KR20230049037A - Resin composition - Google Patents

Abstract

A resin composition comprises (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer, wherein (A) the epoxy resin includes (A-1) an epoxy resin containing an epoxy group and a structure having chelate forming ability. According to the present invention, it is possible to provide: a resin composition capable of obtaining a cured product that suppresses warping and has excellent adhesion to a conductor layer; a cured product of the resin composition; and resin sheets, circuit boards, semiconductor chip packages, and semiconductor devices using the resin composition.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition and a cured product using the resin composition, a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device.

In recent years, the demand for small, highly functional electronic devices such as smart phones and tablet devices has been increasing, and accordingly, sealing materials for semiconductor chip packages used in these small electronic devices are also required to be more highly functional. As such a sealing material, what is formed by hardening a resin composition is known.

On the other hand, there are techniques of Patent Literatures 1 and 2 as techniques for applications other than sealing materials.

Japanese Unexamined Patent Publication No. 2018-80221 Japanese Patent Publication No. 5491276

A resin composition used for a sealing material generally contains an inorganic filler for the purpose of improving insulating properties and sealing properties. Thus, the hardened|cured material of the resin composition containing an inorganic filler tends to generate large warp.

If the cured product contains a fiber base material like a prepray, it is thought that warpage can be suppressed because the rigidity of the entire cured product can be increased or thermal expansion can be reduced by the action of the fiber base material. However, since the sealing material usually does not contain a fiber base material, suppression of warpage was difficult.

Then, this inventor tried to suppress warp by lowering the elastic modulus of the hardened|cured material of a resin composition. Specifically, by adopting a resin composition containing an elastomer, an attempt was made to lower the modulus of elasticity of the cured product and suppress warpage. As a result, suppression of warpage was able to be achieved. However, the hardened|cured material of the resin composition containing an elastomer was inferior in adhesiveness with a conductor layer.

Therefore, the present inventors further studied and tried to improve the adhesion by using an adhesion imparting agent in combination with the elastomer. However, when an adhesive imparting agent was used, although adhesiveness improved, warpage became large. Therefore, in the conventional sealing material, it is difficult to achieve both suppression of warpage and improvement of adhesion.

The present invention has been devised in view of the above problems, and includes a resin composition capable of obtaining a cured product having excellent curvature suppression and adhesion to a conductor layer; a cured product of the resin composition; And to provide a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device using the resin composition.

The present inventors intensively studied in order to solve the above problems. As a result, the present inventors found (A) an epoxy resin, (B) an inorganic filler and (C) an elastomer, and (A) an epoxy resin containing a structure having (A-1) an epoxy group and a chelate forming ability. According to the resin composition containing resin, it was discovered that the said subject could be solved, and this invention was completed.

That is, the present invention includes the following.

[1] (A) containing an epoxy resin, (B) an inorganic filler and (C) an elastomer,

(A) The resin composition in which the epoxy resin contains the epoxy resin containing the structure which has (A-1) epoxy group and chelate formation ability.

[2] The resin composition according to [1], wherein the amount of chelate modification of component (A-1) is 0.3% by mass to 10% by mass.

[3] The ratio W (A-1) / W (C) of the mass W (A-1) of component (A-1) and the mass W (C) of component (C) is 0.01 to 1.0, [1] or the resin composition according to [2].

[4] The resin composition according to any one of [1] to [3], wherein the amount of the component (B) is 40% by mass or more with respect to 100% by mass of the non-volatile component of the resin composition.

[5] The resin composition according to any one of [1] to [4], wherein component (C) has a number average molecular weight of 1,000 or more.

[6] (D) The resin composition according to any one of [1] to [5], further containing a curing agent.

[7] (E) The resin composition according to any one of [1] to [6], further comprising a curing accelerator.

[8] The resin composition according to any one of [1] to [7], which is for a sealing layer.

[9] A cured product of the resin composition according to any one of [1] to [8].

[10] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [8] formed on the support.

[11] A circuit board comprising a cured product of the resin composition according to any one of [1] to [8].

[12] A semiconductor chip package containing a cured product of the resin composition according to any one of [1] to [8].

[13] A semiconductor device comprising the circuit board according to [11] or the semiconductor chip package according to [12].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the cured material excellent in suppression of warp and adhesiveness with a conductor layer; a cured product of the resin composition; And it is possible to provide a resin sheet, a circuit board, a semiconductor chip package and a semiconductor device using the resin composition.

[Fig. 1] Fig. 1 is a cross-sectional view schematically showing a Fan-Out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention are shown and described. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with arbitrary changes within a range not departing from the scope of the claims and their equivalents.

[One. Overview of Resin Composition]

A resin composition according to one embodiment of the present invention includes (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer in combination. And (A) The epoxy resin contains the epoxy resin containing the structure which has (A-1) epoxy group and chelate formation ability. In the following description, "(A-1) epoxy resin containing an epoxy group and a structure having chelate forming ability" may be referred to as "(A-1) chelate type epoxy resin". In addition, in the following description, a "structure having chelate-forming ability" may be referred to as a "chelate-capable structure".

A cured product can be obtained by thermally curing the resin composition according to the present embodiment. And the cured|cured material obtained can be excellent in suppression of curvature and adhesiveness with a conductor layer. In addition, the cured product of the resin composition according to the present embodiment can usually have excellent adhesion to silicone. In addition, the resin composition according to the present embodiment preferably has a low minimum melt viscosity, and it is preferable that a cured product having a small tensile modulus of elasticity can be obtained.

The resin composition according to the present embodiment may further contain an optional component in combination with the above components. For example, the resin composition may contain (D) a hardening agent, (E) a hardening accelerator, etc.

[2. (A) Epoxy Resin]

The resin composition according to the present embodiment contains (A) epoxy resin as component (A). (A) An epoxy resin is a curable resin having an epoxy group.

The (A) epoxy resin according to the present embodiment contains the (A-1) chelate type epoxy resin as the component (A-1). (A-1) A chelate-type epoxy resin contains an epoxy group and a chelate ability structure.

A chelating ability structure represents a structure having a chelating ability. Such a chelating ability structure usually contains at least one type of atom selected from the group consisting of oxygen and nitrogen. In the following description, an atom selected from the group consisting of oxygen and nitrogen may be referred to as a "specific atom". One chelating ability structure usually contains a plurality of specific atoms. Since a plurality of specific atoms are generally not directly bonded, there is a molecular chain linking the specific atoms between these specific atoms. That is, between specific atoms, it is usually connected by a molecular chain. Here, the atoms included in the molecular chain do not include oxygen atoms and nitrogen atoms. The number of atoms in the molecular chain is usually 1 or more, preferably 2 or more, and preferably 6 or less. Here, the number of atoms of the molecular chain linking between specific atoms represents the minimum number of atoms present between specific atoms linked by a molecular chain. Therefore, even when a branch chain branched from the molecular chain is bonded to the molecular chain, the number of atoms included in the branch chain is not included in the number of atoms of the molecular chain. Therefore, the chelate ability structure may be a structure containing preferably 1 or more and 6 or less, more preferably 2 or more and 6 or less atoms adjacent to each other via an atom. In the chelating ability structure, some or all of the specific atoms can function as coordinating atoms.

