TWI731072B - Resin composition, prepreg, resin sheet, laminated resin sheet, laminate, metal foil-clad laminate, and printed wiring board - Google Patents

Abstract

A resin composition containing a cyanate ester compound (A) and a maleimide compound (B), wherein the ratio ([α/β]) of the amount of cyanate ester groups (α) in the cyanate ester compound (A) relative to the amount of maleimide groups (β) in the maleimide compound (B) is 0.30 or greater.

Description

Resin composition, prepreg, resin sheet, laminated resin sheet, laminated board, metal foil-clad laminated board, and printed circuit board

The present invention relates to a resin composition, a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil-clad laminated board, and a printed circuit board.

In recent years, with the development of high-performance and miniaturization of semiconductor packaging widely used in electronic equipment, communication equipment, personal computers, etc., the high integration and high-density mounting of various parts for semiconductor packaging is accelerating. At the same time, the warpage of the semiconductor plastic package caused by the difference in the thermal expansion coefficient between the semiconductor element and the printed circuit board for the semiconductor plastic package has become a problem, and various countermeasures have been sought for this.

One of the countermeasures can be the low thermal expansion of the insulating layer used in the printed circuit board. This is a method of suppressing warpage by making the thermal expansion coefficient of the printed circuit board close to the thermal expansion coefficient of the semiconductor element, and is currently being actively studied (for example, refer to Patent Documents 1 to 3).

As far as methods for suppressing warpage of semiconductor plastic packages are concerned, in addition to the low thermal expansion of printed circuit boards, it has also been studied to increase the rigidity of the laminate (high rigidity) and increase the glass transition temperature of the laminate (high Tgization) (for example, refer to Patent Documents 4 and 5). [Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2013-216884 Patent Document 2: Japanese Patent Publication No. 3173332 Patent Document 3: Japanese Patent Application Publication No. 2009-035728 Patent Document 4: Japanese Patent Application Publication No. 2013-001807 Patent Document 5: Japanese Patent Publication No. 2011-178992

[Problem to be Solved by the Invention] However, the low thermal expansion of the printed circuit board by the conventional method described in Patent Documents 1 to 3 is close to the limit, and it is difficult to further reduce the thermal expansion.

The high rigidity of the laminated board can be achieved by filling the resin composition used in the laminated board with a high filler, and using an inorganic filler with a high elastic modulus such as alumina. However, there is a problem that the high filling of the filler deteriorates the formability of the laminate, and the use of inorganic fillers such as alumina deteriorates the thermal expansion coefficient of the laminate. Therefore, the high rigidity of the laminated board cannot sufficiently suppress the warpage of the semiconductor plastic package.

In addition, using the method of high Tg of the laminated board can improve the elastic modulus during reflow, so the warpage reduction effect of the semiconductor plastic package is displayed. However, the use of high Tg methods will cause the deterioration of moisture absorption and heat resistance due to the increase in crosslinking density and the generation of voids due to the deterioration of formability. Therefore, very high reliability is required in electronic materials. There are many practical problems in the field. Therefore, a solution to these problems is expected.

Furthermore, for the insulating layer of the printed circuit board, high elastic modulus maintenance rate, high copper foil peel strength and excellent plating peel strength are required at the same time. However, there is no report about the availability of a resin composition that can satisfy all of these issues.

The present invention was made in view of the above problems, and aims to provide a resin composition capable of obtaining a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, resin sheet, and laminated resin sheet using the resin composition , Laminated boards, metal-clad laminated boards, and printed circuit boards. [Means to solve the problem]

The inventors of the present application have made diligent studies in order to solve the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved by using a predetermined amount of the cyanate ester compound (A) and the maleimide compound (B), and the present invention has been completed.

(式(1)中，R¹ 各自獨立地表示氫原子或碳數1～4之烷基，R² 各自獨立地表示也可具有選自於由氰酸酯基、羥基及烯丙基構成之群組中之至少一者作為取代基之苯基、氫原子、烯丙基、氰酸酯基、或環氧基，n1為1以上之整數，m為1～4之整數。) ［化2］

(式(2)中，R³ 各自獨立地表示氫原子或碳數1～4之烷基，n2為1以上之整數。) ［3］如［1］或［2］之樹脂組成物，其中，氰酸酯化合物(A)之氰酸酯基當量為100～220g/eq.。 ［4］如［1］～［3］中任一項之樹脂組成物，其中，該氰酸酯化合物(A)含有下列通式(1’’)表示之化合物。 ［化3］

(式(1’’)中，R¹ 各自獨立地表示氫原子或碳數1～4之烷基，n1為1以上之整數。) ［5］如［1］～［4］中任一項之樹脂組成物，其中，該氰酸酯化合物(A)含有下列通式(3)表示之化合物。 ［化4］

［6］如［1］～［5］中任一項之樹脂組成物，其中，該馬來醯亞胺化合物(B)含有選自於由雙(4-馬來醯亞胺苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺苯氧基)-苯基}丙烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、及下式(4)表示之馬來醯亞胺化合物構成之群組中之至少1種。 ［化5］

(式中，R⁴ 各自獨立地表示氫原子或甲基，n3表示1以上之整數。) ［7］如［1］～［6］中任一項之樹脂組成物，其中，該比(［α/β］)為0.45～1.0。 ［8］如［1］～［7］中任一項之樹脂組成物，更含有無機填充材(C)。 ［9］如［8］之樹脂組成物，其中，該無機填充材(C)之含量相對於樹脂固體成分100質量份為25～700質量份。 ［10］如［8］或［9］之樹脂組成物，其中，該無機填充材(C)含有選自於由二氧化矽、軟水鋁石、及氧化鋁構成之群組中之至少1種。 ［11］一種預浸體，具有：基材、及含浸或塗佈於該基材之如［1］～［10］中任一項之樹脂組成物。 ［12］一種樹脂片，係將如［1］～［10］中任一項之樹脂組成物成形為片狀而成。 ［13］一種疊層樹脂片，具有：片基材、及配置在該片基材之單面或兩面之如［1］～［10］中任一項之樹脂組成物。 ［14］一種疊層板，具有1片以上之選自於由如［11］之預浸體、如［12］之樹脂片、及如［13］之疊層樹脂片構成之群組中之至少1種。 ［15］一種覆金屬箔疊層板，具有：選自於由如［11］之預浸體、如［12］之樹脂片、及如［13］之疊層樹脂片構成之群組中之至少1種；及配置在該預浸體、該樹脂片、及該疊層樹脂片之單面或兩面之金屬箔。 ［16］一種印刷電路板，具有絕緣層及形成在該絕緣層之單面或兩面之導體層，該絕緣層含有如［1］～［10］中任一項之樹脂組成物。 ［發明之效果］That is, the present invention is as follows. [1] A resin composition containing a cyanate ester compound (A) and a maleimide compound (B), and the amount of cyanate ester group (α) of the cyanate ester compound (A) is relative to the maleimide compound (A) The ratio ([α/β]) of the amount of maleimide groups (β) of the imine compound (B) is 0.30 or more. [2] The resin composition according to [1], wherein the cyanate ester compound (A) contains a compound represented by the following general formula (1) and/or the following general formula (2). [化1]

