KR20240112225A - Resin composition - Google Patents

Abstract

[Problem] Providing a resin composition with low melt viscosity that can produce a cured product with a high glass transition temperature and low dielectric constant.
[Solution] (A) liquid epoxy resin, (B) epoxy equivalent weight of 200g/eq. A resin composition containing the above solid epoxy resin, (C) a maleimide compound, and (D) a cresol novolak-type phenol resin.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to resin compositions. Additionally, the present invention relates to prepregs, printed wiring boards, semiconductor chip packages, and semiconductor devices obtained using the resin composition.

As an insulating material that can be used as an insulating layer of a semiconductor chip package, for example, a prepreg in which a resin composition is impregnated into a base material such as glass cloth is known (see, for example, Patent Document 1).

Japanese Patent Publication No. 2014-185221

Recently, from the viewpoint of higher functionality, there is a demand for larger semiconductor chip packages. As the semiconductor chip package becomes larger, the stress applied to the insulating layer made of a cured resin composition increases, which may cause the semiconductor chip package to bend. Additionally, as semiconductor chip packages become larger, it is required to increase the glass transition temperature (Tg) in order to improve the mechanical strength of the insulating layer.

A possible method is to use a liquid epoxy resin to suppress the occurrence of warping, and to use a maleimide compound to obtain a cured product with a high glass transition temperature, but there are cases where the dielectric constant of the cured product increases.

In this way, in order to suppress the occurrence of warping, a resin composition that produces a cured product with a low melt viscosity, a high glass transition temperature, and a low dielectric constant is required.

The present invention was created in view of the above problems, and provides a resin composition with a low melt viscosity, which enables obtaining a cured product with a high glass transition temperature and a low dielectric constant; prepreg using the above resin composition; semiconductor chip package; and to provide a semiconductor device.

As a result of intensive study to solve the above problems, the present inventor found that (A) liquid epoxy resin and (B) epoxy equivalent were 200 g/eq. By using a resin composition containing the above solid epoxy resin, (C) maleimide compound, and (D) cresol novolak-type phenol resin in combination as an insulating material, the melt viscosity is low, the glass transition temperature is high, and the dielectric constant is low. The present invention was completed by discovering that it was possible to obtain a cured product.

That is, the present invention includes the following.

[1] (A) liquid epoxy resin,

(B) Epoxy equivalent weight is 200 g/eq. solid epoxy resin,

(C) maleimide compound and

(D) A resin composition containing a cresol novolak-type phenol resin.

[2] The resin composition according to [1], wherein the component (A) contains a bifunctional or higher liquid epoxy resin.

[3] The resin composition according to [1] or [2], wherein the component (B) contains a trifunctional solid epoxy resin.

[4] The resin composition according to any one of [1] to [3], wherein the component (B) includes a resin represented by the following general formula (B-1).

[Chemical formula (B-1)]

In the formula (B-1), R ¹ , R ² and R ³ each independently represent an alkylene group which may have a substituent, an oxygen atom, or an oxyalkylene group which may have a substituent, and R ⁴ has a substituent. It represents an alkyl group or a hydrogen atom which may be present, and R ⁵ represents an alkylene group which may have a substituent.

[5] Any one of [1] to [4], wherein the content of component (A) is 2% by mass or more and 12% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition described.

[6] Any one of [1] to [5], wherein the content of component (B) is 15% by mass or more and 55% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition described.

[7] Any one of [1] to [6], wherein the content of component (C) is 3% by mass or more and 20% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition described.

[8] Any one of [1] to [7], wherein the content of component (D) is 15% by mass or more and 50% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition described.

[9] The resin composition according to any one of [1] to [8], wherein the content of component (D) is greater than the content of component (C).

[10] (E) The resin composition according to any one of [1] to [9], further containing an inorganic filler.

[11] The resin composition according to [10], wherein the content of component (E) is 40% by mass or more and 80% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[12] (F) The resin composition according to any one of [1] to [11], further containing a curing accelerator.

[13] The resin composition according to [12], wherein the component (F) contains an imidazole-based curing accelerator.

[14] The resin composition according to any one of [1] to [13], wherein the resin composition contains 0.5% by mass or more and 3% by mass or less of a solvent based on 100% by mass of all components of the resin composition.

[15] A prepreg comprising a sheet-like fiber base material and the resin composition according to any one of [1] to [14] impregnated into the sheet-like fiber base material.

[16] A circuit board comprising a cured product layer formed by a cured product of the resin composition according to any one of [1] to [14].

[17] A semiconductor chip package comprising the circuit board according to [16] and a semiconductor chip mounted on the circuit board.

[18] A semiconductor device including the semiconductor chip package described in [17].

According to the present invention, a resin composition with a low melt viscosity capable of obtaining a cured product with a high glass transition temperature and a low dielectric constant; prepreg using the above resin composition; printed wiring board; semiconductor chip package; and semiconductor devices.

[Figure 1] Figure 1 is a schematic side view showing an example of two test tubes used to determine the liquid, semi-solid, and solid states of an epoxy resin.

Hereinafter, the present invention will be described by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with arbitrary changes without departing from the scope of the claims and equivalents thereof.

The determination of liquid, solid and semi-solid epoxy resins for liquid epoxy resins, solid epoxy resins and semi-solid epoxy resins is in accordance with the Annex No. 1 of the Ordinance on Testing and Properties of Dangerous Substances (Hesse Autonomous Ordinance No. 1 of the 1st year of Hesse). Carry out in accordance with the “Liquid phase confirmation method” in 2. The specific determination method is as follows.

(1) Device

Constant temperature bath:

Use one equipped with a stirrer, heater, thermometer, and automatic temperature controller (capable of temperature control at ±0.1℃) and with a depth of 150 mm or more.

In addition, in the determination of the epoxy resin used in the examples described later, a combination of a low-temperature constant temperature water tank (model BU300) manufactured by Yamato Chemical Company and an injection-type constant temperature device Thermomate (model BF500) was used, and tap water was used at about 22% Put the liter in a low-temperature constant temperature water tank (model BU300), turn on the power of the thermomate (model BF500) attached to it, set it to the set temperature (20℃ or 60℃), and set the water temperature to the set temperature ±0.1℃. Although it was fine-tuned using the model BF500), any device capable of the same adjustment can be used.

examiner:

As shown in FIG. 1, the test tube is a cylindrical transparent glass flat-bottomed tube with an inner diameter of 30 mm and a height of 120 mm. Marked lines 11A and 12B are marked at heights of 55 mm and 85 mm from the bottom of the tube, respectively, and the entrance of the test tube is marked. The test tube (10a) for liquid determination is sealed with a rubber stopper (13a), and the inlet of the test tube is sealed with a rubber stopper (13b) that is the same size, marked with the same mark, and has a hole in the center for inserting and supporting a thermometer. Then, a test tube (10b) for measuring temperature is used, with a thermometer (14) inserted into a rubber stopper (13b). Hereinafter, the marked line at a height of 55 mm from the bottom of the pipe is called "Line A", and the marked line at a height of 85 mm from the bottom of the pipe is called "Line B".

As the thermometer 14, one for measuring the solidification point (SOP-58 scale range 0 to 100°C) specified in JIS B7410 (1982) “Glass thermometer for petroleum testing” is used, but it can measure the temperature range of 0 to 100°C. It's good if you have it.

(2) Order of conducting the test

A sample left under atmospheric pressure at a temperature of 60 ± 5°C for more than 24 hours was measured up to line 11A in the test tube 10a for liquid determination shown in Fig. 1(a) and the test tube 10b for temperature measurement shown in Fig. 1(b). Put it in. Place two test tubes (10a and 10b) upright in a low-temperature constant temperature water tank so that line 12B is below the water surface. The thermometer should have its lower end 30 mm below line 11A.

After the sample temperature reaches the set temperature ±0.1°C, it is maintained for 10 minutes. After 10 minutes, the test tube (10a) for determining the liquid state is taken out of the low-temperature constant temperature water bath, immediately placed horizontally on a horizontal test table, and the time that the tip of the liquid level in the test tube moves from line 11A to line 12B is measured and recorded with a stopwatch. do.

Similarly, for samples left under atmospheric pressure at a temperature of 20 ± 5°C for more than 24 hours, the same test is performed as when left under atmospheric pressure at a temperature of 60 ± 5°C for more than 24 hours, and the tip of the liquid level in the test tube is deviated from line 11A. Measure and record the time traveled to line 12B with a stopwatch.

A liquid epoxy resin is judged to be a liquid epoxy resin if the time measured at 20°C is within 90 seconds.

A semi-solid epoxy resin is judged to have a time measured at 20°C of more than 90 seconds and a time measured at 60°C of less than 90 seconds.