It is preferable that the chelate ability structure contains an oxygen atom as a specific atom.

It is more preferable that at least one of the oxygen atoms as specific atoms is derived from a hydroxyl group. That is, it is more preferable that the chelate ability structure contains a hydroxyl group, and the oxygen atom contained in the said hydroxyl group is a specific atom of the chelate ability structure.

Moreover, it is more preferable that at least one of the oxygen atoms as a specific atom is derived from a carbonyl group. That is, it is more preferable that the chelate ability structure contains a carbonyl group, and the oxygen atom contained in the carbonyl group is a specific atom of the chelate ability structure.

When the chelating ability structure contains a plurality of oxygen atoms, it is preferable that these oxygen atoms contain oxygen atoms connected by a molecular chain having two atoms. That is, it is preferable that any two oxygen atoms contained in the chelate ability structure are adjacent via two atoms. The chelate ability structure may contain only one pair of the pair of two oxygen atoms adjoining via two atoms as mentioned above, and may contain two or more pairs.

The chelating ability structure usually contains a carbon atom and a hydrogen atom in combination with a specific atom. Moreover, the chelate ability structure may further contain arbitrary heteroatoms other than an oxygen atom and a nitrogen atom. A phosphorus atom and a sulfur atom are mentioned as an arbitrary heteroatom which the chelate ability structure preferably contains. The number of arbitrary heteroatoms may be one or two or more. In addition, the number of arbitrary heteroatoms may be 1 or 2 or more.

Specific examples of the preferred chelating ability structure include a carboxy group and a phosphoric acid group. Especially, a phosphoric acid group is more preferable. The chelate ability structure may exist in any of the basic skeleton, side chain, or terminal of the (A-1) chelate type epoxy resin. (A-1) The chelating ability structure which a chelate type epoxy resin contains may be 1 type, or 2 or more types may be sufficient as it. In addition, the number of chelating ability structures which (A-1) chelate-type epoxy resin contains in 1 molecule may be 1, or 2 or more may be sufficient as it.

(A-1) The number of epoxy groups that the chelate type epoxy resin contains in one molecule may be one or two or more.

(A-1) The chelate type epoxy resin preferably contains an aromatic structure in the molecule. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. When using the (A-1) chelate type epoxy resin containing an aromatic ring structure, the heat resistance of the hardened|cured material of a resin composition can be improved.

(A-1) A chelate type epoxy resin can contain the structure obtained by reacting with the epoxy resin which does not contain a chelate functional structure, and the compound containing a chelate functional structure. For example, the (A-1) chelate-type epoxy resin containing a phosphoric acid group can contain a structure obtained by reacting an epoxy resin and phosphoric acids that do not contain a chelate functional structure. Examples of phosphoric acids include phosphoric acid (H ₃ PO ₄ ), phosphonic acid (H ₃ PO ₃ ), self-phosphoric acid (H ₃ PO ₂ ), diphosphoric acid (H ₄ P ₂ O ₇ ), and polyphosphoric acid such as triphosphoric acid. Phosphoric acid can be mentioned.

(A-1) A chelate-type epoxy resin can be manufactured by the method which includes, for example, glycidyl-etherifying a phenolic or alcoholic hydroxyl group and the hydroxyl group of the compound which has a chelate functional structure. The (A-1) chelate type epoxy resin can be produced, for example, by a method including reacting an epoxy resin not containing a chelate functional structure with a compound containing a chelate functional structure. For example, the (A-1) chelate type epoxy resin containing a phosphoric acid group can be manufactured by the method described in International Publication No. 2021/039380.

In the method for producing a chelate type epoxy resin (A-1) comprising reacting an epoxy resin containing no chelating functional structure with a compound containing a chelating functional structure, the epoxy group of the epoxy resin usually contains a chelating functional structure. The compound reacts to obtain (A-1) chelate type epoxy resin. At this time, the amount of reaction of the compound containing the chelating ability structure is expressed as the amount of chelate modification. Specifically, the amount of chelate modification is expressed as a ratio of a compound containing a chelate functional structure reacted to the epoxy resin with respect to 100% by mass of an epoxy resin containing no chelate functional structure. The amount of chelate modification is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.8% by mass or more, preferably 10% by mass or less, more preferably 5.0% by mass or less, Especially preferably, it is 3.0 mass % or less. When the amount of chelate modification is within the above range, the adhesiveness of the cured product of the resin composition can be effectively improved.

(A-1) As a chelate type epoxy resin, you may use a commercial item. As a commercially available (A-1) chelate type epoxy resin, "EP-49-10P" by ADEKA, "EP-49-10P2" (both are reaction products of bisphenol A type epoxy resin and phosphoric acid); "EP-49-23" by ADEKA Corporation is mentioned.

(A-1) A chelate type epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

Epoxy resins include liquid epoxy resins at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and solid epoxy resins at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). there is The (A-1) chelate type epoxy resin contained in the resin composition may be a liquid epoxy resin alone, a solid epoxy resin alone, or a combination of a liquid epoxy resin and a solid epoxy resin. (A-1) The chelate type epoxy resin preferably contains a liquid epoxy resin, and more preferably contains only a liquid epoxy resin.

(A-1) The epoxy equivalent of the chelate type 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 shows the mass of resin per 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A-1) The weight average molecular weight (Mw) of the chelate type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. Moreover, the number average molecular weight of (A-1) chelate type epoxy resin is less than 5,000 normally, Preferably it is less than 3,000. The weight average molecular weight and number average molecular weight of the resin can be measured as values in terms of polystyrene by a gel permeation chromatography (GPC) method.

The amount of the chelating epoxy resin (A-1) in the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass based on 100% by mass of the non-volatile component of the resin composition. % or more, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. (A-1) When the amount of the chelate type epoxy resin is within the above range, the adhesiveness can be effectively improved while curvature is suppressed, and the minimum melt viscosity can usually be effectively lowered.

The amount of the chelate type epoxy resin (A-1) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass with respect to 100% by mass of the resin component of the resin composition. or more, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Unless otherwise indicated, the resin component of a resin composition represents the component except (B) inorganic filler among the non-volatile components of a resin composition. (A-1) When the amount of the chelate type epoxy resin is within the above range, the adhesiveness can be effectively improved while curvature is suppressed, and the minimum melt viscosity can usually be effectively lowered.

(A) With respect to 100% by mass of the total amount of the epoxy resin, the mass of the (A-1) chelate type epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. (A-1) When the amount of the chelate type epoxy resin is within the above range, the adhesiveness can be effectively improved while curvature is suppressed, and the minimum melt viscosity can usually be effectively lowered.

The ratio W(A-1)/W(C) of the mass W(A-1) of the (A-1) chelate type epoxy resin in the resin composition and the mass W(C) of the (C) elastomer is within a specific range. it is desirable Specifically, the ratio W(A-1)/W(C) is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.04 or more, preferably 1.0 or less, more preferably 0.8 or less, particularly preferably 0.7 or less. When the ratio W(A-1)/W(C) is within the above range, the adhesiveness can be effectively improved while curvature is suppressed, and the minimum melt viscosity can usually be effectively lowered.

