JP7061944B2 - Varnish and its manufacturing method - Google Patents

Description

The present invention is soluble in low boiling point solvents such as methyl ethyl ketone used as laminates, printed wiring boards, adhesives, encapsulants, paints, molded products, etc. that require high heat resistance in electronic and electrical parts. The present invention relates to a good resin composition and a method for producing the same.

Conventionally, thermosetting resins such as epoxy resin, polyimide resin, unsaturated polyester resin, and phenol resin have been used as heat-resistant resins in the field of electronic materials. These thermosetting resins are used properly according to their uses and characteristics. Among these, polyimide resin is widely used in applications requiring high heat resistance because it is excellent in heat resistance and moisture heat resistance (heat resistance after moisture absorption). Further, a modified polyimide resin whose performance has been improved by combining a polyimide resin with another resin such as an epoxy resin or an aromatic diamine is also used.

In recent years, in the field of semiconductor substrates, a mounting method in which a semiconductor chip is directly mounted on a substrate has become widespread. Therefore, the materials used for semiconductors are required to have high heat resistance that can withstand high temperature treatment in the mounting process. Epoxy resins are widely used as semiconductor materials, and studies have been made to meet the demand for improved heat resistance, and resins with excellent heat resistance have been proposed.

For example, modified polyimide resin compositions obtained by reacting maleimide with a specific phenol resin, a specific epoxy resin, and a specific compound have been proposed for semiconductor substrates that require high heat resistance (Patent Documents 1 and 2). ). However, these modified polyimide resin compositions have poor solubility in a general-purpose low boiling point solvent (low boiling point organic solvent), and the stability of the varnish dissolved in the solvent is poor, so that the resin component precipitates during storage. There's a problem.
As a resin composition soluble in methyl ethyl ketone, which is a low boiling point solvent, a modified polyimide resin composition obtained by melting a polymaleimide compound, a phenol resin, a bisphenol A type epoxy resin and another epoxy resin has been proposed (Patent Document 3). ).

Japanese Unexamined Patent Publication No. 2004-315705 Japanese Patent Application Laid-Open No. 2003-73459 Japanese Unexamined Patent Publication No. 2017-101152

In the modified polyimide resin composition described in Patent Document 3, the solubility in methyl ethyl ketone is greatly affected by the melting temperature. Therefore, in order to obtain a modified polyimide resin composition having good solubility in methyl ethyl ketone, it is necessary to strictly control the temperature control at the time of melting, which causes a problem of poor productivity. Further, since the bisphenol A type epoxy resin is used as an essential component in order to improve the solubility in methyl ethyl ketone, there is also a problem that the heat resistance of the cured product of the resin composition is lowered.
Therefore, in the present invention, the influence of the melting temperature on the solubility of the resin composition in a low boiling point solvent is small, the solubility is good in a wide melting temperature range without containing the bisphenol A type epoxy resin, and the productivity is good. It is an object of the present invention to provide a highly heat-resistant resin composition having excellent properties.

（前記式（１）において、ｎ₁は０以上１０以下の整数であり、Ｘ¹はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（２）で表される基、「－ＳＯ₂－」で表される基、「－ＣＯ－」で表される基、酸素原子または単結合であり、Ｒ₁はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である。）

（前記式（２）において、Ｙは芳香環を有する炭素数６以上３０以下の炭化水素基であり、ｎ₂は１～３の整数である。）
（Ｂ）フェノール樹脂とを含む樹脂混合物を溶融して得られた樹脂組成物を、沸点が１２０℃以下かつ誘電率が１０～３０の溶剤に溶解させたワニスであって、前記樹脂混合物に含まれる前記式（１）により表される（Ａ）ポリマレイミド化合物の繰り返し単位の数ｎ₁の平均値が０．０１以上５以下であるワニス。 [1] The (A) polymaleimide compound represented by the formula (1) and

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". A group represented by " _2- ", a group represented by "-CO-", an oxygen atom or a single bond, R ₁ is an independently hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, and b is an integer of 0 or more and 3 or less independently.)

(In the above formula (2), Y is a hydrocarbon group having an aromatic ring and having 6 or more carbon atoms and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3).
(B) A varnish in which a resin composition obtained by melting a resin mixture containing a phenol resin is dissolved in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30 and contained in the resin mixture. A varnish in which the average value of the number n ₁ of the repeating units of the (A) polymaleimide compound represented by the above formula (1) is 0.01 or more and 5 or less.