A time measured at 60°C exceeding 90 seconds is judged to be a solid epoxy resin.

In the following description, “dielectric constant” refers to “relative dielectric constant” unless otherwise specified.

[Resin composition]

The resin composition of the present invention contains (A) a liquid epoxy resin and (B) an epoxy equivalent of 200 g/eq. It contains the above solid epoxy resin, (C) maleimide compound, and (D) cresol novolac type phenol resin. By using such a resin composition, the occurrence of warping is suppressed, and it becomes possible to obtain a cured product with a high glass transition temperature and low dielectric constant. Additionally, it is usually possible to obtain a cured product with a low coefficient of linear thermal expansion.

The resin composition, if necessary, contains (E) an inorganic filler, (F) a curing accelerator, (G) a semi-solid epoxy resin, and (H) an epoxy equivalent of 200 g/eq. It may further contain optional components such as a small amount of solid epoxy resin, (I) organic filler, (J) other additives, and (K) solvent. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Liquid epoxy resin>

The resin composition contains (A) liquid epoxy resin as component (A). By containing component (A) in the resin composition, it becomes possible to lower the melt viscosity, and as a result, it becomes possible to suppress the occurrence of warping of the cured product. (A) Component may be used individually, or may be used in combination of two or more types.

(A) The liquid epoxy resin preferably contains a bifunctional or higher liquid epoxy resin having two or more epoxy groups in one molecule from the viewpoint of significantly obtaining the effects of the present invention. Moreover, it is preferable that the (A) liquid epoxy resin has an aromatic structure, and when two or more types of (A) liquid epoxy resin are used, it is more preferable that at least one type has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic and includes polycyclic aromatics and aromatic heterocycles. The proportion of the (A) liquid epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass, based on 100% by mass of the non-volatile component of the (A) liquid epoxy resin. or more, particularly preferably 70% by mass or more.

(A) Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, and phenol novolak. type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins are preferred. and bisphenol F-type epoxy resin are more preferred.

Specific examples of liquid epoxy resins include "828US", "jER828EL" (bisphenol A-type epoxy resin), "jER807" (bisphenol F-type epoxy resin), and "jER152" (phenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. “630” and “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “ED-523T” (glycirol type epoxy resin (adecaglycirol)), and “EP-3980S” manufactured by ADEKA Corporation. "(glycidylamine type epoxy resin), "EP-4088S" (dicyclopentadiene type epoxy resin); “ZX1059” manufactured by Nittetsu Chemical & Materials (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton), “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nittetsu Chemical & Materials, and “ELM-100” manufactured by Sumitomo Chemical. These may be used individually, or two or more types may be used in combination.

The epoxy equivalent of the liquid epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 50 g/eq. to 3,000 g/eq., more preferably 80 g/eq. to 2,000 g/eq., more preferably 110 g/eq. to 1,000 g/eq. By falling within this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be formed. In addition, the epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the liquid epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(A) The viscosity of the liquid epoxy resin at 25°C is preferably 300 mPa·s or more, more preferably 500 mPa·s or more, and still more preferably 1,000 mPa·s from the viewpoint of obtaining a resin composition with low melt viscosity. or more, preferably 5,000 mPa·s or less, more preferably 4,000 mPa·s or less, and even more preferably 3,000 mPa·s or less. Viscosity can be measured using, for example, an E-type viscometer.

(A) The content of the liquid epoxy resin is preferably 0.1% by mass or more, more preferably 0.5% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a resin composition with low melt viscosity. or more, more preferably 1% by mass or more. The upper limit of the content of the epoxy resin is preferably 20 mass% or less, more preferably 15 mass% or less, and particularly preferably 10 mass% or less from the viewpoint of significantly obtaining the desired effect of the present invention.

In the present invention, unless otherwise specified, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is 100% by mass, and the non-volatile component is the non-volatile component excluding the solvent in the resin composition. It refers to the entire ingredient.

(A) The content of the liquid epoxy resin is preferably 2% by mass or more, when the total content of components (A) to (D) is 100% by mass, from the viewpoint of obtaining a resin composition with low melt viscosity. Preferably it is 3% by mass or more, more preferably 5% by mass or more. (A) The upper limit of the content of the liquid epoxy resin is preferably 12 mass% or less, more preferably 10 mass% or less, and particularly preferably 9 mass% or less from the viewpoint of significantly obtaining the desired effect of the present invention. .

<(B) Epoxy equivalent weight is 200g/eq. Above solid epoxy resin>

The resin composition contains, as component (B), an epoxy equivalent of (B) 200 g/eq. Contains the above solid epoxy resin. The epoxy equivalent of (B) as the component (B) is 200 g/eq. The above solid epoxy resin does not include anything corresponding to the component (A). (B) By containing a solid epoxy resin in the resin composition, it becomes possible to lower the minimum melt viscosity of the resin composition and also increase the glass transition temperature of the cured product of the resin composition. (B) Epoxy equivalent weight is 200 g/eq. The above solid epoxy resins may be used individually, or two or more types may be used in combination.

The component (B) preferably contains a trifunctional or higher solid epoxy resin having three or more epoxy groups in one molecule from the viewpoint of significantly obtaining the effects of the present invention, and contains a trifunctional solid epoxy resin. It is more preferable. Moreover, it is preferable that component (B) has an aromatic structure, and when two or more types of (B) components are used, it is more preferable that at least one type has an aromatic structure. The proportion of component (B) having 3 or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the non-volatile component of component (B), and is particularly preferred. In other words, it is more than 70% by mass. As one embodiment of the component (B), the solid epoxy resin having a trifunctional or higher aromatic structure is preferable, and the solid epoxy resin having a trifunctional aromatic structure is more preferable.

The component (B) preferably contains a resin represented by the general formula (B-1).

[Chemical formula (B-1)]

In the formula, R ¹ , R ² and R ³ each independently represent an alkylene group which may have a substituent, an oxygen atom, or an oxyalkylene group which may have a substituent, and R ⁴ represents an alkyl group or hydrogen which may have a substituent. represents an atom, and R ⁵ represents an alkylene group which may have a substituent.

R ¹ , R ² and R ³ each independently represent an alkylene group which may have a substituent, an oxygen atom, or an oxyalkylene group which may have a substituent.

The alkylene group, which may have a substituent, may be straight-chain, branched, or cyclic. A straight-chain or branched hydrocarbon group is preferable, and a straight-chain hydrocarbon group is more preferable. As the alkylene group, an alkylene group with 1 to 10 carbon atoms is preferable, an alkylene group with 1 to 6 carbon atoms is more preferable, and an alkylene group with 1 to 3 carbon atoms is still more preferable. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkylene group include methylene group, 1,1-dimethylmethylene group, ethylene group, propylene group, n-butylene group, s-butylene group, t-butylene group, pentylene group, hexylene group, heptylene group, Octylene group, nonylene group, decylene group, etc. are mentioned, and among these, methylene group, ethylene group, and propylene group are preferable, and methylene group is more preferable.

The oxyalkylene group, which may have a substituent, may be straight-chain, branched, or cyclic. A straight-chain or branched hydrocarbon group is preferable, and a straight-chain hydrocarbon group is more preferable. As the oxyalkylene group, an oxyalkylene group having 1 to 10 carbon atoms is preferable, an oxyalkylene group having 1 to 6 carbon atoms is more preferable, and an oxyalkylene group having 1 to 3 carbon atoms is still more preferable. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of oxyalkylene groups include oxymethylene group, oxyethylene group, oxypropylene group, oxyn-butylene group, oxys-butylene group, oxyt-butylene group, oxypentylene group, oxyhexylene group, and oxyheptyl. A lene group, an oxyoctylene group, an oxynonylene group, an oxydecylene group, etc. are mentioned, Among them, an oxymethylene group, an oxyethylene group, and an oxypropylene group are preferable, and an oxymethylene group is more preferable.

From the viewpoint of significantly obtaining the effects of the present invention, R ¹ , R ² and R ³ each independently preferably represent an oxyalkylene group that may have a substituent, and more preferably represent an oxymethylene group.

R ⁴ represents an alkyl group or hydrogen atom which may have a substituent. The alkyl group, which may have a substituent, may be linear, branched, or cyclic. The alkyl group is preferably an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 5 carbon atoms, preferably an alkyl group with 1 to 3 carbon atoms, and an alkyl group with 1 or 2 carbon atoms. Particularly desirable. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, and pentyl, with methyl and ethyl being preferred. A methyl group is more preferred.

From the viewpoint of significantly obtaining the effects of the present invention, R ⁴ preferably represents an alkyl group that may have a substituent, and more preferably represents a methyl group.