(A) Even if the epoxy resin contains an epoxy resin other than the chelate type epoxy resin (A-2) (A-1) as the component (A-2) in combination with the (A-1) chelate type epoxy resin good night. In the following description, "(A-2) (A-1) epoxy resin other than chelate type epoxy resin" may be referred to as "(A-2) arbitrary epoxy resin".

(A-2) Examples of arbitrary epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy Resins, cresol novolak type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, Cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, etc. can (A-2) Arbitrary epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.

(A-2) It is preferable that the arbitrary epoxy resin contains the epoxy resin containing an aromatic structure from a viewpoint of obtaining the hardened|cured material excellent in heat resistance. Examples of the optional epoxy resin (A-2) containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type epoxy resin. Resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy Resin, glycidylamine type epoxy resin having an aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, aromatic structure An alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin having an aromatic structure, a cyclohexane dimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, an aromatic tetraphenylethane type epoxy resins having a structure; and the like.

(A-2) It is preferable that arbitrary epoxy resins contain the epoxy resin which has 2 or more epoxy groups in 1 molecule. (A-2) The ratio of the epoxy resin having two or more epoxy groups per molecule to 100% by mass of the non-volatile component of any epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more. , Particularly preferably, it is 70% by mass or more.

(A-2) The optional epoxy resin may be a liquid epoxy resin alone, a solid epoxy resin alone, or a combination of a liquid epoxy resin and a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable. (A-2) As a preferable liquid epoxy resin which can be used as arbitrary epoxy resins, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resins, phenol novolak type epoxy resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

(A-2) As a specific example of the liquid epoxy resin which can be used as arbitrary epoxy resin, DIC Corporation "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin); "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F-type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" by Mitsubishi Chemical Corporation, "630LSD", "604" (glycidylamine type|mold epoxy resin); "ED-523T" by ADEKA (a glycerol-type epoxy resin); "EP-3950L" by ADEKA, "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" by ADEKA (dicyclopentadiene type epoxy resin); "ZX-1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Chemical Co., Ltd.; "PB-3600" by Daicel Co., Ltd., "JP-100" by Nippon Soda Co., Ltd., "JP-200" (epoxy resin having a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon-Stetsu Chemical & Material Co., Ltd. and the like are exemplified. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. (A-2) Preferred solid-state epoxy resins that can be used as any epoxy resin include, for example, bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol furnace Rockfish type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF A type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, and a phenolphthalimidine type epoxy resin are preferable.

(A-2) As a specific example of the solid-state epoxy resin which can be used as arbitrary epoxy resins, "HP4032H" by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" by DIC Corporation, "HP-4710" (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC Corporation (cresol novolak-type epoxy resin); "N-695" by DIC Corporation (cresol novolak-type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin) manufactured by DIC; Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxy naphthalene type epoxy resin) by the Nippon-tsu Chemical & Material company; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX8800" (anthracene-type epoxy resin); Mitsubishi Chemical Corporation "YX7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); "WHR991S" (phenolphthalimidine type epoxy resin) by Nippon Kayaku Co., Ltd., etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A-2) The range of the epoxy equivalent of the arbitrary epoxy resin may be the same as the range of the epoxy equivalent of the (A-1) chelate type epoxy resin.

(A-2) The ranges of the weight average molecular weight and number average molecular weight of the arbitrary epoxy resin may be the same as the ranges of the weight average molecular weight and number average molecular weight of the (A-1) chelate type epoxy resin.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 20:1 to 1:5, more preferably 10 :1 to 1:2, particularly preferably 5:1 to 1:1.

The amount of (A) epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more, based on 100% by mass of the non-volatile component of the resin composition, It is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. (A) When the amount of the epoxy resin is within the above range, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered.

The amount of the epoxy resin (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, based on 100% by mass of the resin component of the resin composition. It is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. (A) When the amount of the epoxy resin is within the above range, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered.

[3. (B) inorganic filler]

The resin composition according to the present embodiment includes (B) an inorganic filler as component (B). (B) An inorganic filler is usually contained in a resin composition in the form of particles.

(B) As a material of an inorganic filler, an inorganic compound is used. (B) Materials for the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, Zirconate barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. are mentioned. Among these, silica and alumina oxide are suitable, and silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. are mentioned, for example. Moreover, as a silica, spherical silica is preferable. (B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) As a commercial item of an inorganic filler, it is "UFP-30" by Denka Chemical Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex; "UFP-30" by Denka Corporation; "Seal Fill NSS-3N", "Seal Fill NSS-4N", and "Seal Fill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" by Adomatex Co., Ltd., etc. are mentioned.

(B) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 10 μm or more, from the viewpoint of significantly obtaining the desired effect of the present invention. μm or less, more preferably 7 μm or less, still more preferably 5 μm or less.

(B) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer and taking the median diameter as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic waves for 10 minutes can be used. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, using blue and red light source wavelengths, and measuring the volume-based particle size distribution of the inorganic filler by a flow cell method, and from the obtained particle size distribution, the median diameter The average particle diameter can be calculated as Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Seisakusho Co., Ltd. and the like.

(B) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 /g or more from the viewpoint of significantly obtaining the desired effect of the present invention. . The upper limit is not particularly limited, but is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area can be measured according to the BET method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) and calculating the specific surface area using the BET multi-point method.

(B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent 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. A ring agent etc. are mentioned. A surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane) Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Co., Ltd. ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc. are mentioned.

The degree of surface treatment with the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of (B) the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.2% by mass to 3% by mass of a surface treatment agent, It is more preferable that the surface is treated with a surface treatment agent of 0.3% by mass to 2% by mass.

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

(B) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant liquid and drying the solid content, 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 Seisakusho Co., Ltd. or the like can be used.

The amount of the inorganic filler (B) in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, especially with respect to 100% by mass of the non-volatile component of the resin composition. It is preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less. In general, when the amount of the inorganic filler is large as described above, the problems of an increase in the minimum melt viscosity of the resin composition and a decrease in the adhesiveness of a cured product of the resin composition tend to occur. In contrast, according to the resin composition according to the present embodiment, even when the inorganic filler is large as described above, the adhesiveness of the cured product can be improved, and more preferably the minimum melt viscosity can be reduced. Therefore, the advantage of the resin composition according to the present embodiment can be particularly effectively utilized when the inorganic filler (B) is included in a large number equal to or greater than the above lower limit. Further, (B) When the amount of the inorganic filler is less than or equal to the above upper limit, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered.

[4. (C) elastomer]

The resin composition according to the present embodiment contains (C) elastomer as component (C). The elastomer (C) does not include those corresponding to the components (A) to (B). (C) The elastomer is a resin having flexibility, and preferably a resin having rubber elasticity or a resin exhibiting rubber elasticity by polymerizing with other components. Examples of rubber elasticity include a resin that exhibits an elastic modulus of 1 GPa or less when a tensile test is performed in accordance with Japanese Industrial Standards (JIS K7161) at a temperature of 25° C. and a humidity of 40% RH. (C) The elastomer is usually an amorphous resin component that can be dissolved in an organic solvent. (C) An elastomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. (C) According to the elastomer, the elastic modulus of the cured product of the resin composition can be lowered.