(In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² each independently represents a group selected from the group consisting of a cyanate group, a hydroxyl group, and an allyl group. In the group where at least one of the substituents is a phenyl group, a hydrogen atom, an allyl group, a cyanate group, or an epoxy group, n1 is an integer of 1 or more, and m is an integer of 1 to 4.) [Chemical 2 ]

(In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbons, and n2 is an integer of 1 or more.) [3] The resin composition as in [1] or [2], wherein , The cyanate ester compound (A) has a cyanate ester group equivalent of 100 to 220 g/eq. [4] The resin composition according to any one of [1] to [3], wherein the cyanate ester compound (A) contains a compound represented by the following general formula (1''). [化3]

(In formula (1''), R ¹ each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and n1 is an integer of 1 or more.) [5] Such as any one of [1] to [4] The resin composition, wherein the cyanate ester compound (A) contains a compound represented by the following general formula (3). [化4]

[6] The resin composition according to any one of [1] to [5], wherein the maleimide compound (B) contains selected from bis(4-maleiminophenyl) methane , 2,2-bis{4-(4-maleimidphenoxy)-phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidphenyl)methane , And at least one of the group consisting of the maleimide compound represented by the following formula (4). [化5]

(In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.) [7] The resin composition of any one of [1] to [6], wherein the ratio ([ α/β]) is 0.45 to 1.0. [8] The resin composition of any one of [1] to [7] further contains an inorganic filler (C). [9] The resin composition according to [8], wherein the content of the inorganic filler (C) is 25 to 700 parts by mass relative to 100 parts by mass of the resin solid content. [10] The resin composition of [8] or [9], wherein the inorganic filler (C) contains at least one selected from the group consisting of silica, boehmite, and alumina . [11] A prepreg having a substrate and a resin composition such as any one of [1] to [10] impregnated or coated on the substrate. [12] A resin sheet formed by molding the resin composition of any one of [1] to [10] into a sheet shape. [13] A laminated resin sheet comprising: a sheet base material, and a resin composition such as any one of [1] to [10] arranged on one or both sides of the sheet base material. [14] A laminated board having one or more sheets selected from the group consisting of a prepreg such as [11], a resin sheet such as [12], and a laminated resin sheet such as [13] At least one. [15] A metal foil-clad laminate having: selected from the group consisting of a prepreg such as [11], a resin sheet such as [12], and a laminated resin sheet such as [13] At least one type; and a metal foil disposed on one or both sides of the prepreg, the resin sheet, and the laminated resin sheet. [16] A printed circuit board having an insulating layer and a conductor layer formed on one or both sides of the insulating layer, the insulating layer containing the resin composition as in any one of [1] to [10]. [Effects of Invention]

According to the present invention, it is possible to provide a resin composition that can obtain a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, resin sheet, laminated resin sheet, laminated board, and laminate using the resin composition. Metal foil laminated boards, and printed circuit boards.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the gist of the present invention.

[Resin composition] The resin composition of this embodiment contains a cyanate ester compound (A) and a maleimide compound (B), and the amount of cyanate ester group (α) of the cyanate ester compound (A) is relative to The ratio ([α/β]) of the amount (β) of the maleimine group in the maleimide compound (B) is 0.30 or more.

[Cyanate Compound (A)] The cyanate compound (A) is not particularly limited as long as it is a compound having at least one cyanate ester group. The cyanate ester compound (A) may have a reactive functional group other than a cyanate ester group, or may not have a reactive functional group other than a cyanate ester group.

Reactive functional groups other than the cyanate group are not particularly limited, and examples include allyl groups, hydroxyl groups, epoxy groups, amino groups, isocyanate groups, glycidyl groups, and phosphoric acid groups. Among them, it is preferably at least one selected from the group consisting of an allyl group, a hydroxyl group and an epoxy group, and an allyl group is more preferable. By having such a reactive functional group, the bending strength, bending elastic modulus, glass transition temperature, and thermal expansion rate of the resin composition tend to be more improved.

The cyanate ester compound (A) may be used alone or in combination of two or more kinds. When two or more types are used, the ones with reactive functional groups other than cyanate ester and those without reactive functional groups other than cyanate ester can be used. Two or more kinds of reactive functional groups other than cyanate ester group can also be used. Substituents are very useful. In this case, the reactive functional groups other than the cyanate group may be the same or different. Among them, the cyanate ester compound (A) preferably contains at least a cyanate ester compound having a reactive functional group other than the cyanate ester group. By using such a cyanate ester compound (A), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved.

The above-mentioned cyanate ester compound (A) is not particularly limited. For example, the compound represented by the following general formula (1), the compound represented by the following general formula (2) (naphthol aralkyl cyanate ester), Novolac type cyanate ester, biphenyl aralkyl type cyanate ester, bis(3,5-dimethyl 4-cyanooxyphenyl)methane, bis(4-cyanooxyphenyl)methane, 1, 3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8-dicyanooxynaphthalene, 2,6-dicyanooxynaphthalene, 2,7-dicyanooxynaphthalene, 1,3,6-tricyanoxynaphthalene Naphthalene, 4,4'-dicyanooxybiphenyl, bis(4-cyanooxyphenyl) ether, bis(4-cyanooxyphenyl) sulfide, bis(4-cyanooxyphenyl) sulfide , And 2,2'-bis(4-cyanooxyphenyl)propane; prepolymers of these cyanate esters. These can be used alone or in combination of two or more. Among them, the compound represented by the following general formula (1) and the compound represented by the following general formula (2) are more preferable.

(式(1)中，R¹ 各自獨立地表示氫原子或碳數1～4之烷基，R² 各自獨立地表示也可具有選自於由氰酸酯基、羥基及烯丙基構成之群組中之至少一者作為取代基之苯基、氫原子、烯丙基、氰酸酯基、或環氧基，n1為1以上之整數，m為1～4之整數。) ［化7］

(式(1’)中，R¹ 各自獨立地表示氫原子或碳數1～4之烷基，R² 各自獨立地表示也可具有選自於由氰酸酯基、羥基及烯丙基構成之群組中之至少一者作為取代基之苯基、氫原子、烯丙基、氰酸酯基、或環氧基，n1為1以上之整數。) ［化8］

(式(1’’)中，R¹ 各自獨立地表示氫原子或碳數1～4之烷基，n1為1以上之整數。)Among the above-mentioned cyanate ester compounds (A), the compound having a reactive functional group other than the cyanate ester group is not particularly limited. For example, it is preferably a compound represented by the following general formula (1), and the following general formula (1' The compound represented by) is more preferred, and the compound represented by the following general formula (1'') is particularly preferred. By including such a cyanate ester compound (A), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved. [化6]

(In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² each independently represents a group selected from the group consisting of a cyanate group, a hydroxyl group, and an allyl group. In the group where at least one of the substituents is a phenyl group, a hydrogen atom, an allyl group, a cyanate group, or an epoxy group, n1 is an integer of 1 or more, and m is an integer of 1 to 4.) [Chemical Formula 7 ]

(In formula (1'), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbons, and R ² each independently represents that it may be selected from the group consisting of a cyanate group, a hydroxyl group, and an allyl group. Where at least one of the groups is a phenyl group, a hydrogen atom, an allyl group, a cyanate group, or an epoxy group as a substituent, n1 is an integer of 1 or more.) [Chemical 8]

(In formula (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.)