R ⁵ represents an alkylene group which may have a substituent, and is the same as the alkylene group which may have a substituent represented by R ¹ . From the viewpoint of significantly obtaining the effects of the present invention, R ⁵ preferably represents a methylene group or a 1,1-dimethylmethylene group, and more preferably represents a 1,1-dimethylmethylene group.

The alkylene group represented by R ¹ , R ² and R ³ , the oxyalkylene group, the alkyl group represented by R ⁴ and the alkylene group represented by R ⁵ may have a substituent. Substituents include, for example, a halogen atom, alkyl group, alkoxy group, aryl group, arylalkyl group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, Oxo group etc. are mentioned.

Resins represented by the general formula (B-1) include, but are not limited to, the following resins.

(B) The component may be a commercially available product. Commercially available products include, for example, “VG3101L” manufactured by Airwater, “1031S” manufactured by Mitsubishi Chemical, “ZX-1542” manufactured by Nittetsu Chemical & Materials, “EX-321” manufactured by Nagase Chemtex, Nippon Kaya. Examples include "NC7000L" and "YL7890" manufactured by Kusa, and "YL7800" and "jER1010" manufactured by Mitsubishi Chemical Corporation.

The epoxy equivalent of component (B) is 200 g/eq from the viewpoint of obtaining a resin composition with a low minimum melt viscosity that yields a cured product with a high glass transition temperature. or more, preferably 205 g/eq. or more, more preferably 208 g/eq. That's it. The upper limit is not particularly limited, but is preferably 5,000 g/eq. or less, more preferably 3,000 g/eq. or less, more preferably 2000 g/eq. Below, 1000g/eq. Below, 500g/eq. It is as follows. In addition, the epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of component (B) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of component (B) is preferably 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining a resin composition with a low melt viscosity that yields a cured product with a high glass transition temperature. , more preferably 3% by mass or more, even more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less, from the viewpoint of significantly obtaining the desired effect of the present invention. , 15% by mass or less.

The content of component (B) is preferably 100 mass% when the total content of components (A) to (D) is 100% by mass from the viewpoint of obtaining a resin composition with a low melt viscosity that yields a cured product with a high glass transition temperature. Preferably it is 15% by mass or more, more preferably 25% by mass or more, even more preferably 35% by mass or more, 40% by mass or more, preferably 55% by mass or less, more preferably 50% by mass or less, especially preferred. Typically, it is 45% by mass or less.

When the content of component (B) when the non-volatile component in the resin composition is set to 100 mass% is b, and the content of component (A) when the non-volatile component in the resin composition is set to 100 mass% is set to a. , from the viewpoint of significantly obtaining the effect of the present invention, a/b is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.15 or more, preferably 0.5 or less, more preferably 0.3 or less. , more preferably 0.2 or less.

<(C) Maleimide compound>

The resin composition contains (C) a maleimide compound as the (C) component. The maleimide compound (C) as the component (C) does not include those corresponding to the component (A) and component (B). (C) By containing a maleimide compound in the resin composition, it becomes possible to increase the glass transition temperature of the cured product of the resin composition. As described above, simply containing a liquid epoxy resin and a maleimide compound in combination tends to increase the dielectric constant of the cured product of the resin composition. In the present invention, by further combining and containing component (B) and component (D) in addition to the liquid epoxy resin and maleimide compound, it becomes possible to obtain a cured product with a high glass transition temperature and low dielectric constant, and melt viscosity. It becomes possible to provide a resin composition with low . (C) Maleimide compounds may be used individually, or may be used in combination of two or more types.

(C) As the maleimide compound, a compound having a 2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group (so-called maleimide group) can be used. (C) The maleimide compound may be in a liquid, semi-solid or solid form, but is preferably in a solid form from the viewpoint of significantly obtaining the effects of the present invention. The liquid phase, semi-solid phase, and solid phase are as described above.

(C) The number of maleimide groups per molecule of the maleimide compound is 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of obtaining a cured product with a high glass transition temperature, and the upper limit is is not limited, but is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Among them, as the (C) maleimide compound, a trifunctional or higher maleimide compound having three or more maleimide groups is preferable.

(C) The maleimide compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or may be an aromatic maleimide compound containing an aromatic amine skeleton. Among them, as the component (C), an aromatic maleimide compound containing an aromatic amine skeleton is preferable from the viewpoint of significantly obtaining the effects of the present invention.

(C) As the maleimide compound, a compound represented by the following general formula (C-1) is preferable.

[Formula (C-1)]

In the formula, X ^{1 and} represents a divalent linking group having skeletal atoms, s represents an integer of 1 or more, and the benzene ring C ¹ , C ² and C ³ are each independently a halogen atom, an alkyl group which may have a substituent, or an alkyl group which may have a substituent. It may be further substituted with 1 to 3 substituents selected from optional alkenyl groups, alkoxy groups which may have a substituent, and aryl groups which may have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The alkyl group, which may have a substituent, may be linear, branched, or cyclic. The alkyl group which may have a substituent is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, Cyclohexyl group, etc. are mentioned.

The alkoxy group, which may have a substituent, may be linear, branched, or cyclic. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and pentyloxy group.

The alkenyl group, which may have a substituent, may be linear, branched, or cyclic. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 3-methyl-2. -Butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group , 2-cyclohexenyl group, etc.

The aryl group that may have a substituent is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, etc., and phenyl group is preferable.

The alkyl group, alkoxy group, alkenyl group and aryl group that C ¹ , C ² and C ³ may have may have a substituent. Substituents include, for example, a halogen atom, alkyl group, alkoxy group, aryl group, arylalkyl group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, Oxo group etc. are mentioned. The number of substituents is preferably 1 to 3, and more preferably 1.

In the formula (C-1), it is preferable that the benzene rings C ¹ , C ² and C ³ are not further substituted.

In the formula (C- ¹ ), X ¹ and More preferably, it is a divalent linking group having 1 to 20 skeleton atoms, and even more preferably it is a divalent hydrocarbon group having 1 to 20 carbon atoms.

The divalent linking group at X ^{1 and} It has atoms. The “divalent linking group” is preferably -[A'-Ph] _a' -A'-[Ph-A'] _b' -[wherein A' is each independently a single bond, -(substituted or unsubstituted alkylene group) -, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- (preferably, a single bond or - (alkylene group) represents -), and a' and b' each independently represent an integer of 0 to 2. It is a divalent group represented by ]. In this specification, “Ph” represents 1,4-phenylene group, 1,3-phenylene group, or 1,2-phenylene group.

The alkylene group in the divalent linking group is the same as the alkylene group represented by R ¹ in the general formula (B-1). The alkylene group may have a substituent. The substituents that the alkylene group may have are as described above, and the number of substituents is preferably 1 to 3, and more preferably 1.

_{The divalent} ^linking _{group at X} ¹ _{and ​ ​ ​ ​ ​} CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -Ph-, -Ph-Ph-, -CH ₂ -Ph-CH ₂ -, -CH ₂ -Ph-Ph-CH ₂ -, -O-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO -, -COO-, -O-Ph-O-, -O-Ph -Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, etc. can be mentioned.

Examples of the divalent hydrocarbon group having 1 to ²⁰ carbon atoms for X ¹ and Examples include 6 to 10 arylene groups or a combination of two or more thereof, each having 1 to 20 carbon atoms. In this specification, “arylene group” refers to a divalent aromatic hydrocarbon group. Examples of arylene groups include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, and 1,8-naph. A thylene group, a 4,4'-biphenylene group, etc. are mentioned.

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in X ¹ and X ² include -CH ₂ -, -CH ₂ CH _{2 -, -CH 2 CH 2 CH 2 - , -CH 2} CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -Ph-, -Ph-Ph-, -CH ₂ -Ph -CH ₂ -, -CH ₂ -Ph-Ph-CH ₂ -, etc. can be mentioned.

In the formula (C-1), s is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Compounds represented by the formula (C-1) include, but are not limited to, the following compounds (C1) and (C2).

(In the formula, s1 represents 1 or 2, and s2 represents 1 or 2.)

(C) A commercial product may be used as the maleimide compound. Commercially available products include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", and "BMI-689" manufactured by Designer Molecules, Inc. “BMI-2500” (maleimide compound containing dimerdiamine structure), “BMI-6100” (aromatic maleimide compound) manufactured by Designer Molecules, “MIR-5000-60T” and “MIR-3000” manufactured by Nippon Kayaku Corporation. -70MT” (biphenyl aralkyl type maleimide compound), “BMI-70” and “BMI-80” manufactured by KAI Kasei, “BMI-2300” and “BMI-TMH” manufactured by Yamato Kasei Kogyo, etc. I can hear it. Additionally, as a maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indan ring skeleton) disclosed in Public Invention Association Publication No. 2020-500211 may be used.