(C) It is preferable that an elastomer is high molecular weight. (C) The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, still more preferably 3,000 or more, and particularly preferably 5,000 or more. (C) When the elastomer has a high molecular weight as described above, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered. The upper limit of the number average molecular weight is not particularly limited, but is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

(C) The elastomer is preferably at least one selected from resins having a glass transition temperature (Tg) of 25°C or less and liquid resins at 25°C or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but may be usually -15°C or higher. The resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a heating rate of 5°C/min.

(C) In the molecule, the elastomer has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polystyrene structure. It is preferable that it is resin which has 1 or more types of structures chosen from structures. "(meth)acrylate" is a term containing methacrylate, acrylate, and combinations thereof. These structures may be included in the main chain or side chain of the (C) elastomer molecule.

(C) As an elastomer, resin containing a polybutadiene structure is mentioned, for example. The polybutadiene structure may be contained in the main chain or in the side chain. In addition, part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure may be referred to as "polybutadiene resin". Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" manufactured by Clay Valley. "(polybutadiene containing an acid anhydride group), "GQ-1000" (hydroxyl group, carboxyl group-introduced polybutadiene) manufactured by Nippon Soda Co., Ltd., "G-1000", "G-2000", "G-3000" (both ends) hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" (both hydroxyl group hydrogenated polybutadiene), "FCA-061L" (hydrogenated polybutadiene backbone epoxy resin) manufactured by Nagase ChemteX Co., Ltd. etc. can be mentioned. Moreover, as a specific example of polybutadiene resin, it is butadiene resin containing a phenolic hydroxyl group; and polyimide resins having a polybutadiene structure, a urethane structure and an imide structure in the molecule. The polyimide resin is a linear polyimide resin (polyi described in Japanese Patent Laid-Open No. 2006-37083 and International Publication No. 2008/153208) using hydroxyl group-terminated polybutadiene, a diisocyanate compound, and tetrabasic acid anhydride as raw materials. mid). The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. The detail of the said polyimide resin can consider description of Unexamined-Japanese-Patent No. 2006-37083 and international publication 2008/153208, The said content is integrated in this specification.

(C) As an elastomer, resin containing a poly(meth)acrylate structure is mentioned, for example. A resin containing a poly(meth)acrylate structure may be referred to as a "poly(meth)acrylic resin". As a specific example of poly(meth)acrylic resin, Teisan Resin by Nagase ChemteX Co., Ltd.; "ME-2000", "W-116.3", "W-197C", "KG-25", "KG-3000" manufactured by Negami Kogyo; "ARUFON UH-2000" by Toagosei Co., Ltd. etc. are mentioned.

(C) As an elastomer, resin containing a polycarbonate structure is mentioned, for example. A resin containing a polycarbonate structure is sometimes referred to as "polycarbonate resin". Specific examples of the polycarbonate resin include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" manufactured by Kuraray, "C-2090", "C-3090" (polycarbonate diol), etc. are mentioned. Further, specific examples of the polycarbonate resin include polyimide resins having an imide structure, a urethane structure, and a polycarbonate structure in the molecule. The polyimide resin can be produced as a linear polyimide resin using a hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. The detail of the said polyimide resin can consider description of international publication 2016/129541, and the said content is integrated in this specification.

(C) As an elastomer, resin containing a polysiloxane structure is mentioned, for example. A resin containing a polysiloxane structure may be referred to as a "siloxane resin". Specific examples of the siloxane resin include "SMP-2006", "SMP-2003PGMEA" and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimide using amine-terminated polysiloxane and tetrabasic acid anhydride as raw materials (International Publication No. 2010 /053185, Japanese Unexamined Patent Publication No. 2002-12667 and Japanese Unexamined Patent Publication No. 2000-319386, etc.).

(C) As an elastomer, resin containing a polyalkylene structure or a polyalkyleneoxy structure is mentioned, for example. A resin containing a polyalkylene structure is sometimes referred to as "alkylene resin". In addition, a resin containing a polyalkyleneoxy structure may be referred to as "alkyleneoxy resin". The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure of 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure of 3 to 10 carbon atoms, and a polyalkylene having 5 to 6 carbon atoms. Oxy structures are particularly preferred. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Seni.

(C) As an elastomer, resin containing a polyisoprene structure is mentioned, for example. A resin containing a polyisoprene structure is sometimes referred to as "isoprene resin". As a specific example of isoprene resin, "KL-610" by the Kuraray company, "KL613", etc. are mentioned.

(C) As an elastomer, resin containing a polyisobutylene structure is mentioned, for example. A resin containing a polyisobutylene structure may be referred to as "isobutylene resin". Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. can

(C) As an elastomer, resin containing a polystyrene structure is mentioned, for example. A resin containing a polystyrene structure may be referred to as "polystyrene resin". The polystyrene resin may be a copolymer containing an arbitrary repeating unit different from the styrene unit in combination with a styrene unit, or may be a hydrogenated polystyrene resin. As the polystyrene resin, for example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene -propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, Hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-maleic anhydride copolymer, etc. are mentioned. Specific examples of the polystyrene resin include hydrogenated styrenic thermoplastic elastomers "H1041", "Taftek H1043", "Taftec P2000", and "Taftec MP10" (manufactured by Asahi Kasei Co., Ltd.); epoxidized styrene-butadiene thermoplastic elastomers "Epopland AT501" and "CT310" (manufactured by Daicel Corporation); hydroxyl group-modified styrenic elastomer "Septon HG252" (manufactured by Kuraray Co., Ltd.); "Taftec N503M", a modified styrenic elastomer having a carboxyl group, "Taftec N501", a modified styrenic elastomer having an amino group, and "Taftec M1913", a modified styrenic elastomer having an acid anhydride group (manufactured by Asahi Kasei Chemicals Co., Ltd.); unmodified styrene-based elastomer "Septon S8104" (manufactured by Kuraray); A styrene-ethylene/butylene-styrene block copolymer "FG1924" (made by Kraton) and "EF-40" (made by CRAY VALLEY) are mentioned.

Among the above, as the elastomer (C), a resin containing at least one structure selected from the group consisting of a polybutadiene structure, a polycarbonate structure and a poly(meth)acrylate structure in a molecule is more preferable. Further, (C) as the elastomer, a resin having a polybutadiene structure or a polycarbonate structure in the molecule is particularly preferable. The (C) elastomer having a polybutadiene structure or a polycarbonate structure generally has low compatibility with the (A-1) chelate type epoxy resin. Accordingly, the elastomer (C) can phase-separate from the (A-1) chelate type epoxy resin microscopically to form minute domains with excellent flexibility. In the cured product of the resin composition, since the modulus of elasticity of the cured product can be effectively lowered by exhibiting the flexibility of the domain, warpage can be particularly effectively suppressed without impairing adhesion.

(C) The elastomer may have a functional group capable of reacting with the (A) epoxy resin. (C) When the elastomer reacts with the (A) epoxy resin, the mechanical strength of the cured product of the resin composition can be increased. (A) The functional group that can react with the epoxy resin includes a functional group that appears by heating. (A) The functional group capable of reacting with the epoxy resin may be at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. Especially, as said functional group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group are preferable, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, and an epoxy group are more preferable, and a phenolic hydroxyl group is particularly preferred. It is preferable that the number average molecular weight (Mn) of (C) elastomer containing a functional group is 5,000 or more.