（前記式（３）中、ｍは０～１０の整数を表す。） [2] The varnish according to [1], wherein the (B) phenolic resin contains a compound having at least two or more OH groups and at least one naphthalene skeleton in the molecule.
[3] The varnish according to [1 ], wherein the resin mixture further contains (C) an epoxy resin.
[4] The varnish according to [3], wherein the (C) epoxy resin has two or more glycidyl groups in the molecule.
[5] The varnish according to [4], wherein the content of the bisphenol A type epoxy resin represented by the formula (3) in 100 parts by mass of the resin mixture is 0 to 10 parts by mass.

(In the above equation (3), m represents an integer of 0 to 10.)

（前記式（１）において、ｎ₁は０以上１０以下の整数であり、Ｘ¹が「－ＣＨ₂－」で表される基であり、Ｒ ¹ はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａ＝０、ｂ＝０である。）
（Ｂ）フェノール樹脂と、（Ｃ）分子中に二つ以上のグリシジル基を有するエポキシ樹脂と、からなり、前記樹脂混合物に含まれる前記式（１）により表される（Ａ）ポリマレイミド化合物の繰り返し単位の数ｎ₁の平均値が０．０１以上５以下である樹脂混合物を溶融して得られた樹脂組成物を、沸点が１２０℃以下かつ誘電率が１０～３０の溶剤に溶解させたワニスであって、前記樹脂混合物中における前記（Ｂ）フェノール樹脂の含有量が、前記（Ａ）ポリマレイミド化合物１００質量部に対して、５～１００質量部であり、前記樹脂混合物中における前記（Ｃ）エポキシ樹脂の含有量が、前記（Ａ）ポリマレイミド化合物１００質量部に対して、１０～３００質量部であるワニス。 [6] The (A) polymaleimide compound represented by the formula (1) and

(In the above equation (1), n ₁ is an integer of 0 or more and 10 or less, X ¹ is a group represented by "-CH _2- ", and R ¹ independently has 1 or more and 6 or less carbon atoms. It is a hydrocarbon group, and a = 0 and b = 0.)
The polymaleimide compound (A) represented by the formula (1) contained in the resin mixture, which comprises (B) a phenol resin and (C) an epoxy resin having two or more glycidyl groups in the molecule. A resin composition obtained by melting a resin mixture having an average value of 0.01 or more and 5 or less of the number n ₁ of repeating units was dissolved in a solvent having a boiling point of 120 ° C. or less and a dielectric constant of 10 to 30. In the varnish, the content of the (B) phenol resin in the resin mixture is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound, and the above () in the resin mixture. C) A varnish having an epoxy resin content of 10 to 300 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound.

[7] The varnish according to [1 ] for a printed wiring board.

The adhesive, sealant and paint containing the varnish according to [1 ] .
A laminated board and a printed wiring board manufactured by using the varnish according to [1 ] .
A molded product obtained by curing the varnish according to [1 ] .

A method for producing a varnish in which the resin mixture according to [1 ] is melt-mixed and the resin composition obtained by melting is dissolved in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30 .

Melting by using a resin mixture containing (A) a polymaleimide compound and (B) a phenol resin having an average value of 0.01 or more and 5 or less of the number n ₁ of the repeating units represented by the formula (1). It is a resin composition having good solubility in a low boiling point solvent regardless of the temperature. Therefore, it is possible to provide a resin composition having a wide range of melting temperatures allowed in melt mixing, good productivity, and good solubility in a low boiling point solvent.

（前記式（１）において、ｎ_１は０以上１０以下の整数であり、Ｘ^１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（２）で表される基、「－ＳＯ_２－」で表される基、「－ＣＯ－」で表される基、酸素原子または単結合であり、Ｒ^１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である。）

（前記式（２）において、Ｙは芳香環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は１～３の整数である。）
本発明において、（Ａ）ポリマレイミド化合物と（Ｂ）フェノール樹脂とを溶融混合する以前のものを「樹脂混合物」といい、溶融混合した後のものを「樹脂組成物」という。 (Resin composition)
The resin composition of the present invention is a resin composition obtained by melting a resin mixture containing (A) a polymaleimide compound represented by the formula (1) and (B) a phenol resin, and is the resin mixture. The average value of the number n ₁ of the repeating units of the (A) polymaleimide compound represented by the above formula (1) contained in the above is 0.01 or more and 5 or less.