In the formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably represents a hydrogen atom or a methyl group, and more preferably represents a methyl group. Moreover, R ² each independently represents a phenyl group, a hydrogen atom, an allyl group, and a cyanic acid group which may have at least one selected from the group consisting of a cyanate ester group, a hydroxyl group, and an allyl group as a substituent. The ester group or epoxy group preferably represents a hydrogen atom or an allyl group. Furthermore, n1 is an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5. Moreover, m is an integer of 1-4, Preferably it is an integer of 1-2.

In the formulas (1') and (1''), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably represents a hydrogen atom or a methyl group, and more preferably represents a methyl group. By using ^{a compound having a bisphenol A skeleton in which R 1} is a methyl group, there is a tendency for copper foil peeling, plating peel strength, and glass transition temperature to be more improved. In addition, by further having an allyl group, flexibility and formability also tend to be more improved. Furthermore, in formulas (1') and (1''), n1 is an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5, and particularly preferably 1.

The compound represented by the general formula (1'') is not particularly limited. For example, a compound represented by the following formula (3) is more preferable. By including such a cyanate ester compound (A), the copper foil peel strength, plating peel strength, glass transition temperature, elastic modulus maintenance rate, flexibility, and formability of the cured product are more improved tendency. [化9]

(式(2)中，R³ 各自獨立地表示氫原子或碳數1～4之烷基，n2為1以上之整數。)On the other hand, among the above-mentioned cyanate ester compounds (A), compounds that do not have reactive functional groups other than cyanate ester groups are not particularly limited. For example, compounds represented by the following general formula (2) are preferred. By including such a cyanate ester compound (A), the copper foil peel strength and the plating peel strength of the cured product obtained tend to be more improved. [化10]

(In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)

In the formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably represents a hydrogen atom. In addition, n2 is an integer of 1 or more, preferably an integer of 1-10, and more preferably an integer of 1-5.

The number of cyanate ester groups in one molecule of the cyanate ester compound (A) is not particularly limited, but is preferably 1-50, more preferably 2-12, and particularly preferably 2-6. When the number of cyanate ester groups in 1 molecule of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product are more improved Tendency to improve.

In addition, the number of reactive functional groups other than the cyanate ester group in 1 molecule of the cyanate ester compound (A) is not particularly limited, and it is preferably 1-50, more preferably 2-12, and particularly preferably 2-6. When the number of reactive functional groups other than the cyanate ester group in 1 molecule of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus of the cured product are obtained. The volume maintenance rate tends to be more improved.

The amount (α) of the cyanate ester compound (A) is not particularly limited, but is preferably 0.075 to 0.5, more preferably 0.085 to 0.4, and particularly preferably 0.095 to 0.3. When the amount (α) of the cyanate ester compound (A) of the cyanate ester compound (A) is within the above-mentioned range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained are more improved. For the tendency to improve. Regarding the amount of cyanate ester group (α), the content (parts by mass) of the cyanate ester compound (A) relative to 100 parts by mass of the resin solid content can be divided by the cyanate group equivalent of the cyanate ester compound (A) And get it. In addition, in the specification of this case, unless otherwise specified, "resin solid content" refers to the components in the resin composition that do not include solvents and inorganic fillers (C), and "100 parts by mass of resin solid content" refers to the resin composition The total of the components excluding the solvent and the inorganic filler (C) is 100 parts by mass.

The content of the cyanate ester compound (A) is not particularly limited, but is preferably 10 to 65 parts by mass, more preferably 15 to 60 parts by mass, and particularly preferably 15 to 55 parts by mass relative to 100 parts by mass of the resin solid content. When the content of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved.

The cyanate ester group equivalent of the cyanate ester compound (A) is preferably 100 to 290 g/eq., more preferably 120 to 270 g/eq., and particularly preferably 150 to 220 g/eq. When the cyanate group equivalent of the cyanate ester compound (A) is within the above range, the copper foil peel strength and the plating peel strength of the cured product obtained tend to be more improved.

(式中，R⁴ 各自獨立地表示氫原子或甲基，n3表示1以上之整數。)[Maleimine compound (B)] The maleimine compound (B) is not particularly limited as long as it is a compound having one or more maleimine groups in the molecule. For example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleiminophenyl)methane, 2,2-bis{4-(4- Maleimidin phenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidinphenyl)methane, bis(3-ethyl-5-methyl-4) -Maleimidyl)methane, bis(3,5-diethyl-4-maleimidphenyl)methane, maleimid compounds represented by the following formula (4), these horses The prepolymer of the leimine compound, or the prepolymer of the maleimide compound and the amine compound. Among them, it is preferably selected from bis(4-maleimidphenyl) methane, 2,2-bis{4-(4-maleimidphenoxy)-phenyl}propane, bis( At least one of the group consisting of 3-ethyl-5-methyl-4-maleimidphenyl)methane and the maleimid compound represented by the following formula (4) is preferred. By including such a maleimide compound (B), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved. In addition, among the above, considering the viewpoint of high glass transition temperature (high Tg), the maleimide compound represented by the following formula (4) is more preferable. [化11]

(In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

In the formula (4), R ⁴ represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom. In addition, in formula (4), n3 represents an integer of 1 or more. n3 is preferably 10 or less, more preferably 7 or less.

The amount (β) of the maleimide group of the maleimide compound (B) is not particularly limited, and is preferably 0.175 to 0.6, more preferably 0.185 to 0.5, and particularly preferably 0.195 to 0.4. When the amount of maleimide group (β) of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus of the cured product are obtained The maintenance rate tends to be more improved. The amount of maleimine group (β) can be obtained by dividing the content (parts by mass) of the maleimine compound (B) relative to 100 parts by mass of the resin solid content by the maleimide compound (B) It is obtained by the equivalent of the maleimide group.

The content of the maleimide compound (B) is not particularly limited, and it is preferably 30 to 80 parts by mass relative to 100 parts by mass of the resin solid content, more preferably 35 to 75 parts by mass, and particularly preferably 40 to 72 parts by mass . When the content of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved.

The maleimide group equivalent of the maleimide compound (B) is preferably 100-350 g/eq., more preferably 150-300 g/eq. When the maleimide group equivalent of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained are Tendency to improve.

In the resin composition of this embodiment, the ratio of the amount (α) of the cyanate ester compound (A) to the amount (β) of the maleimide compound (B) ( [Α/β]) is 0.30 or more, preferably 0.30 to 2.0, more preferably 0.40 to 1.1, particularly preferably 0.45 to 1.0. When the ratio ([α/β]) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved.