The amount of the (C) elastomer in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. It is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. (C) When the amount of the elastomer is within the above range, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered.

The amount of the (C) elastomer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on 100% by mass of the resin component of the resin composition. is 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less. (C) When the amount of the elastomer is within the above range, the effect of suppressing warpage and improving adhesion can be remarkably obtained, and usually, the minimum melt viscosity can be effectively lowered.

[5. (D) curing agent]

The resin composition according to the present embodiment may further contain (D) a curing agent as an optional component in combination with the components (A) to (C). The (D) curing agent as the component (D) does not include those corresponding to the components (A) to (C). (D) The curing agent may have a function of curing the resin composition by reacting with the (A) epoxy resin.

(D) As the curing agent, for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, a carbodiimide-based curing agent, thiol and the like, and among these, a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent are preferred, and a phenol-based curing agent and an active ester-based curing agent are particularly preferred. (D) Curing agent may be used individually by 1 type, and may be used in combination of 2 or more types.

As the phenol-based curing agent and the naphthol-based curing agent, those having a novolak structure are preferable from the viewpoints of heat resistance and water resistance. Further, from the viewpoint of adhesiveness, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, it is "MEH-7700" by a Maywa Kasei company, "MEH-7810", "MEH-7851", "MEH-8000H", for example; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V" manufactured by Nittetsu Chemical & Materials Co., Ltd. "SN-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P" manufactured by DIC, "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75" by Gunei Chemical Co., Ltd., etc. are mentioned.

As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., having two or more ester groups with high reaction activity in one molecule. compounds are preferred. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound, a phenol compound, and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolac, and phenol and active ester-based curing agents containing novolac benzoyl compounds. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H- 65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation) as active ester curing agents containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing a benzoyl compound of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. are mentioned as an active ester type curing agent which is a benzoylation compound of phenol novolac.

Examples of the amine-based curing agent include a curing agent having at least one amino group in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Especially, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylsulfone. , 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl ) Propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-amino) Phenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4 , 4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, etc. are mentioned. A commercially available products may be used as the amine curing agent, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kaya Hard A-A", "Kaya Hard A-B", and "Kaya Hard A-S" manufactured by Nippon Kayaku Co., Ltd. , "Epicure W" by Mitsubishi Chemical Corporation, etc. are mentioned.

Examples of the acid anhydride-based curing agent include a curing agent having at least one acid anhydride group in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromelli anhydride Triacic acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfotetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), and polymeric acid anhydrides such as styrene maleic acid resin obtained by copolymerization of styrene and maleic acid. As a commercial item of an acid anhydride type hardening|curing agent, "MH-700" by Shin Nippon Rika Co., Ltd. etc. are mentioned, for example.

As specific examples of the benzoxazine-based curing agent, "JBZ-OD100" (benzoxazine ring equivalent weight 218 g / eq.), "JBZ-OP100D" (benzoxazine ring equivalent weight 218 g / eq.), "ODA-BOZ" manufactured by JFE Chemical Co., Ltd. (benzoxazine ring equivalent 218g/eq.); "P-d" (benzoxazine ring equivalent 217g/eq.) and "F-a" (benzoxazine ring equivalent 217g/eq.) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" (benzoxazine ring equivalent 432 g/eq.) by Showa Kobunshi Co., Ltd., etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylencyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins, such as nate phenyl) thioether and bis (4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, and the like; and prepolymers in which these cyanate resins are partly triazinated. As specific examples of the cyanate ester curing agent, "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan Co., Ltd. ”, “BA230S75” (a prepolymer obtained by triazation of part or all of bisphenol A dicyanate to form a trimer), and the like.

Specific examples of the carbodiimide-based curing agent include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.) and V-05 (carbodiimide group equivalent: 262 g/eq.) manufactured by Nisshinbo Chemical Co., Ltd. eq.), V-07 (carbodiimide group equivalent: 200 g/eq.); V-09 (carbodiimide group equivalent: 200 g/eq.); and Stabacuzol (registered trademark) P (carbodiimide group equivalent: 302 g/eq.) manufactured by Rhein Chemie.

Specific examples of the thiol-based curing agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. .

(D) The active group equivalent of the curing agent 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 active group equivalent is the mass of the curing agent per 1 equivalent of the active group.

(A) When the number of epoxy groups of the epoxy resin is 1, (D) the number of active groups of the curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 5.0 or less, More preferably, it is 2.0 or less, and particularly preferably 1.0 or less. "The number of epoxy groups of (A) epoxy resin" represents the sum of all values obtained by dividing the mass of non-volatile components of the (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of (D) curing agent" represents a value obtained by dividing the mass of non-volatile components of the (D) curing agent present in the resin composition by the active group equivalent.

The amount of the curing agent (D) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 4% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. It is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

The amount of the curing agent (D) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, based on 100% by mass of the resin component of the resin composition. is 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[6. (E) curing accelerator]

The resin composition according to the present embodiment may further contain (E) a curing accelerator as an optional component in combination with the above components (A) to (D). The (E) hardening accelerator as the component (E) does not include those corresponding to the components (A) to (D). (E) The curing accelerator has a function as a curing catalyst that promotes curing of the (A) epoxy resin.

(E) Examples of the curing accelerator include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, and amine curing accelerators. Among them, an imidazole-based curing accelerator is preferable. (E) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyro Mellitate, 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 tetraphenylborate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methylphenylborate) Aromatic phosphonium salts, such as oxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyl triphenylphosphonium 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 the urea-based curing accelerator include 1,1-dimethylurea; Aliphatic dimethyl urea, such as 1,1,3-trimethyl urea, 3-ethyl-1,1-dimethyl urea, 3-cyclohexyl-1,1-dimethyl urea, and 3-cyclooctyl-1,1-dimethyl urea; 3-phenyl-1,1-dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 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 dimethylurea such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea].

Examples of the guanidine-based curing accelerator 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 , 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Examples of the imidazole-based curing accelerator 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 Imidazole, 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-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(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-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzimidazolium chloride, 2-methylimidazolin, imidazole compounds such as 2-phenylimidazolin, imidazole compounds and epoxy resins The adduct form of Examples of commercially available imidazole curing accelerators include "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”, “Cl1Z-A”; "P200-H50" by the Mitsubishi Chemical Corporation etc. are mentioned.

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

Examples of the amine curing accelerator 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. are mentioned. As an amine-type hardening accelerator, you may use a commercial item, for example, "MY-25" by Ajinomoto Fine Techno Co., Ltd. etc. are mentioned.

The amount of the (E) curing accelerator in the resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more, based on 100% by mass of the non-volatile component of the resin composition, It is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.

The amount of the curing accelerator (E) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, based on 100% by mass of the resin component of the resin composition. It is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.

[7. (F) optional additives]

The resin composition according to the present embodiment may further contain (F) optional additives as optional non-volatile components in combination with the components (A) to (E). (F) Examples of optional additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; 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 antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet 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; Flame retardants such as phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (eg, melamine sulfate), halogen-based flame retardants, inorganic flame retardants (eg, antimony trioxide) ; dispersants such as phosphoric acid ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and 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. (F) Arbitrary additives may be used individually by 1 type, and may be used in combination of 2 or more type.