The maleimide group equivalent of component (C) is preferably 50 g/eq from the viewpoint of significantly obtaining the desired effect of the present invention. to 2,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 150 g/eq. to 500 g/eq. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of a maleimide group.

The content of component (C) is preferably 1% by mass or more, more preferably 1.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a high glass transition temperature. , more preferably 2% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, 10% by mass or less, and 5% by mass or less.

The content of component (C) is preferably 3% by mass or more, more preferably 3% by mass or more, when the total content of components (A) to (D) is 100% by mass, from the viewpoint of obtaining a cured product with a high glass transition temperature. Preferably it is 8 mass% or more, more preferably 10 mass% or more, preferably 20 mass% or less, more preferably 18 mass% or less, and even more preferably 15 mass% or less.

When the content of component (C) when the nonvolatile component in the resin composition is 100% by mass is set to c, and the content of component (A) when the nonvolatile component in the resin composition is set at 100% by mass is set to a. , from the viewpoint of significantly obtaining the effect of the present invention, a/c is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, preferably 1.5 or less, more preferably 1 or less. , more preferably 0.8 or less.

When b is the content of component (B) when the non-volatile component in the resin composition is 100% by mass, b/c is preferably 1 or more, more preferably 1 or more, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 1.5 or more, more preferably 3 or more, preferably 10 or less, more preferably 8 or less, even more preferably 5 or less.

Moreover, (a+b)/c is preferably 1 or more, more preferably 1.5 or more, further preferably 3 or more, preferably 10 or less, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 8 or less, more preferably 5 or less.

<(D) Cresol novolac type phenolic resin>

The resin composition contains (D) a cresol novolak-type phenol resin as the (D) component. The cresol novolak-type phenol resin (D) as the component (D) does not include those corresponding to the components (A) to (C). (D) The cresol novolak-type phenol resin has the function of curing the resin composition by reacting with the component (A) and the component (B). In addition, by containing (D) a cresol novolak-type phenol resin in combination with (C) a maleimide compound in the resin composition, the glass transition temperature of the cured product of the resin composition can be increased, and at the same time, it is possible to obtain a cured product with a low dielectric constant. It becomes possible. (D) Cresol novolac type phenol resin may be used individually or in combination of two or more types.

(D) The number of phenolic hydroxyl groups per molecule of the cresol novolak-type phenolic resin is 1 or more, preferably 2 or more, more preferably 2 or more, from the viewpoint of obtaining a cured product with a high glass transition temperature and low dielectric constant. is 3 or more, and the upper limit is not limited, but is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.

(D) The cresol novolak-type phenol resin is preferably a cresol novolak-type phenol resin having a triazine skeleton and containing a triazine skeleton from the viewpoint of significantly obtaining the effects of the present invention.

(D) A commercial product may be used as the cresol novolak-type phenol resin. Examples of commercial products include "LA3018-50P", "KA-1160", "KA-1163", and "KA-1165" manufactured by DIC Corporation.

(D) The phenolic hydroxyl group equivalent of the cresol novolac type phenol resin is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The phenolic hydroxyl group equivalent is the mass of the compound per 1 equivalent of the phenolic hydroxyl group.

The amount ratio between component (A) and component (B) and all (D) components is the ratio of [total number of epoxy groups of component (A) and component (B)]:[total number of active groups of component (D)]. The range is preferably 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:2. Here, “the total number of epoxy groups of component (A) and component (B)” is the sum of the mass of the non-volatile components of component (A) and component (B) present in the resin composition divided by the epoxy equivalent. It is a value. “The total number of active groups of component (D)” is a value obtained by dividing the mass of non-volatile components of component (D) present in the resin composition by the active group equivalent. By keeping the amount ratio of component (A), component (B), and component (D) within this range, the effect of the present invention can be significantly achieved.

The amount ratio of component (A) and all (D) components is in the range of 1:0.01 to 1:1 in the ratio of [total number of epoxy groups of component (A)]:[total number of active groups of component (D)]. is preferable, 1:0.03 to 1:0.5 is more preferable, and 1:0.05 to 1:0.3 is still more preferable. Here, “the total number of epoxy groups of the epoxy resin of component (A)” is the sum of all the values obtained by dividing the mass of the non-volatile component of component (A) present in the resin composition by the epoxy equivalent. By keeping the amount ratio of component (A) and component (D) within this range, the effects of the present invention can be significantly achieved.

The amount ratio of component (B) and all (D) components is in the range of 1:0.01 to 1:1 in the ratio of [total number of epoxy groups of component (B)]:[total number of active groups of component (D)]. is preferable, 1:0.03 to 1:0.5 is more preferable, and 1:0.05 to 1:0.3 is still more preferable. Here, “the total number of epoxy groups of the epoxy resin of component (B)” is a value obtained by dividing the mass of the non-volatile component of component (B) present in the resin composition by the epoxy equivalent. By keeping the amount ratio of component (B) and component (D) within this range, the effects of the present invention can be significantly achieved.

The content of component (D) is preferably 1 mass% or more, more preferably 1 mass% or more when the non-volatile component in the resin composition is 100 mass% from the viewpoint of obtaining a cured product with a high glass transition temperature and low dielectric constant. 3% by mass or more, more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, 15% by mass or less, and 10% by mass or less. am.

The content of component (D) is preferably 15% by mass or more, more preferably 15% by mass or more, when the total content of components (A) to (D) is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention. Preferably it is 20 mass% or more, more preferably 30 mass% or more, preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less.

The content of component (D) is preferably greater than the content of component (C) from the viewpoint of obtaining a cured product with a low dielectric constant. Specifically, the content of component (D) when the non-volatile component in the resin composition is set to 100 mass% is d, and the content of component (C) when the non-volatile component in the resin composition is set to 100 mass% is When c is used, c/d is preferably less than 1, more preferably 0.8 or less, even more preferably 0.5 or less, 0.4 or less, preferably 0.05 or more, more preferably 0.08 or more, even more preferably is greater than 0.1.

<(E) Weapon Filler>

The resin composition may further include (E) an inorganic filler as an optional component in combination with the components (A) to (D). (E) By containing an inorganic filler in the resin composition, it becomes possible to obtain a cured product with a low coefficient of linear thermal expansion.

(E) An inorganic compound is used as the material for the inorganic filler. (E) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Examples include barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Additionally, spherical silica is preferred as silica. (E) Inorganic fillers may be used individually, or two or more types may be used in combination at any ratio.

(E) Commercially available inorganic fillers include, for example, “SP60-05” and “SP507-05” manufactured by Nittetsu Chemical &Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Adomatex Corporation; “UFP-30”, “DAW-03”, and “FB-105FD” manufactured by Denka Corporation; “Actual writing NSS-3N”, “Actual writing NSS-4N”, and “Actual writing NSS-5N” manufactured by Tokuyama Corporation; “Cell Spears” and “MGH-005” manufactured by Taiheyo Cement Co., Ltd.; and "BA-1" manufactured by Nikki Shokubai Kasei.

(E) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, even more preferably 2 μm or less, especially Preferably it is 1.5㎛ or less. (E) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more. . (E) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the intermediate diameter can be measured as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial bottle and dispersing them by ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction type particle size distribution measuring device, use a light source wavelength of blue and red, measure the volume-based particle size distribution of the inorganic filler using a flow cell method, and determine the median diameter from the obtained particle size distribution. The average particle diameter was calculated as . Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Sesakusho Co., Ltd.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m2/g or more, more preferably 0.5 m2/g or more, further preferably 1 m2/g or more, especially preferably 3. It is more than ㎡/g. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m2/g or less, more preferably 70 m2/g or less, even more preferably 50 m2/g or less, even more preferably Typically, it is 30 m2/g or less, particularly preferably 10 m2/g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas to the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. there is.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned. In addition, one type of surface treatment agent may be used individually, and two or more types may be used in arbitrary combination.

Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, Shin-Etsu Chemical “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Corporation, “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyo Corporation, and “KBM-4803” (long chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Kogyo Corporation ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 mass% of the inorganic filler is preferably surface treated with 0.2 mass% to 5 mass% of a surface treatment agent, more preferably 0.2 mass% to 3 mass%, and 0.3 mass%. It is more preferable that the surface is treated in an amount of 2 to 2% by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and even more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, 1.0 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

(E) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Sesakusho, etc. can be used.

(E) The content of the inorganic filler is 40% by mass or more, preferably 55% by mass or more, more preferably 55% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a low coefficient of linear thermal expansion. Preferably it is 60 mass% or more, preferably 80 mass% or less, more preferably 78 mass% or less, and even more preferably 75 mass% or less.