[Inorganic Filler (C)] The resin composition of this embodiment may further include an inorganic filler (C). The inorganic filler (C) is not particularly limited. For example, natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, hollow silica and other silicas; white carbon And other silicon compounds; metal oxides such as titanium white, zinc oxide, magnesium oxide, zirconium oxide; metal nitrides such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.; metal sulfates such as barium sulfate; hydroxide Aluminum and aluminum hydroxide heat-treated products (aluminum hydroxide is heated to reduce a part of the crystal water), boehmite, magnesium hydroxide and other metal hydrates; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, tin Zinc compounds such as zinc acid; alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber (including E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, etc. The inorganic filler (C) may be used alone or in combination of two or more kinds.

Among them, it is preferable to include at least one selected from the group consisting of silica, boehmite, and alumina. By using such an inorganic filler (C), the bending strength, the bending elastic modulus, and the coefficient of thermal expansion tend to be more improved.

The content of the inorganic filler (C) is preferably 25 to 700 parts by mass relative to 100 parts by mass of the resin solid content, more preferably 50 to 500 parts by mass, and particularly preferably 75 to 300 parts by mass. When the content of the inorganic filler (C) is within the above range, the copper foil peel strength and the plating peel strength of the cured product obtained tend to be more improved.

[Silicane coupling agent and wetting and dispersing agent] The resin composition of this embodiment may further include a silane coupling agent and wetting and dispersing agent. By including a silane coupling agent and a wetting and dispersing agent, the dispersibility of the above-mentioned inorganic filler (C), the resin component, the adhesive strength of the inorganic filler (C), and the substrate described later tend to be more improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic substances. For example, γ-aminopropyltriethoxysilane, N-β- (Aminoethyl)-γ-aminopropyltrimethoxysilane and other amino silane compounds; γ-glycidoxypropyl trimethoxysilane and other oxirane compounds; γ-propylene oxysilane Acrylic silane compounds such as propyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; phenyl Silane-based compounds, etc. The silane coupling agent can be used singly or in combination of two or more.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used in coatings. For example, DISPER-110, 111, 118, 180, 161, BYK-W996, W9010 manufactured by BYK-Japan Co., Ltd. , W903, etc.

[Other resins, etc.] The resin composition of this embodiment may further contain epoxy resin (D), alkenyl substituted nadicimide compound (E), and amine modified polysiloxane compound (F) if necessary . By including such other resins, the peeling strength, bending strength, and bending elastic modulus of the copper foil are more improved, and the linear thermal expansion coefficient tends to decrease.

[Epoxy resin (D)] The resin composition of this embodiment may further contain an epoxy resin (D). By further containing the epoxy resin (D), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained tend to be more improved. In addition, when the cyanate ester compound (A) has an epoxy group, when the epoxy resin (D) is used, the epoxy resin (D) is referred to as other than the epoxy group-containing cyanate ester compound (A) Compound.

The epoxy resin (D) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, Bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, Naphthalene type epoxy resin, 3-functional phenol type epoxy resin, 4-functional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, Aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, epoxy resin containing isocyanurate ring, or These halides. Among them, it is preferably at least one selected from the group consisting of naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthalene type epoxy resin.

The content of the epoxy resin (D) is preferably 2.5 to 20 parts by mass, more preferably 5.0 to 17.5 parts by mass, and particularly preferably 7.5 to 15 parts by mass relative to 100 parts by mass of the resin solid content. When the content of the epoxy resin (D) is within the above range, the flexibility, copper foil peeling strength, chemical resistance, and desmear resistance of the obtained cured product tend to be more improved.

(式中，R⁵ 各自獨立地表示氫原子、或碳數1～6之烷基，R⁶ 表示碳數1～6之伸烷基、伸苯基、伸聯苯基、伸萘基、或下式(6)或(7)表示之基團。) ［化13］

(式中，R⁷ 表示亞甲基、異亞丙基、或CO、O、S、或SO₂ 表示之取代基。) ［化14］

(式中，R⁸ 各自獨立地表示碳數1～4之伸烷基、或碳數5～8之環伸烷基。)[Alkenyl-substituted Nadicimidin Compound (E)] Alkenyl-substituted Nadicimidin Compound (E), as long as it has one or more alkenyl-substituted nadicimines in the molecule An amino compound is sufficient, and it is not particularly limited. Among them, a compound represented by the following formula (5) is preferred. By using such an alkenyl-substituted nadicimide compound (E), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus maintenance rate of the cured product obtained are more improved tendency. [化12]

(In the formula, R ⁵ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons, and R ⁶ represents an alkylene group with 1 to 6 carbons, phenylene, biphenylene, naphthylene, or The group represented by the following formula (6) or (7).) [化 13]

(In the formula, R ⁷ represents a substituent represented by methylene, isopropylene, or CO, O, S, or SO ₂ .) [Chemical 14]

(In the formula, R ⁸ each independently represents an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.)

The alkenyl-substituted nadicimidin compound (E) is preferably a compound represented by the following formula (9) and/or (10). By using such an alkenyl-substituted nadicimide compound (E), the thermal expansion coefficient of the obtained cured product tends to be lowered, and the heat resistance tends to be more improved. [化15]

In addition, a commercially available product can also be used for the alkenyl-substituted nadicimidin compound (E). Commercial products are not particularly limited. For example, BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., a compound represented by formula (9)), BANI-X (manufactured by Maruzen Petrochemical Co., Ltd., represented by formula (10) The compound) and so on. One of these can be used, or two or more of them can be used in combination.

The content of the alkenyl-substituted nadicimidin compound (E) is not particularly limited, and it is preferably 20 to 45 parts by mass, more preferably 25 to 40 parts by mass, and more preferably 25 to 40 parts by mass relative to 100 parts by mass of the resin solid content 30 to 35 parts by mass. When the content of the alkenyl-substituted nadicimide compound (E) is within the above range, the copper foil peel strength and the plating peel strength of the cured product obtained tend to be more improved.

[Amine-modified silicone compound (F)] The amine-modified silicone compound (F) is not particularly limited as long as it has one or more amine groups in the molecule. Specific examples thereof include compounds represented by the following general formula (11). [化16]

In the formula (11), R ⁸ each independently represents a hydrogen atom, a methyl group, or a phenyl group, and among them, a methyl group is preferred. R ⁹ each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms and/or an arylene group. R ⁹ may also be one in which an alkylene group having 1 to 8 carbon atoms is connected to an arylene group to form a divalent group. Among them, R ^{9 is} preferably an alkylene group having 2 to 4 carbon atoms. In formula (11), n ₄ each independently represents an integer of 1 or more.

The amine group equivalent of the amine-modified polysiloxane compound (F) is preferably 130-6000, more preferably 400-3000, and particularly preferably 600-2500. By using such an amine-modified silicone compound (F), a resin composition with a good elastic modulus maintenance rate and a lower thermal expansion rate can be obtained.

The content of the amine-modified polysiloxane compound (F) is not particularly limited. It is preferably 1-40 parts by mass, more preferably 3-30 parts by mass, and particularly preferably 5-20 parts by mass relative to 100 parts by mass of the resin solid content Copies. When the content of the amine-modified silicone compound (F) is within the above range, the elastic modulus maintenance rate and the thermal expansion rate of the cured product obtained tend to be more improved.