[8. (G) Solvent]

The resin composition according to the present embodiment may further contain (G) a solvent as an optional volatile component in combination with the non-volatile components such as the components (A) to (F). (G) As a solvent, an organic solvent is usually used. Examples of the organic solvent include ketone 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 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 solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon solvents, such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, etc. are mentioned. (G) A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

(G) The amount of the solvent is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, It can be 15 mass % or less, 10 mass % or less, etc., and 0 mass % may be sufficient.

[9. Manufacturing method of resin composition]

The resin composition according to the present embodiment can be produced by mixing the above components, for example. Some or all of the above components may be mixed simultaneously or sequentially. In the process of mixing each component, the temperature may be set appropriately, so you may heat and/or cool temporarily or continuously. In addition, in the process of mixing each component, you may perform stirring or shaking.

[10. Characteristics of resin composition and cured product thereof]

According to the resin composition according to the present embodiment, a cured product capable of suppressing warpage can be obtained. Therefore, when a layered product is obtained by forming a layer of a cured product of a resin composition (hereinafter sometimes referred to as a "cured product layer") on a substrate such as a silicon wafer, the amount of warpage of the layered product can be reduced. For example, when a laminate is manufactured by the method described in the [Evaluation of warpage] section of the examples described later and the warpage amount thereof is measured, the warpage amount can be 1.5 mm or less.

According to the resin composition according to the present embodiment, a cured product having excellent adhesion to the conductor layer can be obtained. Therefore, when the cured product layer of the resin composition is formed so as to contact the conductor layer, peeling of the conductor layer and the cured product layer can be suppressed. For example, when the copper foil adhesion strength is measured by the method described in the [Evaluation of Copper Foil Adhesion Strength] section of Examples described later, it is preferably 0.53 kgf/cm or more, more preferably 0.57 kgf/cm or more, particularly Preferably, copper foil adhesion strength of 0.60 kgf/cm or more can be obtained.

According to the resin composition according to the present embodiment, a cured product having excellent adhesion to silicone can usually be obtained. Therefore, when the cured product layer of the resin composition is formed so as to come into contact with a member formed of silicone, separation between the member and the cured product layer can be suppressed. For example, when the Si adhesion strength is measured by the method described in the [Evaluation of Si adhesion strength] section of the examples described later, it is preferably 550 kgf/cm 2 or more, more preferably 570 kgf/cm 2 or more, particularly preferably can obtain Si adhesion strength of 590 kgf/cm 2 or more.

According to the resin composition according to the present embodiment, a cured product having a small elastic modulus can usually be obtained. This inventor considers that the hardened|cured material has such a small modulus of elasticity as one of the reasons why the excellent adhesiveness and the effect of suppressing warpage are obtained as described above. For example, when the tensile modulus of elasticity of a cured product of a resin composition is measured by the method described in the [Measurement of Elastic Modulus] section of Examples described later, it is preferably 16 GPa or less, more preferably 15 GPa or less, and particularly preferably 14.5 A tensile modulus of elasticity of GPa or less can be obtained. The lower limit is not particularly limited, but may be, for example, 5 GPa or more.

According to the resin composition according to the present embodiment, it can usually have a low minimum melt viscosity. Therefore, when sealing with a resin composition, formation of the gap|interval which is not filled with a resin composition can be suppressed. For example, when the minimum melt viscosity of the resin composition is measured by the method described in the [Measurement of Melt Viscosity] section of Examples below, it is preferably 9,000 poise or less, more preferably 8,000 poise or less, particularly preferably Preferably, the lowest melt viscosity of 7,500 poise or less can be obtained. The lower limit is not particularly limited, but may be preferably 500 poise or more, more preferably 1,000 poise or more, and particularly preferably 2,000 poise or more.

Since the resin composition has the above characteristics, it can be suitably used as a resin composition for a sealing layer, and in particular, a resin composition for sealing a semiconductor (resin composition for semiconductor sealing), preferably a resin composition for sealing a semiconductor chip ( It can be suitably used as a resin composition for sealing semiconductor chips). In addition, you may use a resin composition as a resin composition for insulation layers other than a sealing use. For example, the resin composition is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board). It can be suitably used as (resin composition for insulating layers of circuit boards).

As the semiconductor chip package, for example, FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package) , a fan-in type PLP.

In addition, the resin composition may be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

In addition, the resin composition can be used for a wide range of applications in which the resin composition is used, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, die bonding materials, hole filling resins, and parts embedding resins.

[11. resin sheet]

A resin sheet according to an embodiment of the present invention has a support and a resin composition layer formed on the support. Since the resin composition layer is a layer formed of a resin composition, it usually contains the resin composition, and preferably contains only the resin composition.

The thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, still more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less, from the viewpoint of thinning. am. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more.

Examples of the support include a film made of plastic material, metal foil, and release paper, and a film made of plastic material and metal foil are preferable.

When using a film made of a plastic material as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN") with) polyesters such as; polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefin; triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; Polyimide etc. are mentioned. Especially, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using metal foil as a support body, as a metal foil, copper foil, aluminum foil, etc. are mentioned, for example. Especially, copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) good night.

The surface of the support to be bonded to the resin composition layer may be subjected to a treatment such as a mat treatment, a corona treatment, or an antistatic treatment.

Moreover, as a support body, you may use the support body with a release layer which has a release layer on the surface to which it joins with a resin composition layer. As a release agent used for the release layer of the support body with a release layer, 1 or more types of release agents selected from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. As a commercial item of a release agent, "SK-1" by a Lintec company, "AL-5", "AL-7" etc. which are alkyd resin type release agents are mentioned, for example. In addition, as a support body with a mold release layer, it is "Lumira T60" by a Toray company, for example; "Purex" by Teijin; "Uni-Peel" manufactured by Unitica Co., Ltd., and the like are exemplified.

The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. On the other hand, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

A resin sheet can be manufactured, for example by applying a resin composition onto a support using a coating device such as a die coater. Further, if necessary, a resin composition may be dissolved in a solvent to prepare a resin varnish, and the resin varnish may be applied to prepare a resin sheet. By using a solvent, the viscosity can be adjusted and applicability can be improved. When a resin varnish is used, usually, after application, the resin varnish is dried to form a resin composition layer.

As a solvent, what was described as the solvent which a resin composition can contain can be used, for example. A solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

You may perform drying by a well-known method, such as heating and hot air spray. Drying conditions are made to dry so that content of the solvent in a resin composition layer may be 10 mass % or less normally, Preferably it is 5 mass % or less. Although different depending on the boiling point of the solvent, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, drying at 50°C to 150°C for 3 minutes to 10 minutes can form a resin composition layer. can

The resin sheet may contain arbitrary layers other than a support body and a resin composition layer as needed. For example, in the resin sheet, a protective film conforming to the support may be provided on the surface of the resin composition layer not bonded to the support (ie, the surface on the opposite side to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. With the protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be prevented. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, it is possible to wind up and preserve|save a resin sheet in roll shape.

A resin sheet can be suitably used for sealing semiconductor chips (resin sheet for sealing semiconductor chips). Examples of applicable semiconductor chip packages include fan-out type WLP, fan-in type WLP, fan-out type PLP, and fan-in type PLP. In addition, a resin sheet can be used to seal a circuit board (resin sheet for sealing of a circuit board), for example.

