interlayer insulating layers, coverlays, copper foils with resin, prepregs, etc. can be made into cured products by heating and pressure molding with a hot press machine or the like.

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

Synthesis Example 1 (Synthesis of end-modified polymer compound)
24 parts (0.0141 mol) of polyphenylene ether resin (SA-90, manufactured by Savik LLC, number average molecular weight 1,700) having phenolic hydroxyl groups at both ends in a flask equipped with a thermometer, a cooling tube, and a stirrer. , 16 parts (0.0053 mol) of polybutadiene resin (G-3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3,000) having alcoholic hydroxyl groups at both ends and 50 parts of toluene were added and dissolved by stirring, and then the catalyst was used. As a result, 5 parts of triethylamine was added. The solution obtained above was heated to 105 ° C., 3.29 parts (0.0162 mol) of terephthalic acid dichloride dissolved in 30 parts of toluene was added dropwise over 10 minutes, and the mixture was further reacted at 105 ° C. for 2 hours. It was. After lowering the temperature in the system to 80 ° C., 0.678 parts (0.0064 mol) of methacrylic acid chloride was added, and the mixture was further reacted at 80 ° C. for 2 hours. Then, the triethylamine hydrochloride produced by the reaction was removed by filtration, the obtained filtrate was concentrated under reduced pressure, the remaining triethylamine was distilled off at the same time as toluene, and the amount of toluene was adjusted to adjust the amount of the terminal-modified polymer compound. 123 parts of a 35% toluene solution was obtained. The weight average molecular weight of the terminally modified polymer compound obtained above was 85,000, and the number average molecular weight was 11,000.

Synthesis Example 2 (Synthesis of modified polystyrene compound)
40 parts of Epocross RPS-1005 (manufactured by Nippon Catalyst Co., Ltd.), 0.88 parts of methacrylic acid (0.257 mmol), 50 parts of toluene and 0.2 parts of methquinone were placed in a flask equipped with a thermometer, a cooling tube and a stirrer. In addition, after stirring and dissolving, the temperature was raised to 105 ° C. and the reaction was carried out under reflux for 6 hours. Then, the amount of toluene was adjusted to obtain 136 parts of a 30 mass% toluene solution of the modified polystyrene compound. The modified polystyrene compound obtained above had a number average molecular weight of 78,000 and a weight average molecular weight of 175,000.

Examples 1 to 3, Comparative Examples 1 and 2
The composition of the terminal-modified polymer compound obtained in Synthesis Example 1, the modified polystyrene compound obtained in Synthesis Example 2, and dicumyl peroxide as a radical initiator is shown in Table 1 (the values in Table 1 are solids excluding the solvent component). The resin composition for the present invention and comparison was obtained by uniformly mixing the mixture in parts by mass in terms of minutes. Each of the resin compositions obtained above was applied onto a polyimide film to a thickness of 200 μm using an applicator, heated at 90 ° C. for 10 minutes to dry the solvent, and then further in a vacuum oven at 180 ° C. 1 By heating for hours, cured products of each resin composition of Examples and Comparative Examples were obtained. The thickness of the obtained cured product was 75 μm, and it was possible to form a film by itself.

(Measurement of tensile strength, elastic modulus, glass transition temperature and dielectric properties)
For the cured product of each resin composition of Examples and Comparative Examples, the tensile strength and elastic modulus were measured using Autograph AGX-50 (manufactured by Shimadzu Corporation), and the dynamic viscoelasticity measuring device EXSTAR6000 (manufactured by Seiko Epson Co., Ltd.) was used. ) Was used to measure the glass transition temperature, and a network analyzer 8719ET (manufactured by Azilent Technology) was used to measure the dielectric modulus and dielectric loss tangent at 10 GHz by the cavity resonance method. The results are shown in Table 1. Since the cured product of the resin composition of Comparative Example 1 was brittle, it could not be used for measuring the tensile strength.

(Measurement of adhesive strength and evaluation of solder resistance)
Each of the resin compositions of Examples and Comparative Examples was placed on a mat surface of a low-roughness copper foil for high frequency (CF-T4X-SV: manufactured by Fukuda Metal Foil Powder Co., Ltd.) having a thickness of 12 μm using an applicator and having a thickness of 50 μm. And dried at 90 ° C. for 10 minutes to dry the solvent to obtain copper foils having a film-like adhesive composed of the resin compositions of Examples and Comparative Examples, respectively. A matte surface of a copper foil having a film-like adhesive made of the same resin composition is superposed on the adhesive surface of the copper foil obtained above, and the pressure is 3 MPa and the temperature is 180 ° C. for 1 hour in a vacuum press. After curing under the conditions, the 90 ° peeling strength (adhesive strength) between the copper foil and the cured product of the resin composition was measured using Autograph AGX-50 (manufactured by Shimadzu Corporation). Further, the bonded copper foil was floated on a solder bath at 288 ° C., and the time until an abnormality such as swelling or peeling occurred was measured. The results are shown in Table 1.