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". A group represented by " _2- ", a group represented by "-CO-", an oxygen atom or a single bond, R ¹ is an independently hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, and b is an integer of 0 or more and 3 or less independently.)

(In the above formula (2), Y is a hydrocarbon group having an aromatic ring and having 6 or more carbon atoms and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3).
In the present invention, the compound before the melt-mixing of the (A) polymaleimide compound and the (B) phenol resin is referred to as a "resin mixture", and the one after the melt-mixing is referred to as a "resin composition".

(A) Polymaleimide compound The resin mixture is a polymaleimide compound having a repeating unit (structural site) enclosed in parentheses in the formula (1), and the average value of the number n ₁ of the repeating units is 0.01 or more and 5 or less. It is contained in a certain proportion. That is, the polymaleimide compound represented by the formula (1) contained in the resin mixture is a polymaleimide compound having an average value of n ₁ of 0.01 or more and 5 or less. Therefore, the resin composition has good solubility in a low boiling point solvent regardless of the melting temperature at which the resin mixture is melted. In the present invention, "a polymaleimide compound having an average value of n ₁ of 0.01 or more and 5 or less" means a polymaleimide compound composed of one or more kinds.

The content of the polymaleimide compound represented by the formula (1) in 100 parts by mass of the resin mixture is preferably 20 to 80 parts by mass, more preferably 25 to 75 parts by mass. In the present invention, the numerical range "A to B" means "A or more and B or less".

The polymaleimide compound represented by the formula (1) is used as one kind of compound or a mixture of two or more kinds of compounds so that the average value of the number n ₁ of the repeating units is in the range of 0.01 or more and 5 or less. ..

The polymaleimide compound represented by the formula (1) is preferably a polymaleimide compound in which X ₁ is −CH _2- , a is 0, and b is 0. Examples of such commercially available polymaleimide compounds include BMI-2000 and BMI-2300 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., phenylenemaleimide).

(B) Phenol resin The phenol resin (B) used in the present invention includes phenol novolac resin, cresol novolak resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, and naphthol-cresol. Shrinked novolak resin, dicyclopentadienephenol addition type resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, biphenyl modified phenol resin, biphenyl aralkyl type phenol resin, biphenyl modified naphthol resin, biphenyl aralkyl type naphthol resin, aminotriazine modified phenol resin, etc. Polyhydric phenol compound of. In particular, a compound having at least two or more OH groups and at least one naphthalene skeleton in the molecule is preferable, and examples thereof include those composed of a phenol compound represented by the following general formula (4).

（式中、Ａｒ^１、Ａｒ^２は、それぞれ下記一般式（５）で示されるフェニレン基または下記一般式（６）で示されるナフタレン基であり、Ａｒ^２が複数ある場合、それぞれが同一であっても異なっていてもよい。Ｘ^２は直接結合、炭素数１～４のアルキレン、芳香環を含む炭素数８～１５のアルキレン、Ｏ、ＳまたはＳＯ_２のいずれかを示す。ｏは０以上の整数である。但しｏが０の場合は、Ａｒ^１は少なくとも１個のヒドロキシ基（水酸基）を有するものであり、Ａｒ^１、Ａｒ^２およびＸ^２のいずれか一つはナフタレン基である。）
アルキレン基としてはメチレン等が挙げられ、芳香環を含む炭素数８～１５のアルキレンとしてはフェニレン、ナフタレン、ビフェニレン構造を含むもの等が挙げられる。

(In the formula, Ar ¹ and Ar ² are phenylene groups represented by the following general formula (5) or naphthalene groups represented by the following general formula (6), respectively, and when there are a plurality of Ar ² , they are the same. X ² indicates a direct bond, an alkylene having 1 to 4 carbon atoms, an alkylene having 8 to 15 carbon atoms including an aromatic ring, O, S or SO ₂ , and o is 0 or more. However, when o is 0, Ar ¹ has at least one hydroxy group (hydroxyl group), and any one of Ar ¹ , Ar ² and X ² is a naphthalene group. )
Examples of the alkylene group include methylene and the like, and examples of the alkylene having 8 to 15 carbon atoms containing an aromatic ring include those containing a phenylene, naphthalene and biphenylene structures.