In addition, a resin sheet can be suitably used in order to form an insulating layer in manufacture of a semiconductor chip package (resin sheet for insulation of a semiconductor chip package). For example, a resin sheet can be used to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board). As an example of a package using such a board|substrate, an FC-CSP, MIS-BGA package, and ETS-BGA package are mentioned.

Moreover, you may use a resin sheet as the material of the MUF used after connecting a semiconductor chip to a board|substrate.

In addition, the resin sheet can be used for a wide range of other applications requiring high insulation reliability. For example, a resin sheet can be suitably used in order to form the insulating layer of circuit boards, such as a printed wiring board.

[12. circuit board]

A circuit board according to an embodiment of the present invention includes a cured product of a resin composition. Usually, the circuit board includes a cured product layer formed of a cured product of a resin composition. Such a cured product layer can usually function as an insulating layer or a sealing layer, and it is preferable to function as a sealing layer. The circuit board can be manufactured by, for example, a manufacturing method including the following steps (1) and (2).

(1) A step of forming a resin composition layer on a substrate.

(2) A step of curing the resin composition layer to form a cured product layer.

In step (1), a substrate is prepared. Examples of the base material include substrates such as glass epoxy substrates, metal substrates (stainless steel, cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. there is. In addition, 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 the base material which has the 1st metal layer and the 2nd metal layer which can be peeled on both surfaces. In the case of using such a base material, usually, a conductor layer as a wiring layer capable of functioning as circuit wiring is formed on the surface 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, material of a conductor layer described later, and the like, and copper foil is preferable. As a base material which has a metal layer, ultra-thin copper foil "Micro Thin" with carrier copper foil by Mitsui Kinzoku Kogyo Co., Ltd. is mentioned, for example.

In addition, a conductor layer may be formed on one or both surfaces of the base material. 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". As the conductor material contained in the conductor layer, 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 are exemplified. As the conductor material, a single metal may be used or an alloy may be used. Examples of the alloy include alloys of two or more types of metals selected from the above groups (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and alloys of nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys as alloys are preferred. Among them, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and a nickel-chromium alloy are more preferred, and a simple metal of copper is particularly preferred.

The conductor layer may be subjected to pattern processing in order to function as a wiring layer, for example. At this time, the line (circuit width)/space (inter-circuit width) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10. μm or less, more preferably 5/5 μm or less, still more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch may be uniform or non-uniform over the entire 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, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 30 μm. It is 20 μm.

After preparing the substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, it is preferable to form the resin composition layer so that the conductor layer is embedded in the resin composition layer.

Formation of the resin composition layer is performed, for example, by laminating a resin sheet and a base material. Such lamination can be performed by, for example, bonding the resin composition layer to the substrate by heat-pressing the resin sheet to the substrate from the support side. As a member for heat-pressing a resin sheet to a substrate (hereinafter sometimes referred to as a "heat-compression member"), a heated metal plate (such as a SUS head plate) or a metal roll (such as a SUS roll) is exemplified. . On the other hand, it is preferable not to directly press the hot-compression member to the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the irregularities on the surface of the base material.

Lamination of the base material and the resin sheet may be performed by, for example, a vacuum lamination method. Lamination conditions may be as follows, for example. The heat compression temperature is preferably in the range of 60°C to 160°C, and more preferably in the range of 80°C to 140°C. The heat compression pressure is preferably in the range of 0.098 MPa to 1.77 MPa, and more preferably in the range of 0.29 MPa to 1.47 MPa. The heat pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions at a pressure of 13 hPa or less.

After lamination, the laminated resin sheets may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the hot-compression bonding member from the support body side. The press conditions for the smoothing treatment can be the same conditions as the thermal compression conditions for the above laminate. In addition, you may perform lamination|stacking and a smoothing process continuously using a vacuum laminator.

After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form a cured product layer. Although the thermal curing conditions of the resin composition layer may vary depending on the type of resin composition, the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170°C to 240°C). 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

Before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment by heating at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer is usually at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). You may preheat normally for 5 minutes or more (preferably from 5 minutes to 150 minutes, more preferably from 15 minutes to 120 minutes).

As described above, a circuit board having a cured product layer formed of a cured product of the resin composition can be manufactured. Moreover, the manufacturing method of a circuit board may further include arbitrary steps.

For example, when manufacturing a circuit board using a resin sheet, the manufacturing method of a circuit board may include the process of peeling the support body of a resin sheet. The support may be peeled off before thermal curing of the resin composition layer or after thermal curing of the resin composition layer.

The manufacturing method of the circuit board may include, for example, a step of polishing the surface of the cured product layer after forming the cured product layer. The polishing method is not particularly limited. Examples of the polishing method include a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as buffing, a surface grinding method by rotating a grindstone, and the like.

The method for manufacturing a circuit board may include, for example, step (3) of interlayer connection of conductor layers. As a method of interlayer connection, a method of perforating the cured product layer is exemplified. By punching, holes such as via holes and through holes can be formed in the cured product layer. Examples of the via hole formation method include laser irradiation, etching, mechanical drilling, and the like. The size and shape of the via hole may be appropriately determined according to the design of the circuit board. On the other hand, in step (3), interlayer connection may be performed by polishing or grinding the cured product layer.

After forming the via hole, it is preferable to perform a step of removing smear in the via hole. The said process is sometimes called a desmear process. For example, when the formation of the conductor layer over the cured product layer is performed by a plating process, a wet desmear treatment may be performed on the via hole. In addition, when forming the conductor layer on the cured product layer by a sputtering process, you may perform a dry desmear process such as a plasma treatment process. Moreover, a roughening process may be given to the hardened|cured material layer by the desmear process.

In addition, you may perform a roughening process with respect to the hardened|cured material layer before forming a conductor layer on a hardened|cured material layer. According to this roughening treatment, the surface of the cured material layer including the inside of the via hole is usually roughened. As a roughening process, you may perform any roughening process of a dry process and a wet process. Plasma treatment etc. are mentioned as an example of a dry roughening process. Moreover, as an example of a wet conditioning process, the method of performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralization liquid in this order is mentioned.

After forming the via hole, you may form a conductor layer on the cured material layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material conduct, and interlayer connection is performed. As for the formation method of a conductor layer, a plating method, sputtering method, vapor deposition method etc. are mentioned, for example. For example, a conductor layer having a desired wiring pattern may be formed by plating the surface of the cured product layer by an appropriate method such as a semi-additive method or a full additive method. Further, for example, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern may be formed by a subtractive method. The material of the conductor layer formed may be a simple metal or an alloy. In addition, such a conductor layer may have a single-layer structure, or may have a multi-layer structure containing two or more layers of different types of materials.

Here, an example of an embodiment in which a conductor layer is formed on the cured product layer will be described in detail. A plating seed layer is formed on the surface of the cured product layer by electroless plating. Then, on the formed plating seed layer, a mask pattern exposing a part of the plating seed layer is formed corresponding to a desired wiring pattern. After forming an electrolytic plating layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by processing such as etching to form a conductor layer having a desired wiring pattern.