<(F) Curing accelerator>

The resin composition may further include a curing accelerator (F) as an optional component in combination with the components (A) to (D). The curing accelerator (F) as the component (F) does not include those corresponding to the components (A) to (E). (F) The curing accelerator has a function as a curing catalyst that promotes curing of the component (A), the component (B), and the component (G) described later.

(F) As a curing accelerator, a compound that promotes curing of the epoxy resin can be used. Examples of such (F) curing accelerators include imidazole-based curing accelerators, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, an imidazole-based curing accelerator is preferable from the viewpoint of significantly obtaining the effects of the present invention. (F) A hardening accelerator may be used individually, or may be used in combination of two or more types.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid addition Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and imidazole compounds and epoxy resins Adduct type may be mentioned. Commercially available imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kasei Kogyo Co., Ltd. PW”, “2PHZ”, “2PHZ-PW”, “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “C11Z-A”; and “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyrro. Melitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium Aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphonium tetraphenyl borate, tris (2-methyl aromatic phosphonium salts such as toxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of urea-based curing accelerators include 1,1-dimethylurea; Aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), and aromatic dimethyl ureas such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluene bisdimethylurea].

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8. -Diazabicyclo(5,4,0)-undecene, etc. can be mentioned. As an amine-type hardening accelerator, a commercial item may be used, for example, "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

(F) The content of the curing accelerator is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. , more preferably 0.015 mass% or more, preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and even more preferably 0.1 mass% or less.

<(G) Semi-solid epoxy resin>

The resin composition may further include (G) a semi-solid epoxy resin as an optional component in combination with the components (A) to (D). The semi-solid epoxy resin (G) as the component (G) does not include the components corresponding to the components (A) to (D). (G) Semi-solid epoxy resin may be used individually or in combination of two or more types.

(G) Semi-solid epoxy resins include, for example, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, and glycidylamine-type epoxy resin. Resins, phenol novolak-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure, etc. are included, and naphthalene-type epoxy resins are more preferred. desirable.

(G) The semi-solid epoxy resin preferably contains a semi-solid epoxy resin having two or more epoxy groups in one molecule. The ratio of the semi-solid epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the semi-solid epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferred. In other words, it is more than 70% by mass.

(G) As the semi-solid epoxy resin, a semi-solid epoxy resin having two or more epoxy groups per molecule is preferable, and an aromatic semi-solid epoxy resin having two or more epoxy groups per molecule is more preferable.

(G) Specific examples of the semi-solid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation, etc. are mentioned. These may be used individually or in combination of two or more types.

(G) The epoxy equivalent of the semi-solid epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 3,000 g/eq., more preferably 80 g/eq. to 2,000 g/eq., particularly preferably 110 g/eq. to 1,000 g/eq. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(G) The weight average molecular weight (Mw) of the semi-solid epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(G) The content of the semi-solid epoxy resin is preferably 1% by mass or more, more preferably 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. Preferably it is 3% by mass or more, particularly preferably 3.5% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, 20% by mass or less, and 15% by mass. % or less.

<(H) Epoxy equivalent weight is 200g/eq. Solid epoxy resin >

The resin composition is combined with the components (A) to (D), and the epoxy equivalent of (H) is 200 g/eq as an optional component. It may further contain a small amount of solid epoxy resin. The (H) epoxy equivalent as the (H) component is 200 g/eq. The solid epoxy resin having a smaller amount does not include those corresponding to the components (A) to (D). (H) Epoxy equivalent weight is 200 g/eq. One type of solid epoxy resin may be used individually, or two or more types may be used in combination.

(H) Components include, for example, tetramethylbisphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl type. Examples include epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, phenol aralkyl-type epoxy resins, phenolphthalimidine-type epoxy resins, and trisphenylmethane epoxy resins, with naphthalene-type epoxy resins being more preferable.

As the (H) component, it has two or more epoxy groups in one molecule and has an epoxy equivalent of 200 g/eq. It is preferable to contain a solid epoxy resin having an epoxy equivalent of 200 g/eq, which has three or more epoxy groups per molecule. It is more preferable to contain a solid epoxy resin having an epoxy equivalent of 200 g/eq, which has 3 or more epoxy groups in one molecule. An aromatic solid epoxy resin with less than 100% is more preferred. Epoxy equivalent weight is 200g/eq. The epoxy equivalent having two or more epoxy groups in one molecule is 200 g/eq. The proportion of solid epoxy resin is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

Specific examples of the (H) component include "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. (trisphenolmethane type epoxy resin); “ESN375” (dihydroxynaphthalene novolac type epoxy resin) manufactured by Nittetsu Chemical &Materials; "YX4000H", "YX4000", and "YX4000HK" manufactured by Mitsubishi Chemical Corporation, and "YL6121" manufactured by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); and "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

The epoxy equivalent weight of component (H) is 200 g/eq. less than, preferably 195 g/eq. Hereinafter, more preferably 190 g/eq. It is as follows. The lower limit is not particularly limited, but is preferably 80 g/eq. or more, more preferably 100 g/eq. or more, more preferably 120 g/eq. That's it.

The weight average molecular weight (Mw) of component (H) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500.

The content of component (H) is preferably 1% by mass or more, more preferably 3% by mass, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. % by mass or more, particularly preferably 3.5 mass % or more, preferably 40 mass % or less, more preferably 35 mass % or less, further preferably 30 mass % or less, 20 mass % or less, and 15 mass % or less. .

<(I) Organic filler>

The resin composition may further contain (I) an organic filler as an optional component in combination with the components (A) to (D). The (I) organic filler as the (I) component does not include those corresponding to the components (A) to (H). As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board can be used, and examples include rubber particles, polyamide fine particles, and silicon particles.

As the rubber particles, commercially available products may be used, and examples include "EXL2655" manufactured by Dow Chemical Nippon Corporation, "AC3401N" and "AC3816N" manufactured by Aika Kogyo Corporation.

(I) The content of the organic filler is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. , more preferably 0.3 mass% or more, preferably 5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.

<(J) Other additives>

The resin composition layer may contain (J) other additives as arbitrary non-volatile components. (J) Other additives include, for example, radically polymerizable compounds (excluding those corresponding to component (C)); Hardeners (excluding those corresponding to component (D)); thermoplastic resin; elastomer; polymerization initiator; Organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improvers such as urea silane; Adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; Antioxidants such as hindered phenolic antioxidants; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Phosphorus-based flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide), etc. flame retardants; Dispersants such as phosphoric acid ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; Stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers; Photopolymerization initiation aids such as tertiary amines; Photosensitizers such as pyrarizones, anthracenes, coumarins, xanthone types, and thioxanthone types can be mentioned. (J) Other additives may be used individually or in combination of two or more types.

<(K) Solvent>

The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile component described above. (K) As a solvent, a known solvent can be used as appropriate, and the type is not particularly limited, and an organic solvent is preferable. (K) Examples of the solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; Ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; Ether alcohol-based solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); Amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; Sulfoxide-based solvents such as dimethyl sulfoxide; Nitrile-based solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (K) Solvents may be used individually, or two or more types may be used in combination at any ratio.

From the viewpoint of significantly obtaining the effects of the present invention, the resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (K) solvent relative to 100% by mass of all components of the resin composition. Specifically, the solvent (K) is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, based on 100% by mass of all components of the resin composition. It is preferable that it contains 0.5 mass% or more, more preferably 0.8 mass% or more, and even more preferably 1 mass% or more.

The resin composition can be manufactured, for example, by mixing the above components in any order. Additionally, in the process of mixing each component, heating and/or cooling may be performed by appropriately adjusting the temperature. Additionally, during or after mixing each component, stirring may be performed using a stirring device such as a mixer to uniformly disperse each component. Additionally, if necessary, the resin composition may be subjected to defoaming treatment.

<Physical properties and uses of resin composition>

Since the resin composition contains components (A) to (D) in combination, it becomes a resin composition with a low melt viscosity that can produce a cured product with a high glass transition temperature (Tg) and low dielectric constant. In addition, the resin composition usually makes it possible to obtain a cured product with a low coefficient of linear thermal expansion (CTE).