（式（５）および（６）において、Ｒ^２は、それぞれ独立に炭化水素基または水酸基であり、ｃは、それぞれ独立に０～３の整数である。）

(In formulas (5) and (6), R ² is an independently hydrocarbon group or a hydroxyl group, and c is an independently integer of 0 to 3.)

Examples of the alkylene group in the formula (5) include methylene and the like, and examples of the alkylene having 8 to 15 carbon atoms including an aromatic ring include those containing a phenylene, naphthalene and biphenylene structures.

Examples of such phenolic resins include hydroxynaphthalene such as 1-naphthol, 2-naphthol, 1,4 dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 1,3-dihydroxynaphthalene. Novolak resin, which is a reaction product of hydroxynaphthalene and phenols such as phenol, cresol and resorcinol, and aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glioxal and alkandial, and the above hydroxynaphthalene. Examples thereof include aralkyl resin, which is a reactive organism between the class and the aralkyl alcohol derivative or the aralkyl halide derivative. The above-mentioned aralkyl alcohol derivative is preferably p-xylylene glycol, p-xylylene glycol dimethyl ether and the like, and the aralkyl hydride derivative is preferably p-xylylene chloride chloride and the like.

Among these compounds, 1-naphthol, 2-naphthol and an aralkyl resin thereof are particularly preferable. These compounds may be used alone or in combination of two or more. The content of the (B) phenol resin with respect to 100 parts by mass of the (A) polymaleimide compound in the resin mixture is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass.

(C) Epoxy resin The resin composition of the present invention may further contain an epoxy resin in the resin mixture. The content of the epoxy resin in 100 parts by mass of the resin mixture is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass. The content of the epoxy resin in the resin mixture is preferably 10 to 300 parts by mass, more preferably 20 to 280 parts by mass, and further preferably 30 to 250 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound. preferable.

The epoxy resin may be a compound having an epoxy group, but from the viewpoint of improving the heat resistance of the cured product of the resin composition, it is represented by a biphenyl aralkyl type epoxy resin, an epoxy resin containing a naphthalene ring, and the formula (7). A compound having three epoxy groups to be used is preferable. Examples of the commercially available epoxy resin represented by the formula (7) include VG3101L (product name, manufactured by Printec Co., Ltd., highly heat-resistant trifunctional epoxy resin).

Epoxy resins other than the above include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol F novolak type epoxy resin. , Triphenylol type epoxy resin, dicyclopentadiene type epoxy resin and the like. These epoxy resins can be used alone or in combination of two or more.

The bisphenol A type epoxy resin represented by the following formula (3) has an effect of improving the solubility of the resin composition in a low boiling point solvent such as methyl ethyl ketone. However, when the content of the bisphenol A type epoxy resin in the resin mixture increases, the heat resistance of the cured product of the resin composition tends to decrease. The resin composition of the present embodiment has good solubility in methyl ethyl ketone by using the (A) polymaleimide compound having an average value of 0.01 or more and 5 or less of the number n ₁ of the repeating units in the formula (1). become. Therefore, the content of the bisphenol A type epoxy resin in the resin mixture can be reduced. Therefore, for example, even if the content of the bisphenol A type epoxy resin in 100 parts by mass of the resin mixture is 0 to 10 parts by mass, a resin composition having good solubility in methyl ethyl ketone can be obtained.

From the viewpoint of improving the heat resistance of the cured product of the resin composition, it is preferable that the resin mixture does not contain the bisphenol A type epoxy resin. Here, the term "not containing bisphenol A type epoxy resin" means that it is not substantially contained, that is, it does not contain an amount of bisphenol A type epoxy resin that affects the properties of the resin mixture.

The resin composition of the present invention is obtained by melting a resin mixture composed of (A) a polymaleimide compound, (B) a phenol resin, and (C) an epoxy resin having two or more glycidyl groups in the molecule. It can be carried out as a obtained resin composition. In this case, the content of the (B) phenol resin in the resin mixture is 5 to 100 parts by mass, preferably 10 to 70 parts by mass, and 25 to 45 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound. Part is more preferable. The content of the epoxy resin in the resin mixture is 10 to 300 parts by mass, preferably 20 to 280 parts by mass, and more preferably 30 to 250 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound.