啉、三乙醇胺、三乙二胺、四甲基丁二胺、N-甲基哌啶等3級胺類；苯酚、二甲酚、甲酚、間苯二酚、兒茶酚等酚類；環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、油酸錫、蘋果酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯基丙酮鐵等有機金屬鹽；將該等有機金屬鹽溶解於苯酚、雙酚等含羥基之化合物而得者；氯化錫、氯化鋅、氯化鋁等無機金屬鹽；二辛基氧化錫、其他烷基錫、烷基氧化錫等有機錫化合物等。該等中，三苯基咪唑促進硬化反應，有玻璃轉移溫度、熱膨脹率優異的傾向，故特佳。[Curing accelerator] The resin composition of this embodiment may further contain a curing accelerator. The hardening accelerator is not particularly limited, and examples include triphenylimidazole, benzyl peroxide, laurel peroxide, acetyl peroxide, p-chlorobenzyl peroxide, and di-tert-butyl diperphthalate. Organic peroxides; azo compounds such as azobisnitriles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethyl Anilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl

Tertiary amines such as morpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone, etc.; Organic metal salt is obtained by dissolving in phenol, bisphenol and other hydroxyl-containing compounds; tin chloride, zinc chloride, aluminum chloride and other inorganic metal salts; dioctyl tin oxide, other alkyl tin oxide, alkyl tin oxide, etc. Organotin compounds, etc. Among these, triphenylimidazole accelerates the hardening reaction and tends to be excellent in glass transition temperature and thermal expansion coefficient, so it is particularly preferred.

[Solvent] The resin composition of this embodiment may further contain a solvent. By including the solvent, the viscosity during the preparation of the resin composition is reduced, the operability is more improved, and the impregnation of the substrate described later tends to be more improved.

The solvent is not particularly limited as long as it can dissolve part or all of the resin components in the resin composition. For example, ketones such as acetone, methyl ethyl ketone, and methyl serosol; aromatic hydrocarbons such as toluene and xylene. Class; Dimethylformamide and other amides; Propylene glycol monomethyl ether and its acetate, etc. One type of solvent may be used alone, or two or more types may be used.

[Glass transition temperature (Tg)] The glass transition temperature of the resin composition of the present embodiment is preferably 270 to 360°C, more preferably 290 to 355°C, and particularly preferably 310 to 350°C. The glass transition temperature can be measured by the method described in the examples.

[Elastic modulus maintenance rate] The elastic modulus maintenance rate of the resin composition of the present embodiment is preferably 75 to 99%, more preferably 80 to 95%, and particularly preferably 85 to 95%. "Elastic modulus retention rate" is measured in accordance with JIS C6481 for bending elastic modulus at 27°C and 260°C, and calculated according to the following formula to obtain the bending elastic modulus (a) at 27°C and the bending elasticity at 260°C. Derived from the difference in modulus (b). In addition, the elastic modulus retention rate is excellent, which means that, for example, the difference between the bending elastic modulus at 27°C and the bending elastic modulus (thermal elastic modulus) at 260°C is small. Elastic modulus maintenance rate = [(b)/(a)]×100

[Manufacturing Method of Resin Composition] The manufacturing method of the resin composition of the present embodiment is not particularly limited. For example, a method of mixing each component in a solvent in order and thoroughly stirring it can be mentioned. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading treatment may be performed. Specifically, it is possible to improve the dispersibility of the inorganic filler (C) with respect to the resin composition by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer with appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be suitably performed using, for example, a device for mixing such as a ball mill or a bead mill, or a well-known device such as a revolution or auto-type mixing device.

Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. The specific examples are as described above.

[Use] The resin composition of this embodiment can be ideally used as a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil-clad laminated board, or a printed circuit board. Hereinafter, a description will be given of a prepreg, a resin sheet, a laminated resin sheet, a laminated board, a metal foil-clad laminated board, or a printed circuit board.

[Prepreg] The prepreg of this embodiment has a substrate and the above-mentioned resin composition impregnated or coated on the substrate. The manufacturing method of the prepreg can be carried out in accordance with a conventional method, and is not particularly limited. For example, by impregnating or coating the resin component of this embodiment on a substrate, and then heating it in a dryer at 100 to 200°C for 1 to 30 minutes to semi-harden (B-stage), this embodiment can be made Form of prepreg.

The content of the resin composition (including the inorganic filler (C).) relative to the total amount of the prepreg is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and particularly preferably 40 to 80% by mass . When the content of the resin composition is within the above range, the moldability tends to be more improved.

唑(Zylon(註冊商標)，東洋紡(股)公司製)、聚醯亞胺等有機纖維。該等中，考量低熱膨脹率的觀點，宜為選自於由E玻璃布、T玻璃布、S玻璃布、Q玻璃布、及有機纖維構成之群組中之至少1種較佳。該等基材可1種單獨使用，亦可將2種以上倂用。The base material is not particularly limited, and well-known products used in various printed circuit board materials can be appropriately selected according to the intended use and performance. The specific examples of the fibers constituting the substrate are not particularly limited. For example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass, etc.; glass fibers other than quartz, etc. Inorganic fiber; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolymerized paraphenylene terephthalamide, 3,4'oxydiphenylene terephthalamide, and terephthalamide (Technora (registered trademark), manufactured by Teijin technoproducts (stock)) and other wholly aromatic polyamides; 2,6-hydroxynaphthoic acid (naphthoic acid) and p-hydroxybenzoic acid (Vectran (registered trademark), Kuraray (stock) ) Company), Zxion (registered trademark, manufactured by KB SEIREN) and other polyesters; polyparaphenylene benzo

Organic fibers such as azole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. Among them, considering the viewpoint of low thermal expansion rate, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber is preferable. These substrates may be used alone, or two or more of them may be used.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, strand mats, and surface mats. The weaving method of the weaving cloth is not particularly limited. For example, plain weave, basket weave, twill weave, etc. are known, and can be appropriately selected and used from those known in accordance with the intended use and performance. In addition, it is desirable to use a glass woven fabric obtained by subjecting these to a fiber-opening treatment, or surface-treated with a silane coupling agent or the like. The thickness and quality of the substrate are not particularly limited, but usually about 0.01 to 0.3 mm can be ideally used. In particular, considering strength and water absorption, the substrate should preferably be a ^{glass woven fabric with a thickness of 200μm or less and a mass of 250g/m 2} or less, and a glass woven fabric composed of glass fibers of E glass, S glass, and T glass is more preferred. good.

[Resin Sheet] The resin sheet of this embodiment is formed by molding the above-mentioned resin composition into a sheet shape. The manufacturing method of the resin sheet can be performed according to a common method, and is not specifically limited. For example, the following manufacturing method of the laminated resin sheet can be cited. The solution obtained by dissolving the resin composition of this embodiment in a solvent is applied to the sheet base material and dried, and then the sheet base material is removed from the laminated resin sheet The method of peeling or etching. In addition, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied to a mold having sheet-like cavities, and dried, etc., to form a sheet, and the sheet base material may not be used. A single-layer resin sheet (resin sheet) was obtained.