As described above, the cured product of the resin composition of the present invention has high flexibility and exhibits excellent heat resistance, dielectric properties, and adhesiveness.

Claims (10)

A terminally modified polymer compound, which is a reaction product of a random copolymer compound and a compound having a substituent (D) capable of reacting with a hydroxyl group and an unsaturated double bond group.
A resin composition containing a modified polystyrene compound having an unsaturated double bond in the side chain and a radical initiator.
The random copolymer compound
(A) Polyphenylene ether resin having phenolic hydroxyl groups at both ends,
(B) Aliphatic polymers having alcoholic hydroxyl groups at both ends,
(C) A random copolymer compound with an acid dichloride compound which is a binder, and the number of moles a of the (A) polyphenylene ether resin, the number b of the (B) aliphatic polymer, and the (C). ) A resin composition in which the number of moles c of the acid dichloride compound as a binder satisfies the relationship of (a + b)> c. The resin composition according to claim 1, wherein the number of moles a of the polyphenylene ether resin (A) and the number b of the (B) aliphatic polymer satisfy the relationship of a> b. The terminal-modified polymer compound has the following formula (1).

In the formula (1), RA is (A) a divalent linking group obtained by removing two hydrogen atoms from the phenolic hydroxyl groups at both ends of a polyphenylene ether resin having phenolic hydroxyl groups at both ends, and RB is (B). A divalent linking group obtained by removing two hydrogen atoms from the alcoholic hydroxyl groups at both ends of an aliphatic polymer having alcoholic hydroxyl groups at both ends is represented by the following formula (2).

(In the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups from the acid dichloride compound which is the binder (C)), and Z represents a divalent linking group. The following formula (3)

(In the formula (3), RD represents a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule.) The substituents represented by d and e are represented by d and e. Is the average value of the number of repeating units and independently represents a real number in the range of 1 to 100. )
The resin composition according to claim 2, which comprises the compound represented by. RA is the following formula (4)

(In formula (4), X is a divalent linking group excluding two phenolic hydroxyl groups of a compound having two phenolic hydroxyl groups, and R is independently a methyl group, an ethyl group, a propyl group, an allyl group or an allyl group. The phenyl group, g and h are the average values of the number of repeating units, each independently representing a real number in the range of 1 to 100, and y each independently represents an integer of 1 to 4). The resin composition according to claim 3, which is a linking group of. The resin composition according to claim 4, wherein X is a divalent linking group obtained by removing two phenolic hydroxyl groups from bisphenol A, tetramethylbisphenol A, bisphenol F or 4,4'-biphenol. The resin composition according to any one of claims 3 to 5, wherein the RB is a divalent linking group obtained by removing two hydrogen atoms from the alcoholic hydroxyl groups at both ends of the polybutadiene rubber having alcoholic hydroxyl groups at both ends. Stuff. A modified polystyrene compound having an unsaturated double bond in the side chain is represented by the following formula (9).

(In the formula, G represents a hydrogen atom or an alkyl group, and when a plurality of Gs are present, the respective Gs may be the same or different from each other. Q is a compound having a radically polymerizable double bond and a carboxy group. Represents a residue obtained by removing a hydrogen atom from a carboxy group, and when a plurality of Qs are present, the Qs may be the same or different from each other. M and n are the average values of the number of repeating units and are independent of each other. It represents a real number in the range of 1 to 2,000 and satisfying the relationship of 0.01 ≦ n / (n + m) ≦ 0.05.)
The resin composition according to any one of claims 1 to 6, which is a compound having a repeating unit represented by. The resin composition according to claim 7, wherein Q is a residue obtained by independently removing a hydrogen atom from the carboxy group of methacrylic acid, acrylic acid, pentene acid or vinyl benzoic acid. A film-like adhesive comprising the resin composition according to any one of claims 1 to 8. The resin composition according to any one of claims 1 to 8, or the cured product of the film-like adhesive according to claim 9.