The resin composition according to the present invention and the resin mixture before melt mixing may contain components other than the above (A), (B) and (C).

Using the resin composition of the present invention, an organic or inorganic filler can be used in order to obtain a base material which is cured to be a molded product. Examples of fillers are oxides such as silica, diatomaceous earth, alumina, zinc chloride, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites; calcium hydroxide, magnesium hydroxide, hydroxide. Hydroxides such as aluminum and basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite and hydrotalcite; sulfates such as calcium sulfate, barium sulfate and gypsum fiber; calcium silicate (Wollastonite, zonotrite), talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balun and other silicates; aluminum nitride, boron nitride, nitride Nitrides such as silicon; carbons such as carbon black, graphite, carbon fiber, carbon balun, charcoal powder; other various metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber , Zinc borate, various magnetic powders, slag fibers, ceramic powders and the like.

The shape of the filler is preferably spherical or phosphorus pieces, and these may be used alone or in combination of two or more. Also, if necessary, a silane coupling agent having two or more different reactive groups in the molecule (one is a reactive group that chemically reacts with an inorganic material and the other is a reactive group that chemically reacts with an organic material) is used in combination. You can also do it.

When an organic or inorganic filler is used, the content thereof is preferably 5.0 to 250 parts by mass with respect to 100 parts by mass of the resin composition.

(D) Curing Accelerator When using the resin composition according to the present invention, a curing accelerator may be added and used. Examples of the timing for adding the curing accelerator include when the resin composition is used as a varnish dissolved in a solvent, when it is made into a prepreg, or when a base material or a laminated board is manufactured.

Examples of the curing accelerator include imidazoles such as dicumylperoxide, 4,4'-diaminodiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptymidazole; triethanolamine, triethylenediamine, and the like. Amines such as N-methylmorpholin; organic phosphines such as triphenylphosphine and tritrylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diazabicyclo (5) , 4,0) Undecene-7 and its derivatives; examples thereof include organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt tefateate, and cobalt octylate. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide, an azo compound or the like may be used in combination.

The content of these curing accelerators is preferably blended so as to obtain the desired gelation time of the varnish or prepreg, but generally, it is 0. It is used in the range of 01 to 5.00 parts by mass.

(Melting and mixing process)
The resin composition is produced by a melt-mixing step in which a resin mixture containing (A) a polymaleimide compound and (B) a phenol resin represented by the above-mentioned formula (1) is heated and mixed in a melted state. .. Ordinary mixing means can be used in the melt mixing step. As the mixing means, a kneader, a twin-screw kneader, or the like is preferable. The temperature at the time of melting and mixing may be the temperature at which the resin mixture melts or more and 400 ° C. or lower, but more preferably 130 ° C. or higher and 230 ° C. or lower, and further preferably 150 ° C. or higher and 210 ° C. or lower. As described above, since the polymaleimide compound (A) having an average value of 0.01 or more and 5 or less of the number n ₁ of the repeating units in the formula (1) is used, it can be used in a wide melting temperature range in the melting and mixing step. , A resin composition having good solubility in a low boiling point solvent can be obtained. The melting and mixing step is usually carried out for about 0.1 to 10 minutes.

After the melt-mixing step, the resin composition of the present invention is obtained by cooling by natural cooling or forced cooling.
The cooling method can be appropriately selected from known methods. For example, a method of natural cooling in an environment of 5 to 100 ° C. or a method of forced cooling using a refrigerant of −20 to 80 ° C. can be adopted. Further, a method of cooling after melting and mixing and placing the product in an environment of 30 to 300 ° C. in a constant temperature device may be adopted.

After cooling, the obtained resin composition can be pulverized and stored in a dry state (dry), and used as a solid resin composition in a later step.

In the melt-mixing step, at least a part of the (A) polymaleimide compound contained in the resin mixture is modified by reacting with (B) a phenol resin and / or (C) an epoxy resin, and is soluble in a low boiling solvent. Can obtain a good resin composition.

A flame retardant can be added to the resin composition if necessary. Examples of the flame retardant include organic flame retardants such as brom compounds such as brominated epoxy resins and phosphorus compounds such as condensed phosphoric acid esters, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, tin compounds and antimony compounds. .. These flame retardants may be used alone or in combination of two or more.