[Laminated Resin Sheet] The laminated resin sheet of this embodiment has a sheet base material and the above-mentioned resin composition laminated on one or both sides of the sheet base material. The laminated resin sheet is used as a method of sheeting. For example, a thermosetting resin (including an inorganic filler) used in a prepreg or the like can be directly coated on a support such as a metal foil or a film, and then dried to produce it.

The sheet base material is not particularly limited, and known products used in various printed circuit board materials can be used. For example, polyimide film, polyimide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film can be cited , Polyethylene (PE) film, aluminum foil, copper foil, gold foil, etc. Among them, electrolytic copper foil and PET film are preferred.

The coating method includes, for example, a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a sheet substrate using a coating bar, die coater, doctor blade, Baker coater, or the like.

The laminated resin sheet is preferably obtained by applying the above-mentioned resin composition to the sheet base material and then semi-curing (B-staged). Specifically, for example, the following methods can be cited: after the above resin composition is applied to a sheet substrate such as copper foil, it is heated in a dryer at 100 to 200°C for 1 to 60 minutes. Half-cured to produce a laminated resin sheet. The adhesion amount of the resin composition to the sheet substrate is preferably in the range of 1 to 300 μm based on the resin thickness of the laminated resin sheet.

[Laminated Board] The laminated board of this embodiment has one or more sheets of at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet.

[Metal Foil Clad Laminate] The metal foil clad laminate of this embodiment has: at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet, and Metal foil arranged on one side or both sides of the prepreg, the resin sheet, and the laminated resin sheet. That is, the metal foil-clad laminate of this embodiment is formed by laminating at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet, and metal foil Layer and harden to obtain.

The insulating layer may be composed of the above-mentioned resin composition, a single-layer prepreg, a resin sheet, or a laminated resin sheet, or may be composed of two or more layers of the above-mentioned resin composition, prepreg, resin sheet, or It is made of laminated resin sheets.

The conductor layer can be metal foil such as copper and aluminum. The metal foil used here is not particularly limited as long as it is used for a printed circuit board material, and it is preferably a known copper foil such as rolled copper foil and electrolytic copper foil. In addition, the thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, and more preferably 1.5 to 35 μm.

The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and the methods and conditions of general laminates and multilayer boards for printed circuit boards can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used when forming a metal-clad laminate. In addition, when forming the metal foil-clad laminate, the temperature is generally 100 to 300°C, the pressure is generally 2 to 100 kgf/cm ² , and the heating time is generally in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing may be performed at a temperature of 150 to 300°C. In addition, it is also possible to form a multilayer board by combining the above-mentioned prepreg and a separately produced inner-layer wiring board and laminating and forming it.

[Printed Circuit Board] The printed circuit board of this embodiment includes an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the above-mentioned resin composition. The above-mentioned metal foil-clad laminate can be suitably used as a printed circuit board by forming a predetermined wiring pattern. Furthermore, the above-mentioned metal-clad laminate has a low thermal expansion rate, good formability and chemical resistance, and can be particularly effectively used as a printed circuit board for semiconductor packages that require these properties.

Specifically, the printed circuit board of this embodiment can be manufactured by the following method, for example. First, the above-mentioned metal-clad laminate (copper-clad laminate, etc.) is prepared. Etching is applied to the surface of the metal foil-clad laminate to form an inner layer circuit and make an inner layer substrate. The surface of the inner circuit of the inner substrate is treated with a surface treatment for improving the adhesion strength as needed, and then the required number of the above-mentioned prepregs are stacked on the surface of the inner circuit, and the outer circuit is further laminated on the outer side of the prepreg. The metal foil used is heated and pressurized and integrally formed. In this way, a multilayer laminated board in which a base material and an insulating layer composed of a cured product of a thermosetting resin composition are formed between the inner layer circuit and the outer layer circuit metal foil is manufactured. Then, after drilling through holes and via holes on the multilayer laminate, in order to remove the scum from the resin residue contained in the resin component of the hardened layer (smear), implement de-smear treatment. Then, a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit with the metal foil for the outer layer circuit, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit to form a printed circuit board.

For example, the above-mentioned prepreg (the substrate and the above-mentioned resin composition attached to the substrate) and the resin composition layer of the metal foil-clad laminate (layer composed of the above-mentioned resin composition) constitute the resin composition Insulation.

Moreover, when a metal foil-clad laminate is not used, a conductor layer that becomes a circuit can be formed on the prepreg, the laminate resin sheet, or the resin composition to form a printed circuit board. At this time, the formation of the conductor layer can use an electroless plating method.

Regarding the printed circuit board of this embodiment, the above-mentioned insulating layer maintains an excellent elastic modulus at the reflow temperature during semiconductor packaging, and can effectively suppress the warpage of the semiconductor plastic packaging, so it can be particularly effectively used as a printing for semiconductor packaging. Circuit board. [Example]

Hereinafter, the present invention will be explained more specifically using examples and comparative examples. The present invention is not limited to the following examples.

[Synthesis example 1: Synthesis of diallyl bisphenol A type cyanate ester compound] 700 g of diallyl bisphenol A (hydroxyl equivalent 154.2 g/eq.) (4.54 mol in terms of OH group) (DABPA, Yamato Chemical Industry) (Stock)) and 459.4 g (4.54 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxyl group) were dissolved in 2,100 g of dichloromethane, and this was used as solution 1.

474.4 g (7.72 mol) of cyanogen chloride (1.7 mol relative to 1 mol of hydroxyl), 1106.9 g of methylene chloride, 735.6 g (7.26 mol) of 36% hydrochloric acid (1.6 mol relative to 1 mol of hydroxyl) , Water 4560.7g, keep the liquid temperature at -2～-0.5℃ under stirring, add solution 1 in 90 minutes. After the filling of solution 1 is completed, stir at the same temperature for 30 minutes, and then add 459.4 g (4.54 mol) of triethylamine (1.0 mol relative to 1 mol of hydroxyl) over 25 minutes and dissolve in 459.4 g of dichloromethane. Get the solution (solution 2). After the filling of solution 2 is completed, stir at the same temperature for 30 minutes to complete the reaction.

After that, the reaction liquid was left to stand and separated into an organic phase and an aqueous phase. The obtained organic phase was washed with 2L of 0.1N hydrochloric acid, and then washed with 2000g of water 6 times. The conductivity of the wastewater from the sixth water washing was 20 μS/cm. It was confirmed that the ionic compounds to be removed were sufficiently removed by the water washing.

The organic phase washed with water was concentrated under reduced pressure, and finally concentrated and dried at 90°C for 1 hour to obtain the desired diallyl bisphenol A cyanate compound (DABPA-CN, Cyanate group equivalent: 179g/eq.) 805g. The obtained IR spectrum of DABPA-CN showed ^{an absorption of 2264 cm -1} (cyanate ester group), and did not show an absorption of a hydroxyl group.