Since the resin composition contains components (A) to (D) in combination, it exhibits the characteristic of low melt viscosity. Therefore, when a cured product is formed from such a resin composition, it becomes possible to obtain a cured product in which the occurrence of warping is suppressed. The melt viscosity of the resin composition is preferably less than 5,000 poise, more preferably less than 5,000 poise, and even more preferably less than 4,900 poise, less than 4,000 poise, less than 3,000 poise, and less than 2,000 poise. The lower limit is not particularly limited, but is preferably 1 poise or more, more preferably 100 poise or more, and even more preferably 200 poise or more. Melt viscosity can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 200°C for 90 minutes exhibits a high glass transition temperature (Tg). Therefore, when an insulating layer is formed with such a cured material, an insulating layer with a high glass transition temperature can be obtained. The glass transition temperature of the cured product is preferably 235°C or higher, more preferably 240°C or higher, and even more preferably 245°C or higher or 250°C or higher. The upper limit is not particularly limited, but can be, for example, 500°C or lower. The glass transition temperature can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 200°C for 90 minutes exhibits the characteristic of low dielectric constant. Therefore, when an insulating layer is formed with such a cured material, an insulating layer with a low dielectric constant can be obtained. The dielectric constant of the cured product is preferably less than 3.7, more preferably 3.7 or less, and even more preferably 3.6 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more. The dielectric constant can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 200°C for 90 minutes usually exhibits the characteristic of low linear thermal expansion coefficient. Therefore, when an insulating layer is formed with such a cured material, an insulating layer with a low coefficient of linear thermal expansion can be obtained. The linear thermal expansion coefficient of the cured product is preferably less than 22 ppm/°C, more preferably 22 ppm/°C or less, and even more preferably 20 ppm/°C or less and 15 ppm/°C or less. The lower limit is not particularly limited, but can be, for example, 0.01 ppm/°C or higher. The linear thermal expansion coefficient can be measured by the method described in the Examples described later.

The resin composition of the present invention is suitable as a resin composition for insulation purposes, and is particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). In addition, the resin composition is suitable as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. do. Additionally, the resin composition is suitable as a resin composition for forming an insulating layer of a rigid substrate (a resin composition for forming an insulating layer of a rigid substrate). The resin composition also includes sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealants, hole filling resins, component filling resins, multi-chip packages, package-on-packages, wafer-level packages, It can be used in a wide range of applications where the resin composition can be used, such as panel level packaging and system-in-package.

[Sheet-like laminated material]

Although the resin composition of the present invention can be used by applying it in the form of a varnish, it is generally suitable for use industrially in the form of a sheet-like laminated material containing the resin composition. As the sheet-like laminated material, prepregs and resin sheets shown below are preferable, and prepregs are more preferable.

<Prepreg>

The prepreg of the present invention includes a sheet-like fiber base material and the resin composition of the present invention impregnated into the sheet-like fiber base material.

The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.

The warp density and weft density of the sheet-like fiber base are each independently, preferably 60 yarns/25mm or more, more preferably 70 yarns/25mm or more, further preferably 80 yarns/25mm or more, especially preferably is 90 pieces/25mm or more, preferably 120 pieces/25mm or less, more preferably 110 pieces/25mm or less, and even more preferably 100 pieces/25mm or less. When a sheet-like fiber base material having warp and weft densities in these ranges is used, it is possible to manufacture a trench smoothly.

As a specific example of a glass cloth that can be used as a sheet-like fiber substrate, style WEA1027 manufactured by Nitto Boseki (warp density 74/25mm, weft density 74/25mm, fabric mass 19g/m2, thickness 20㎛) manufactured by Asahi Schuebel. "Style 1027MS" (warp density 75 pieces/25mm, weft density 75 pieces/25mm, fabric weight 20g/m2, thickness 19㎛), "Style 1037MS" (warp density 70 pieces/25mm, weft yarn) manufactured by Asahi Schuebel. Density: 73/25mm, fabric weight: 24g/m2, thickness: 28㎛), “1078” manufactured by Arisawa Sesakusho (warp density: 54/25mm, weft density: 54/25mm, fabric weight: 48g/m2, thickness: 43) ㎛), “1037NS” manufactured by Arisawa Sesakusho (warp density 72/25mm, weft density 69/25mm, fabric weight 23g/㎡, thickness 21㎛), “1027NS” manufactured by Arisawa Sesakusho ( Warp density 75/25mm, weft density 75/25mm, fabric weight 19.5g/㎡, thickness 16㎛), “1015NS” manufactured by Arisawa Sesakusho (warp density 95/25mm, weft density 95/25mm) , fabric weight 17.5g/㎡, thickness 15㎛), “1000NS” manufactured by Arisawa Sesakusho (warp density 85/25mm, weft density 85/25mm, fabric weight 11g/㎡, thickness 10㎛), etc. I can hear it. In addition, specific examples of liquid crystal polymer nonwoven fabrics include "Vecrus" (neck weight 6 g/m2 to 15 g/m2) and "Vectoran" manufactured by Kuraray Co., Ltd. using a melt blow method of aromatic polyester nonwoven fabric. You can.

From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the prepreg is preferably 100 μm or less, more preferably 75 μm or less, further preferably 55 μm or less, even more preferably 50 μm or less, and preferably is 5㎛ or more, more preferably 10㎛ or more, even more preferably 15㎛ or more.

The prepreg of the present invention may have metal foil laminated thereon as needed. The metal foil includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The metal foil may be a single metal layer or an alloy layer, and the alloy layer is, for example, formed of an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). You can hear the layers. Among them, from the viewpoint of the versatility of forming the metal foil, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, copper-nickel alloy, or copper titanium An alloy layer of an alloy is preferable, and a monometallic layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of a nickel-chromium alloy is more preferable, and a monometallic layer of copper is still more preferable. Additionally, the metal foil may be one in which a plurality of metal foils are laminated.

Additionally, between the prepreg and the metal foil, if necessary, a primer layer may be provided from the viewpoint of forming wiring on the prepreg by a semi-additive method. As the resin composition used in the primer layer, a resin composition conventionally used as a primer layer can be used.

The prepreg of the present invention can be manufactured by known methods such as hot melt method and solvent method. In the hot melt method, the resin composition is coated once on a release paper with good peelability, without dissolving it in an organic solvent, and then laminated on a sheet-like fiber base material or applied directly to the sheet-like fiber base material using a die coater. Prepare prepreg. In addition, in the solvent method, the sheet-like fiber base material is impregnated with the resin composition by immersing the sheet-like fiber base material in a varnish in which the resin composition is dissolved in an organic solvent, and the sheet-like fiber base material is then dried to produce a prepreg. Additionally, prepreg can also be manufactured by sandwiching a sheet-like fiber base material between two resin sheets made of a resin composition from both sides and continuously thermally laminating them under heating and pressurizing conditions. Meanwhile, the organic solvent is as described above.

The prepreg manufacturing method may be performed by a roll-to-roll method or a batch method using a long sheet-like fiber base material.

<Resin sheet>

The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. More preferably, it is 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). (in some cases), polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic, such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), poly Ether sulfide (PES), polyether ketone, polyimide, etc. can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintech, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Torres, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unichika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

In one embodiment, the resin sheet may further include other layers as needed. Examples of such other layers include a protective film similar to the support provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be manufactured, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater, etc., and further drying to form a resin composition layer. You can. The organic solvent is as described above.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the organic solvent in the resin varnish, but for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin is dried at 50°C to 150°C for 3 to 10 minutes. A composition layer can be formed.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it becomes usable by peeling the protective film.

[Circuit board and manufacturing method thereof]

The circuit board of the present invention includes a cured product layer formed by the cured product of the resin composition of the present invention. The cured material layer can be an insulating layer or a sealing layer. A printed wiring board is a type of circuit board, and a printed wiring board may be a rigid board or a flexible board. The cured product of the resin composition of the present invention has a high glass transition temperature and the occurrence of warping is suppressed, so it is suitable when the circuit board is a rigid board.

The circuit board of the present invention can be manufactured, for example, by a method including the following steps (I) and (II) using the above prepreg.

(I) Process of laminating prepreg on a substrate so that it is bonded to the substrate

(II) Process of forming an insulating layer by heat curing the prepreg

In step (I), the substrate is prepared. The base material may be an inner layer substrate used in a printed wiring board. As a substrate, a member that becomes the substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate (stainless steel or cold rolled steel sheet (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenyl substrate. Substrates such as lene ether substrates can be mentioned. Additionally, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, you may use a base material which has a peelable first metal layer and a second metal layer on both surfaces. When using such a substrate, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on the side of the second metal layer opposite to the first metal layer. Examples of the material of the metal layer include copper foil, copper foil with a carrier, and the material of the conductor layer described later, and copper foil is preferable. In addition, as a base material having such a metal layer, a commercial item can be used, for example, ultra-thin copper foil with carrier copper foil "Micro Thin" manufactured by Mitsui Kinzoku Kogyo Co., Ltd., etc.

Additionally, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as a “substrate with a wiring layer.” The conductor material included in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Materials containing the above metals can be mentioned. As the conductor material, a simple metal or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoint of versatility in forming the conductor layer, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; And as alloys, alloys of nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy are preferable. Among them, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are more preferable, and the single metal of copper is particularly preferable.