The content of the flame retardant is preferably an amount necessary to have sufficient flame retardancy (for example, passing the V-0 condition in the UL94 standard) without impairing the heat resistance and moisture heat resistance of the resin composition. In the case of an organic flame retardant, it is generally in the range of 1 to 20 parts by mass with respect to a total of 100 parts by mass of the resin component including the organic flame retardant in the resin composition, and in the case of an inorganic flame retardant, the resin component. It is preferably used in the range of 10 to 300 parts by mass with respect to 100 parts by mass in total.

In using the resin composition according to the present invention, other additives can be added depending on the intended use. Examples of other additives include various silicone oils, thermoplastic resins, synthetic rubbers such as NBR, and leveling agents. The other additives are used in a blending amount range in which the content of the other additives in the total 100 parts by mass of the other additives and the resin component in the resin composition is 0.0001 to 5 parts by mass. Is preferable.

(varnish)
The varnish of the resin composition according to the present invention is obtained by dissolving the resin composition obtained by the above-mentioned production method in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30.
Examples of the solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30 include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as propylene glycol monomethyl ether, ethanol, 1-propanol and 2-propanol. Examples thereof include alcohol solvents such as 1-butanol. In consideration of operability and the like, a ketone solvent is preferably used among the exemplified solvents. These solvents may be used alone or in combination of two or more. Further, it may contain a solvent other than those exemplified above.

The content of the resin composition in 100 parts by mass of the varnish is usually 40 to 80 parts by mass, preferably 50 to 70 parts by mass. The varnish can be obtained by dissolving the resin composition in a solvent. When it is melted under heating, it does not take a particularly long time. Although it depends on the boiling point of the solvent, the general conditions for dissolution are a temperature of about 50 to 200 ° C. and a time of about 0.1 to 24 hours.

The prepreg can be produced by applying or impregnating the varnish on a substrate and then drying to remove the solvent.
As the base material, known base materials used for conventional prepregs such as glass non-woven fabric, glass cloth, carbon fiber cloth, organic fiber cloth, and paper can be used.

After applying or impregnating the varnish on the substrate, a prepreg is produced through a drying step, but the coating method, impregnation method, and drying method are not particularly limited, and conventionally known methods can be adopted. The drying conditions are appropriately determined by the boiling point of the solvent used, but a high temperature is not preferable. It is desirable to dry the prepreg so that the amount of the solvent remaining in the prepreg is 3% by mass or less.

The resin composition of the present invention is suitable for a printed wiring board, and the present invention can be carried out as a molded product obtained by curing the resin composition. Examples of the molded product include a cured product obtained by curing only the resin composition, a composite material composited with other raw materials, a laminate, and the like.

The composite material and the laminated body can be obtained by heating and curing one prepreg under pressure with a hot press or the like, or by laminating a plurality of prepregs and heating under pressure to integrate them. The heating and pressurizing conditions for producing the composite material are not particularly limited, but the heating temperature is 100 to 300 ° C., preferably 150 to 250 ° C., the pressure is 10 to 100 kg / cm ² , and the heating is performed. The pressurization time is about 10 to 300 minutes.

A metal foil or a metal plate can be laminated and integrated on one side or both sides of the laminated material to form a laminated body that can be used for a multilayer printed wiring board or the like. Such a laminate may be obtained by laminating a metal foil or a metal plate on one or both sides of a single prepreg and heat-pressing it, or by hot-pressing the metal foil or a metal plate on one or both sides of the outermost layer of a plurality of laminated prepregs. Can be manufactured by laminating and hot pressing to heat-cure and integrate the prepreg.

As the metal foil or metal plate, copper, aluminum, iron, stainless steel or the like can be used. For example, a laminated plate using copper as a metal foil is a copper-clad laminated plate (CPL). The conditions for heat curing are preferably the same as the conditions for producing the composite material. Further, the inner layer core material may be used as a laminated board for a multilayer printed wiring board.

The present invention can also be carried out as an adhesive, a sealant and a paint containing the above-mentioned resin composition.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The test methods and raw materials used in the examples and comparative examples are as follows.

1. 1. Test method (1) Solvent solubility 60 parts by mass of the measurement sample (resin composition) and 40 parts by mass of methyl ethyl ketone (solvent) are mixed under room temperature conditions, and dissolved by applying ultrasonic vibration for 1 hour. Was visually evaluated using the following criteria.
〇: Clear liquid at room temperature ×: Liquid or semi-liquid state turbid at room temperature

(2) Gel time The measurement was performed with a gel time measuring machine SG-70.