[Synthesis example 2: Synthesis of α-naphthol aralkyl type cyanate ester compound] In the reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., Nippon Steel Chemical ( Stock) system: including the naphthol aralkyl group, the number of repeating units n is 1 to 5.) 0.47 mol (in terms of OH group) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to the solution. While maintaining the temperature at -10°C, 300 g of a 0.93 mol chloroform solution of cyanogen chloride was added dropwise to the reactor over 1.5 hours, and stirred for 30 minutes after the addition was completed. After that, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further added dropwise to the reactor, and the mixture was stirred for 30 minutes to complete the reaction. After filtering the by-product triethylamine hydrochloride from the reaction solution, the obtained filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water and repeated 4 times. After drying it with sodium sulfate, it was evaporated at 75°C, and degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl cyanate resin (SNCN). The obtained α-naphthol aralkyl cyanate ester resin (SN495-V-CN, cyanate group equivalent: 261g/eq.) was analyzed by infrared absorption spectroscopy. As a result, it was confirmed that cyanic acid was near ^{2264cm -1} Absorption of ester groups.

[Example 1] DABPA-CN obtained in Synthesis Example 1 of 48.3 parts by mass, novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.), maleimide group equivalent: 186g /eq.) 27 parts by mass, bismaleimide compound (BMI-80, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide group equivalent: 285g/eq.) 14.7 parts by mass, amine-modified polysilicon Oxygen compound (X-22-161B, manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1500g/eq.) 10 parts by mass, slurry silica (SC-5050MOB, average particle size 1.5μm, Admatechs (stock) Made) 100 parts by mass, wetting and dispersing agent (DISPERBYK-161, manufactured by BYK-Japan) 1 part by mass, leveling agent (manufactured by BYK-Japan, "BYK-310") 0.05 parts by mass, hardening promotion 0.5 parts by mass of an agent (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass fabric with a thickness of 0.1 mm, and heated and dried at 140° C. for 3 minutes to obtain a prepreg with a resin content of 44% by mass. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.270, and the amount of maleimine groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide equivalent) is 0.197, and the ratio ([α/β]) is 1.37.

[Example 2] The usage amount of DABPA-CN was set to 40.3 parts by mass, and the usage amount of BMI-2300 was set to 35 parts by mass, except for this, the same method as in Example 1 was used to obtain a prepreg. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) was 0.225, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.240, and the ratio ([α/β]) is 0.94.

[Example 3] Except that the usage amount of DABPA-CN was 27.3 parts by mass and the usage amount of BMI-2300 was 48 parts by mass, the same method as in Example 1 was used to obtain a prepreg. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.153, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide equivalent) is 0.310, and the ratio ([α/β]) is 0.49.

[Example 4] The usage amount of DABPA-CN was set to 19.3 parts by mass, and the usage amount of BMI-2300 was set to 56 parts by mass, except for this, the same method as in Example 1 was used to obtain a prepreg. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) was 0.108, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.353, and the ratio ([α/β]) is 0.31.

[Comparative Example 1] Except that the usage amount of DABPA-CN was set to 14.3 parts by mass and the usage amount of BMI-2300 was set to 61 parts by mass, the same method as in Example 1 was used to obtain a prepreg. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.080, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide equivalent) is 0.380, and the ratio ([α/β]) is 0.21.

[Example 5] 52.7 parts by mass of SN495-V-CN obtained in Synthesis Example 2, novolac maleimide compound (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide equivalent : 186g/eq.) 37.3 parts by mass, biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290g/eq.) 10 parts by mass, slurry silica (SC-5050MOB, average particle size 1.5μm, Admatechs Co., Ltd.) 100 parts by mass, wetting and dispersing agent (DISPERBYK-161, BYK-Japan Co., Ltd.) 1 mass part, leveling agent (BYK-Japan (stock) ), "BYK-310") 0.05 parts by mass, and 0.5 parts by mass of a hardening accelerator (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass fabric with a thickness of 0.1 mm, and heated and dried at 140° C. for 3 minutes to obtain a prepreg with a resin content of 48% by mass. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) was 0.202, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.201, and the ratio ([α/β]) is 1.01.

[Comparative Example 2] Except for setting the usage amount of SN495-V-CN to 25.3 parts by mass and the usage amount of BMI-2300 to 64.7 parts by mass, the same method as in Example 5 was used to obtain a prepreg. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.097, and the amount of maleimine groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.348, and the ratio ([α/β]) is 0.28.

[Example 6] 24.9 parts by mass of SN495-V-CN obtained in Synthesis Example 2, novolac maleimide compound (BMI-2300, manufactured by Daiwa Chemical Co., Ltd., maleimide equivalent : 186g/eq.) 43.3 parts by mass, 31.8 parts by mass of bisallylnadic imide (manufactured by Maruzen Petrochemical Company, "BANI-M"), slurry silica (SC-5050MOB, average particle size 1.5 μm, 200 parts by mass of Admatechs (manufactured by Admatechs), 1 part by mass of wetting and dispersing agent (DISPERBYK-161, manufactured by BYK-Japan), and leveling agent (manufactured by BYK-Japan, "BYK-310") 0.05 parts by mass and 0.5 parts by mass of a hardening accelerator (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass fabric with a thickness of 0.1 mm, and heated and dried at 140° C. for 3 minutes to obtain a prepreg with a resin content of 48% by mass. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.095, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.233, and the ratio ([α/β]) is 0.41.

[Comparative Example 3] The usage amount of SN495-V-CN was set to 5 parts by mass, the usage amount of BMI-2300 was set to 49 parts by mass, the usage amount of BANI-M was set to 36 parts by mass, and biphenylarane was used Except for 10 parts by mass of a base epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g/eq.), a prepreg was obtained in the same manner as in Example 6 except for this. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.019, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide equivalent) is 0.263, and the ratio ([α/β]) is 0.07.

[Example 7] A bisphenol A type cyanate ester compound (CA210, manufactured by Mitsubishi Gas Chemical Co., Ltd., cyanate ester equivalent: 139 g/eq.) 40.5 parts by mass, and a maleimide compound (BMI-70, Maleimide equivalent 221g/eq, 29.8 parts by mass of K･I Chemical Co., Ltd., biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290g/eq.) 15 parts by mass, bismaleimide compound (BMI-80, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide group equivalent: 285g/eq.) 14.7 parts by mass, slurry dioxide 100 parts by mass of silicon (SC-5050MOB, average particle size 1.5μm, manufactured by Admatechs Co., Ltd.), 1 mass part of wetting and dispersing agent (DISPERBYK-161, manufactured by BYK-Japan Co., Ltd.), leveling agent (BYK-Japan ( Co., Ltd., "BYK-310") 0.05 parts by mass, and 0.5 parts by mass of a hardening accelerator (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to obtain a varnish. The varnish was diluted with methyl ethyl ketone, impregnated and coated on a T glass fabric with a thickness of 0.1 mm, and heated and dried at 140° C. for 3 minutes to obtain a prepreg with a resin content of 44% by mass. In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) was 0.291, and the amount of maleimide groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.186, and the ratio ([α/β]) is 1.56.