The conductor layer may be pattern-processed to function as a wiring layer, for example. At this time, the line (circuit width)/space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 ㎛ or less (i.e., pitch 40 ㎛ or less), more preferably 10/10 ㎛. Below, more preferably 5/5 ㎛ or less, even more preferably 1/1 ㎛ or less, particularly preferably 0.5/0.5 ㎛ or less. The pitch need not be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm. It is ㎛.

The conductor layer is, for example, a process of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern to obtain a patterned dry film. It can be formed by a method including a step of forming a conductor layer by a plating method such as electrolytic plating using the developed patterned dry film as a plating mask, and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, for example, a dry film formed of a resin such as novolak resin or acrylic resin can be used. The conditions for laminating the base material and the dry film may be the same as the conditions for laminating the base material and the prepreg described later. Peeling of the dry film can be performed, for example, using an alkaline peeling liquid such as sodium hydroxide solution.

Lamination of the base material and the prepreg can be performed, for example, by heat-pressing the prepreg to the base material. Examples of the member that heat-presses the prepreg to the substrate (hereinafter also referred to as “heat-press member”) include a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the heat-compression member directly on the prepreg, but to press it through an elastic material such as heat-resistant rubber so that the prepreg sufficiently follows the surface irregularities of the substrate.

Lamination of the base material and prepreg is preferably performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.7MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Sesakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurized laminator.

After lamination, the laminated prepreg may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a heat-pressing member from the prepreg side. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-described lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

In step (II), the prepreg is heat-cured to form an insulating layer. The heat curing conditions of the prepreg are not particularly limited, and conditions normally employed when forming the insulating layer of a printed wiring board may be used. The prepreg may be cured by irradiation of active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

For example, the heat curing conditions of the prepreg vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 240°C). 200°C), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before heat curing the prepreg, the prepreg may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the prepreg, the prepreg is cured for 5 minutes at a temperature of 50°C to 120°C (preferably 60°C to 110°C, more preferably 70°C to 100°C). You may preheat it for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be additionally performed. Additionally, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

Process (III) is a process of drilling into the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined appropriately according to the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The order and conditions of the roughening process are not particularly limited. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

Examples of the swelling liquid used in the roughening treatment include an alkaline solution and a surfactant solution, and an alkaline solution is preferred. As an alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Deep Securiganth P" and "Swelling Deep Securiganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid of 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 to 15 minutes.

Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

As a neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. Treatment with a neutralizing liquid can be performed by immersing the treated surface, which has undergone roughening treatment with an oxidizing agent, in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after roughening treatment may be preferably less than 500 nm, more preferably less than 200 nm, more preferably less than 100 nm, and even more preferably less than 100 nm. The lower limit is not particularly limited and may be, for example, 1 nm or more, 2 nm or more, etc. Moreover, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy) ) can include a layer formed of. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a semi-additive method, a full additive method, or the like. From the viewpoint of ease of manufacture, it is preferable to form by the semi-additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

A plating layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

In another embodiment, the printed wiring board of the present invention can also be manufactured using the resin sheet. The manufacturing method of the printed wiring board is the same as when using prepreg.

[Semiconductor chip package and manufacturing method thereof]

The semiconductor chip package of the present invention includes the circuit board and a semiconductor chip mounted on the circuit board. Such a semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

The bonding conditions between a circuit board and a semiconductor chip, such as a silicon chip, can be any condition that allows for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip chip mounting of semiconductor chips can be adopted. Additionally, for example, the semiconductor chip and the circuit board may be joined through an insulating adhesive.

An example of a bonding method is a method of pressing a semiconductor chip to a circuit board. As for the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds. range (preferably from 5 to 30 seconds).

Additionally, another example of a bonding method is a method of bonding a semiconductor chip to a circuit board by reflowing it. Reflow conditions may be in the range of 120°C to 300°C.

After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As such a mold underfill material, the above resin composition may be used, or the resin composition layer of the above resin sheet may be used.

[Semiconductor device]

A semiconductor device according to an embodiment of the present invention includes the circuit board or semiconductor chip package. Such a semiconductor device can be manufactured using the circuit board or semiconductor chip package.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). You can.

[Example]

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In addition, the operations described below were performed in an environment of normal temperature and pressure, unless otherwise specified.

[Example 1]

1) Preparation of resin composition

15 parts of naphthalene-type epoxy resin (“HP-4032SS” manufactured by DIC, epoxy equivalent of approximately 145 g/eq.), 30 parts of trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent of 210 g/eq.), bisphenol-type epoxy 5 parts of resin (“ZX1059” manufactured by Nittetsu Chemical, epoxy equivalent approximately 165 g/eq.), 16 parts of naphthalene type epoxy resin (“HP4710” manufactured by DIC, epoxy equivalent approximately 170 g/eq.), phenylmethane type maleimide 9 parts of resin (“BMI2300” manufactured by Yamato Kasei Kogyo Co., Ltd.), 3 parts of organic filler (“AC3816N” manufactured by Aika Kogyo Co., Ltd.), phenol-based curing agent having a triazine skeleton and cresol novolak structure (“LA-3018-” manufactured by DIC Co., Ltd. 50P”, phenol equivalent approximately 151 g/eq., 2-methoxypropanol solution with 50% solid content), 50 parts, 2 parts of imidazole-based reaction accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution with 5% solid content) , inorganic filler (surface treatment amount: inorganic) surface-treated with 30 parts of methyl ethyl ketone (MEK) and an amino-based silane coupling agent (“KBM573”, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 200 parts (0.6% by mass of amino-based silane coupling agent relative to 100% by mass of filler) were uniformly dispersed using a mixer to prepare a varnish of a resin composition.

2) Preparation of prepreg

The varnish of the obtained resin composition was impregnated into style WEA1027 manufactured by Nitto Boseki (warp density 74/25mm, weft density 74/25mm, fabric mass 19g/m2, thickness 20㎛, surface treatment 0.3% by mass), and a vertical shape ( A prepreg was produced by drying in a drying furnace at 105°C for 5 minutes. The resin composition content in the prepreg was 75% by mass, and the thickness of the prepreg was 50 μm. Additionally, the length of the prepreg in the vertical direction was 30 cm, and the length in the horizontal direction was 20 cm.

[Example 2]

In Example 1, 3 parts of organic filler (“AC3816N” manufactured by Aika Kogyo Co., Ltd.) was not used. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Example 3]

In Example 2, 16 parts of a naphthalene type epoxy resin (“HP-4710” manufactured by DIC, epoxy equivalent of approximately 170 g/eq.) was mixed with a special multifunctional epoxy resin (“1031S” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 224 g/eq.). eq.) changed to 16 parts. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 2 except for the above.

[Example 4]

In Example 2,

1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical, epoxy equivalent weight approximately 165 g/eq.) was changed from 5 parts to 20 parts,

2) Replace 15 parts of naphthalene-type epoxy resin (“HP4032SS” manufactured by DIC, epoxy equivalent approximately 145 g/eq.) with 16 parts of naphthalene-type epoxy resin (“HP-4710” manufactured by DIC, epoxy equivalent approximately 170 g/eq.). It was. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 2 except for the above.

[Example 5]

In Example 1, 200 parts of the inorganic filler surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (surface treatment amount: 0.6% by mass of amino-based silane coupling agent based on 100% by mass of inorganic filler) was not used. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Example 6]

In Example 1, the amount of inorganic filler surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (surface treatment amount: 0.6% by mass of amino-based silane coupling agent based on 100% by mass of inorganic filler) was 200 parts. Changed to 270 copies. Other than that, varnish and prepreg of the resin composition were obtained in the same manner as in Example 1.

[Comparative Example 1]

In Example 1, 30 parts of a trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent 210 g/eq.) was mixed with a trisphenylethane type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku, epoxy equivalent 170 g/eq. ) changed to 30 copies. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Comparative Example 2]

In Example 1,

1) Do not use 30 parts of trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent weight 210 g/eq.),

2) The amount of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC, epoxy equivalent weight approximately 145 g/eq.) was changed from 15 parts to 45 parts.

Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Comparative Example 3]

In Example 1, 9 parts of phenylmethane type maleimide resin (“BMI2300” manufactured by Yamato Kasei Kogyo Co., Ltd.) was not used. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Comparative Example 4]

In Example 1,

1) 50 parts of a phenolic curing agent having a triazine skeleton and a cresol novolak structure (“LA-3018-50P” manufactured by DIC, a phenol equivalent of about 151, a 2-methoxypropanol solution with a solid content of 50%), a triazine skeleton and Change to 45 parts of a phenol-based curing agent having a phenol novolak structure (“LA-7054-60M” manufactured by DIC, phenol equivalent weight of approximately 125 g/eq., methyl ethyl ketone solution with a solid content of 60%),

2) The amount of inorganic filler surface treated with N-phenyl-3-aminopropyltrimethoxysilane (surface treatment amount: 0.6% by mass of amino silane coupling agent based on 100% by mass of inorganic filler) was changed from 200 parts to 190 parts. .

Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Comparative Example 5]

In Example 1, 5 parts of a bisphenol-type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical, epoxy equivalent of about 165 g/eq.) was mixed with 5 parts of a trisphenylethane-type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku, epoxy equivalent of 170 g). /eq.) Changed to part 5. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 1 except for the above.

[Comparative Example 6]

In Example 5, 30 parts of a trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent 210 g/eq.) was mixed with a trisphenylethane type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku, epoxy equivalent 170 g/eq. ) Changed to 30 copies. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 5 except for the above.

[Comparative Example 7]

In Example 5, 30 parts of the trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent 210 g/eq.) was replaced with 45 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC, epoxy equivalent approximately 145 g/eq.). changed it Varnish and prepreg of the resin composition were obtained in the same manner as in Example 5 except for the above.

[Comparative Example 8]

In Example 5, 9 parts of phenylmethane type maleimide resin (“BMI2300” manufactured by Yamato Kasei Kogyo Co., Ltd.) was not used. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 5 except for the above.

[Comparative Example 9]

In Example 5,

1) 50 parts of a phenol-based curing agent (“LA-3018-50P” manufactured by DIC, phenol equivalent weight of approximately 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) having a triazine skeleton and a cresol novolac structure, Change to 45 parts of a phenol-based curing agent (“LA-7054-60M” manufactured by DIC, phenol equivalent weight of approximately 125 g/eq., methyl ethyl ketone solution with a solid content of 60%) having an azine skeleton and a phenol novolak structure,

2) The amount of naphthalene type epoxy resin (“HP4710” manufactured by DIC, epoxy equivalent weight approximately 170 g/eq.) was changed from 16 parts to 8 parts.

Varnish and prepreg of the resin composition were obtained in the same manner as in Example 5 except for the above.

[Comparative Example 10]

In Example 6, 30 parts of a trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent 210 g/eq.) was mixed with a trisphenylethane type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku, epoxy equivalent 170 g/eq. ) changed to 30 copies. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 6 except for the above.

[Comparative Example 11]

In Example 6, 30 parts of the trifunctional epoxy resin (“VG3101L” manufactured by Airwater, epoxy equivalent 210 g/eq.) was replaced with 45 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC, epoxy equivalent approximately 145 g/eq.). changed it Varnish and prepreg of the resin composition were obtained in the same manner as in Example 6 except for the above.

[Comparative Example 12]

In Example 6, 9 parts of phenylmethane type maleimide resin (“BMI2300” manufactured by Yamato Kasei Kogyo Co., Ltd.) was not used. Varnish and prepreg of the resin composition were obtained in the same manner as in Example 6 except for the above.

[Comparative Example 13]

In Example 6,

1) 50 parts of a phenol-based curing agent (“LA-3018-50P” manufactured by DIC, phenol equivalent weight of approximately 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) having a triazine skeleton and a cresol novolac structure, Change to 45 parts of a phenol-based curing agent (“LA-7054-60M” manufactured by DIC, phenol equivalent weight of approximately 125 g/eq., methyl ethyl ketone solution with a solid content of 60%) having an azine skeleton and a phenol novolak structure,

2) The amount of naphthalene type epoxy resin (“HP4710” manufactured by DIC, epoxy equivalent weight approximately 170 g/eq.) was changed from 16 parts to 8 parts.

Varnish and prepreg of the resin composition were obtained in the same manner as in Example 6 except for the above.

<Measurement of melt viscosity>

The prepregs prepared in the examples and comparative examples were cut to a diameter of 18 mm, and 20 pieces were stacked to obtain a sample for measurement. The minimum melt viscosity of the obtained measurement sample was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Corporation). Specifically, the temperature was raised in the temperature range from the starting temperature of 60°C to 200°C, the dynamic viscoelasticity was measured, and the minimum melt viscosity (poise) was calculated. The measurement conditions were a temperature increase rate of 5°C min, a measurement temperature interval of 2.5°C, a frequency of 1Hz, and a strain rate of 1deg. And the melt viscosity was evaluated based on the following evaluation criteria.

○: Melt viscosity is less than 5,000 poise

×: Melt viscosity is 5,000 poise or more

<Production of hardened prepreg products>

The prepregs produced in the examples and comparative examples were spread on a polyimide film (“Kapton H” manufactured by Torre DuPont, thickness 50 μm) using a vacuum pressurized laminator (“MVLP-500” manufactured by Makey Sesakusho). After vacuum suction at 100°C for 30 seconds, the prepreg is laminated by pressing for 30 seconds through a heat-resistant rubber at 100°C and a pressure of 0.7 MPa, and then heat-cured at 200°C for 90 minutes to form a layer of prepreg. A cured product was obtained.

<Evaluation of glass transition temperature>

The obtained cured product was measured in “tensile mode” using a thermomechanical analysis device ((DMA), manufactured by Seiko Instruments, DMS-6100). The measurement was performed in the range of 25°C to 240°C with a temperature increase of 5°C/min. Then, the glass transition temperature (Tg) was evaluated based on the following evaluation criteria.

○: Glass transition temperature is 235°C or higher.

×: Glass transition temperature is less than 235℃

<Evaluation of permittivity>

The obtained cured product was cut into test pieces with a width of 2 mm and a length of 80 mm. For the above test piece, the dielectric constant was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Measurements were made on two test pieces and the average value was calculated. And the dielectric constant was evaluated based on the following evaluation criteria.

○: Dielectric constant is less than 3.7

×: dielectric constant of 3.7 or more

<Evaluation of coefficient of linear thermal expansion (CTE)>

The obtained cured product was measured in “tensile mode” with a load of 1N using a thermomechanical analysis device ((TMA), manufactured by Hitachi High-Tech Science, TMA/SS7100). The measurement is performed twice, the first time in the range of 25°C to 200°C with a temperature increase of 5°C, the second time in the range of 25 to 260°C, and the linear thermal expansion of 30 to 150°C among the results of the second measurement. The coefficient (ppm/℃) was calculated. And the linear thermal expansion coefficient was evaluated based on the following evaluation criteria.

○: Coefficient of linear thermal expansion is less than 22ppm/℃

×: Coefficient of linear thermal expansion is 22ppm/℃ or more

Claims (18)

(A) liquid epoxy resin,
(B) Epoxy equivalent weight is 200 g/eq. solid epoxy resin,
(C) maleimide compound and
(D) A resin composition containing a cresol novolak-type phenol resin. The resin composition according to claim 1, wherein component (A) contains a bifunctional or higher liquid epoxy resin. The resin composition according to claim 1, wherein component (B) contains a trifunctional solid epoxy resin. The resin composition according to claim 1, wherein component (B) contains a resin represented by the following general formula (B-1).
[Chemical formula (B-1)]

In the formula (B-1), R ¹ , R ² and R ³ each independently represent an alkylene group which may have a substituent, an oxygen atom, or an oxyalkylene group which may have a substituent, and R ⁴ has a substituent. It represents an alkyl group or a hydrogen atom which may be present, and R ⁵ represents an alkylene group which may have a substituent. The resin composition according to claim 1, wherein the content of component (A) is 2% by mass or more and 12% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition according to claim 1, wherein the content of component (B) is 15% by mass or more and 55% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition according to claim 1, wherein the content of component (C) is 3% by mass or more and 20% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition according to claim 1, wherein the content of component (D) is 15% by mass or more and 50% by mass or less when the total amount of components (A) to (D) is 100% by mass. The resin composition according to claim 1, wherein the content of component (D) is greater than the content of component (C). The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition according to claim 10, wherein the content of component (E) is 40% by mass or more and 80% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, further comprising (F) a curing accelerator. The resin composition according to claim 12, wherein component (F) contains an imidazole-based curing accelerator. The resin composition according to claim 1, wherein the resin composition contains 0.5% by mass to 3% by mass of the solvent based on 100% by mass of all components of the resin composition. A prepreg comprising a sheet-like fiber base material and the resin composition according to any one of claims 1 to 14 impregnated into the sheet-like fiber base material. A circuit board comprising a cured product layer formed by a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor chip package comprising the circuit board according to claim 16 and a semiconductor chip mounted on the circuit board. A semiconductor device comprising the semiconductor chip package according to claim 17.