(3) Glass transition point (Tg)
The cured resin composition obtained by curing the resin composition was cut (cut out) to a predetermined size and used as a sample for measuring the glass transition point. The glass transition temperature (° C) of the sample was measured under the following conditions.
Measuring equipment: Thermo plus TMA8310 manufactured by Rigaku Co., Ltd.
Sample dimensions: width (length) 5 mm x length (width) 5 mm x height 4 mm
Atmosphere: N ₂
Measurement temperature: 30-350 ° C
Temperature rise rate: 10 ° C / min.
Measurement mode: compression

(4) Thermogravimetric change According to JIS K7120, the temperature is raised from 30 ° C. to 10 ° C. per minute, and the mass is reduced by 1% (Td (1%)) and 5% (Td). (5%)) was measured.
(5) Solution stability The solution obtained by dissolving the resin composition in methyl ethyl ketone was left at room temperature, and the dissolved state after a predetermined time (after 24 hours and after 7 days) was determined using the following criteria. It was evaluated visually.
〇: Clear liquid △: Turbid liquid ×: Precipitation or insoluble matter is found in the liquid

2. 2. Raw material (A) Polymaleimide compound, BMI-1000 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., 4,4'-diphenylmethanebismaleimide)
BMI-2300 (product name, manufactured by Daiwa Kasei Kogyo Co., Ltd., polyphenylmethane polymaleimide): The average value of n ₁ of the compound represented by the formula (1) is 0.01 or more and 5 or less, and X ¹ is A polymaleimide compound represented by -CH _2- , in which a is 0 and b is 0.

(B) Phenol resin SN485 (Product name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol aralkyl type phenol resin containing phenylene skeleton)
(C) Epoxy resin JER1001 (Product name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin)
VG3101L (Product name, manufactured by Printec Co., Ltd., high heat resistant trifunctional epoxy resin)
・ NC3000H (Product name, manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl epoxy resin)
(D) Benzoxazine compound-BZO: (Pd type) benzoxazine (manufactured by Shikoku Chemicals Corporation)

(Example 1-6, Comparative Example 1)
The raw materials having the compositions shown in Tables 1 to 3 were melt-mixed on a hot plate at the temperatures shown in Tables 1 to 3 (150 ° C. to 210 ° C.) for 90 seconds to produce a resin composition. The results of measuring the solvent solubility and solution stability of each resin composition are shown in Tables 1 to 3. In Tables 1 to 3, the content of each component is shown by mass.

From the results shown in Tables 1 to 3, the following was found.
As shown in Comparative Examples 1 to 4, as the polymaleimide compound, 4,4'-diphenylmethane bismaleimide (BMI-1000), a phenol resin (SN485), a bisphenol A type epoxy resin (JER1001), and a benzoxazine compound (BZO) ) Is melt-mixed at 190 ° C. to obtain a resin composition having good solvent solubility and solution stability. However, when the melting temperatures at the time of melting and mixing the resin mixture are 150 ° C. and 170 ° C., a resin composition that dissolves in methyl ethyl ketone at room temperature cannot be obtained. Further, when the melting temperature is 210 ° C., the solubility in methyl ethyl ketone becomes low and the solution stability also deteriorates. It is probable that the deterioration of solubility and solution stability at the melting temperature of 210 ° C. was due to the excessive progress of the reaction during melting and mixing.

That is, when 4,4'-diphenylmethanebismaleimide (BMI-1000) is used as the (A) polymaleimide compound, the solvent solubility and solution stability of the resin composition are greatly affected by the melting temperature. Therefore, in order to obtain a resin composition that dissolves in methyl ethyl ketone at room temperature, it is necessary to maintain the melting temperature at around 190 ° C. As described above, it is not preferable from the viewpoint of production efficiency and production cost that the range of the melting temperature allowed in the production of the resin composition is narrow and strict temperature control is required.