[Comparative Example 4] The use amount of bisphenol A type cyanate ester compound (CA210, manufactured by Mitsubishi Gas Chemical Co., Ltd., cyanate ester equivalent: 139 g/eq.) was set to 12 parts by mass, maleimide compound (BMI-70, maleimide equivalent 221g/eq, manufactured by K･I Chemical Co., Ltd.) The usage amount was set to 58.3 parts by mass, except for this, the prepreg was obtained in the same manner as in Example 7 . In addition, the amount of cyanate groups (α) (parts by mass/eq. of cyanate groups) of the cyanate ester compound (A) is 0.086, and the amount of maleimine groups (β) of the maleimide compound (B) ) (Parts by mass/maleimide group equivalent) is 0.315, and the ratio ([α/β]) is 0.27.

[Production of metal-clad laminated board] The obtained prepregs are superimposed on 4 or 8 pieces of each, and 12μm thick electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) is placed on the top and bottom. A pressure of 30kgf/cm ² and a temperature of 220°C were laminated and molded for 120 minutes to obtain a metal-clad laminated board with an insulating layer thickness of 0.4mm and 0.8mm. Using the obtained metal-clad laminate, the following measurements of glass transition temperature (Tg), linear thermal expansion rate, and copper foil peel strength were performed.

[Copper Foil Peeling Strength] Using the obtained metal-clad laminate (insulating layer thickness 0.8 mm), the copper foil peeling strength (kg/cm) was measured in accordance with JIS C6481.

[Plating peel strength] The surface layer copper foil of the metal-clad laminate (insulating layer thickness 0.4mm) obtained by etching is removed, using Uemura Kogyo's electroless copper plating process (use chemical name: MCD-PL , MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2) Apply electroless copper plating of about 0.5μm, and dry at 130°C for 1 hour. Then, electrolytic copper plating was applied so that the thickness of the plated copper was 18 μm, and drying was performed at 180° C. for 1 hour. In this way, a printed circuit board sample in which a conductor layer (plated copper) with a thickness of 18 μm was formed on an insulating layer with a thickness of 0.4 mm was produced. Using a printed circuit board sample with an insulating layer thickness of 0.4 mm made according to the above procedure, the adhesion of the copper plating was measured three times in accordance with JIS C6481, and the average value (kg/cm) was obtained.

[Glass transition temperature (Tg)] The obtained metal-clad laminate (insulation layer thickness 0.8mm) is cut into a size of 12.7×2.5mm with a dicing saw, and then the copper foil on the surface is removed by etching to obtain a sample for measurement . Using this measurement sample, the glass transition temperature (average value of n=3) was measured by the DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instrument) in accordance with JIS C6481.

[Elastic modulus maintenance rate] The obtained metal-clad laminate (insulating layer thickness 0.8mm) was used as a sample, and the copper foil was removed. According to the method specified in JIS C6481, Autograph (manufactured by Shimadzu Corporation) AG-Xplus) The flexural modulus of elasticity was measured at 27°C and 260°C, respectively. From the measured flexural modulus (a) at 27°C and the flexural modulus (b) at 260°C measured above, the elastic modulus maintenance rate was calculated according to the following formula. Elastic modulus maintenance rate=(b)/(a)×100

[Flexibility] Wrap the obtained prepreg on a rod with a predetermined diameter and bend it 180°. Observe the bent part of the prepreg. When the prepreg is broken, it is evaluated as broken, and if it is not broken, it is evaluated. No damage. A: No damage to the 3mmφ prepreg. B: No damage to the 5mmφ prepreg. C: No damage to the 10mmφ prepreg. D: There is damage to the 10mmφ prepreg.

【Table 1】

This application is based on a Japanese patent application (Japanese Patent Application 2016-92758) filed with the Japan Patent Office on May 2, 2016, the content of which is incorporated herein by reference. [Industrial availability]

The resin composition of the present invention has industrial applicability as a material for prepregs, resin sheets, laminated resin sheets, metal foil-clad laminates, and printed circuit boards.

Claims (16)

A resin composition containing a cyanate ester compound (A), a maleimide compound (B), and an amine modified polysiloxane compound (F), and the amount of cyanate ester group of the cyanate ester compound (A) (α) The ratio ([α/β]) of the amount (β) of the maleimide group to the maleimide compound (B) is 0.30 or more. For example, the resin composition of item 1 of the scope of patent application, wherein the cyanate ester compound (A) contains the compound represented by the following general formula (1) and/or the following general formula (2);

In formula (1), R ¹ each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and R ² each independently represents a group selected from the group consisting of a cyanate group, a hydroxyl group, and an allyl group. At least one of the substituents is a phenyl group, a hydrogen atom, an allyl group, a cyanate group, or an epoxy group, n1 is an integer of 1 or more, and m is an integer of 1 to 4;

In formula (2), R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more. For example, the resin composition of item 1 or 2 in the scope of patent application, wherein the cyanate group equivalent of the cyanate ester compound (A) is 100~220g/eq. For example, the resin composition of item 1 or 2 of the scope of patent application, wherein the cyanate ester compound (A) contains a compound represented by the following general formula (1");

In formula (1"), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more. For example, the resin composition of item 1 or 2 of the scope of patent application, wherein the cyanate ester compound (A) contains a compound represented by the following general formula (3);

For example, the resin composition of item 1 or 2 in the scope of the patent application, wherein the maleimide compound (B) contains selected from the group consisting of bis(4-maleiminophenyl) methane, 2,2-bis {4-(4-Maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, and the following formula (4 ) Represents at least one of the group consisting of maleimide compounds;

In the formula, R ⁴ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more. For example, the resin composition of item 1 or 2 in the scope of patent application, wherein the ratio ([α/β]) is 0.45~1.0. For example, the resin composition of item 1 or 2 of the scope of patent application further contains inorganic filler (C). Such as the resin composition of item 8 of the scope of patent application, wherein the content of the inorganic filler (C) is 25 to 700 parts by mass relative to 100 parts by mass of the resin solid content. Such as the resin composition of item 8 of the scope of patent application, wherein the inorganic filler (C) contains at least one selected from the group consisting of silica, boehmite, and alumina. A prepreg has: a substrate; and a resin composition such as any one of items 1 to 10 in the scope of patent application impregnated or coated on the substrate. A resin sheet is formed by molding the resin composition of any one of items 1 to 10 in the scope of the patent application into a sheet shape. A laminated resin sheet has: a sheet base material; and a resin composition such as any one of items 1 to 10 in the scope of patent application arranged on one or both sides of the sheet base material. A laminated board having one or more prepregs selected from the prepreg of the 11th patent application, the resin sheet of the 12th patent application, and the laminated resin sheet the 13th patent application At least one of the constituted groups. A metal foil-clad laminate having: a prepreg selected from the prepreg of the 11th patent application, the resin sheet of the 12th patent application, and the laminated resin sheet the 13th patent application At least one of the constituent groups; and a metal foil arranged on one or both sides of the prepreg, the resin sheet, and the laminated resin sheet. A printed circuit board has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition as in any one of items 1 to 10 in the scope of the patent application.