On the other hand, in the resin compositions of Examples 1 to 17 containing the polymaleimide compound in which the average value of the number n ₁ of the repeating units in the formula (1) is 0.01 to 5, the resin mixture is 150 ° C. or higher and 210 ° C. By melting in the following, both solvent solubility and solution stability are improved. The resin composition of the present invention has a wide range of melting temperatures allowed to obtain a resin composition that dissolves in methyl ethyl ketone at room temperature. Therefore, it is not necessary to strictly control the melting temperature in the melting and mixing step of the resin mixture, which is preferable from the viewpoint of manufacturing efficiency and production cost. Therefore, a resin composition having good solubility in methyl ethyl ketone and solution stability can be easily and stably produced. Furthermore, it was possible to obtain a resin composition that dissolves in methyl ethyl ketone at room temperature without using a bisphenol A type epoxy resin (JER1001).

The resin compositions of Examples 7 and 9 were heated at a curing temperature of 230 ° C. for 4 hours and cured to prepare a cured resin. Table 4 shows the results of measuring the gel time (GT), the glass transition temperature (Tg), and the thermogravimetric change temperature (Td (1%), Td (5%)) for each cured resin product.

From the results shown in Table 4, it can be seen that the resin compositions of Examples 7 and 9 have a high glass transition temperature (Tg) and a thermogravimetric change temperature (Td), and a cured resin product having good heat resistance can be obtained.

The present invention is a resin composition having excellent solubility in a low boiling point solvent and storage stability, and the resin composition can be used as an adhesive, a sealant, a paint, a molded product, a laminate and a laminate having good heat resistance. It can be used as a raw material for printed circuit boards.

Claims (14)

The (A) polymaleimide compound represented by the formula (1) and

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ¹ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (2), "-SO". A group represented by " _2- ", a group represented by "-CO-", an oxygen atom or a single bond, R ₁ is an independently hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is each. Independently, it is an integer of 0 or more and 4 or less, and b is an integer of 0 or more and 3 or less independently.)

(In the above formula (2), Y is a hydrocarbon group having an aromatic ring and having 6 or more carbon atoms and 30 or less carbon atoms, and n ₂ is an integer of 1 to 3).
(B) A varnish obtained by dissolving a resin composition obtained by melting a resin mixture containing a phenol resin in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30 .
A varnish in which the average value of the number n ₁ of the repeating units of the (A) polymaleimide compound represented by the formula (1) contained in the resin mixture is 0.01 or more and 5 or less. The varnish according to claim 1 , wherein the phenol resin (B) contains a compound having at least two or more OH groups and at least one naphthalene skeleton in the molecule. The varnish according to claim 1 , wherein the resin mixture further contains (C) an epoxy resin. The varnish according to claim 3, wherein the epoxy resin (C) has two or more glycidyl groups in the molecule. The varnish according to claim 4, wherein the content of the bisphenol A type epoxy resin represented by the formula (3) in 100 parts by mass of the resin mixture is 0 to 10 parts by mass.

(In the above equation (3), m represents an integer of 0 to 10.) The (A) polymaleimide compound represented by the formula (1) and

(In the above equation (1), n ₁ is an integer of 0 or more and 10 or less, X ¹ is a group represented by "-CH _2- ", and R ¹ independently has 1 or more and 6 or less carbon atoms. It is a hydrocarbon group, and a = 0 and b = 0.)
(B) Phenolic resin and
(C) The number of repeating units n ₁ of the (A) polymaleimide compound represented by the above formula (1), which comprises an epoxy resin having two or more glycidyl groups in the molecule and contained in the resin mixture. A varnish obtained by dissolving a resin composition obtained by melting a resin mixture having an average value of 0.01 or more and 5 or less in a solvent having a boiling point of 120 ° C. or less and a dielectric constant of 10 to 30 .
The content of the (B) phenol resin in the resin mixture is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound.
A varnish in which the content of the (C) epoxy resin in the resin mixture is 10 to 300 parts by mass with respect to 100 parts by mass of the (A) polymaleimide compound. The varnish according to claim 1 , which is for a printed wiring board. The adhesive containing the varnish according to claim 1 . The varnish -containing sealant according to claim 1 . The paint containing the varnish according to claim 1 . A laminated board manufactured by using the varnish according to claim 1 . A printed wiring board manufactured by using the varnish according to claim 1 . A molded product obtained by curing the varnish according to claim 1 . A method for producing a varnish in which the resin mixture according to claim 1 is melt-mixed and the resin composition obtained by melting is dissolved in a solvent having a boiling point of 120 ° C. or lower and a dielectric constant of 10 to 30 .