The manufacturing method of a circuit board may include the process (4) of removing a base material. By removing the substrate, a circuit board having a cured product layer and a conductor layer embedded in the cured product layer can be obtained. The said process (4) can be performed, for example, when using the base material which has a peelable metal layer.

[13. semiconductor chip package]

A semiconductor chip package according to an embodiment of the present invention includes a cured product of a resin composition. As such a semiconductor chip package, the following are mentioned, for example.

A semiconductor chip package according to the first example includes the circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

As the bonding condition between the circuit board and the semiconductor chip, any condition under which terminal electrodes of the semiconductor chip and circuit wiring of the circuit board can be connected by conductor can be adopted. For example, conditions used in flip chip mounting of semiconductor chips can be employed. Further, for example, you may bond between a semiconductor chip and a circuit board through an insulating adhesive agent.

As an example of the bonding method, a method of press-bonding a semiconductor chip to a circuit board is exemplified. As compression conditions, the compression 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 compression time is usually 1 second to 60 seconds. range (preferably in the range of 5 seconds to 30 seconds).

As another example of the bonding method, a method of reflowing and bonding a semiconductor chip to a circuit board is exemplified. 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 the mold underfill material, it is preferable to use the resin composition according to the above embodiment.

A semiconductor chip package according to the second example includes a semiconductor chip and a cured product of a resin composition for sealing the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second example include a fan-out type WLP and a fan-out type PLP.

1 is a cross-sectional view schematically showing a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention. A semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110 as shown in FIG. 1; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a redistribution formation layer 130 as an insulating layer provided on the surface of the semiconductor chip 110 opposite to the sealing layer 120; a redistribution layer 140 as a conductor layer; A solder resist layer 150 and bumps 160 are provided.

The manufacturing method of such a semiconductor chip package,

(A) a step of laminating a temporarily fixed film on a substrate;

(B) a process of temporarily fixing a semiconductor chip on a temporarily fixing film;

(C) a step of forming a sealing layer on the semiconductor chip;

(D) a step of peeling the substrate and temporarily fixed film from the semiconductor chip;

(E) a step of forming a redistribution layer on the surface of the semiconductor chip from which the base material and temporarily fixed film are peeled off;

(F) a step of forming a redistribution layer as a conductor layer on the redistribution forming layer; and

(G) a step of forming a solder resist layer on the redistribution layer.

In addition, the manufacturing method of the semiconductor chip package,

(H) You may include a process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them.

(Process (A))

Step (A) is a step of laminating a temporarily fixed film on a base material. The lamination conditions of the substrate and the temporarily fixed film may be the same as the lamination conditions of the substrate and the resin sheet in the manufacturing method of the circuit board.

As a base material, it is a silicon wafer, for example; glass wafer; glass substrate; Metal substrates, such as copper, titanium, stainless steel, and a cold-rolled steel plate (SPCC); substrates, such as FR-4 substrates, in which glass fibers are impregnated with an epoxy resin or the like and subjected to a thermal curing treatment; and substrates made of bismaleimide triazine resins such as BT resin.

Temporarily fixing film can use any material that can be separated from the semiconductor chip and can also temporarily fix the semiconductor chip. As a commercial item, the Nitto Denko Corporation "Reva Alpha" etc. are mentioned.

(Process (B))

A process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixing film. Temporary fixation of the semiconductor chip can be performed using an apparatus such as a flip chip bonder or a die bonder, for example. The layout and number of batches of semiconductor chips can be appropriately set according to the shape, size, and number of production targets of semiconductor chip packages of the temporarily fixed film. For example, semiconductor chips may be aligned and temporarily fixed in a matrix of multiple rows and multiple columns.

(Process (C))

Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer can be formed of a cured product of the resin composition according to the above embodiment. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a cured product layer as the sealing layer. The formation of the resin composition layer on the semiconductor chip can be performed in the same manner as the method for forming the resin composition layer on the substrate described in the above circuit board manufacturing method, except that, for example, a semiconductor chip is used instead of the substrate. .

After the resin composition layer is formed on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thereby, sealing of the semiconductor chip by the hardened|cured material of a resin composition is performed. The conditions for thermal curing of the resin composition layer may be the same conditions as those for thermal curing of the resin composition layer in the manufacturing method of the circuit board. Further, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment by heating at a temperature lower than the curing temperature. As the treatment conditions for the preheating treatment, the same conditions as those for the preheating treatment in the circuit board manufacturing method may be used.

(Process (D))

Step (D) is a step of peeling the substrate and temporarily fixed film from the semiconductor chip. Peeling method, it is preferable to use an appropriate method according to the material of the temporarily fixed film. As a peeling method, the method of peeling by heating, foaming, or expanding a temporarily fixed film is mentioned, for example. Further, as a peeling method, for example, a method of irradiating ultraviolet rays to a temporarily fixed film through a base material to reduce the adhesive strength of the temporarily fixed film and peeling is mentioned.

In the method of peeling the temporarily fixed film by heating, foaming or expanding, the heating conditions are usually 100 ° C to 250 ° C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling by irradiating ultraviolet rays to reduce the adhesive strength of the temporarily fixed film, the irradiation amount of ultraviolet rays is usually, 10mJ / cm 2 to 1,000mJ / cm 2 .

When peeling the substrate and temporarily fixed film from the semiconductor chip as described above, the surface of the sealing layer is exposed. The manufacturing method of a semiconductor chip package may include polishing the surface of the said exposed sealing layer. Polishing can improve the smoothness of the surface of the sealing layer. As the polishing method, the same method as described in the circuit board manufacturing method can be used.

(Process (E))

Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and temporarily fixed film are peeled off. Usually, such a rewiring forming layer is formed on the semiconductor chip and the sealing layer. The rewiring forming layer can be formed of, for example, a photosensitive resin composition or a thermosetting resin composition. In addition, after forming the redistribution layer, via holes are usually formed in the redistribution layer in order to interlayer connect the semiconductor chip and the redistribution layer.

(Process (F))

Step (F) is a step of forming a redistribution layer as a conductor layer on the rewiring formation layer. A method of forming the redistribution layer on the redistribution forming layer may be the same as the method of forming the conductor layer over the cured product layer in the circuit board manufacturing method. Alternatively, steps (E) and (F) may be repeatedly performed to alternately stack the rewiring layer and the rewiring formation layer (build-up).

(Process (G))

Step (G) is a step of forming a solder resist layer on the redistribution layer. Any material having insulating properties can be used as the material of the solder resist layer. Especially, from a viewpoint of the ease of manufacture of a semiconductor chip package, a photosensitive resin composition and a thermosetting resin composition are preferable.

In step (G), a bumping process for forming bumps may be performed as needed. The bumping process can be performed by a method such as solder ball or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in Step (E).

(Process (H))

The method for manufacturing a semiconductor chip package may include a step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them. A method of dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

As a semiconductor chip package according to the third example, in the semiconductor chip package 100 shown as an example in FIG. Semiconductor chip packages formed by

[14. semiconductor device]

A semiconductor device according to an embodiment of the present invention includes the circuit board or semiconductor chip package. As the semiconductor device, for example, electric appliances (eg, computers, mobile phones, smart phones, tablet-type devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (eg, motorcycles, automobiles) , trains, ships, aircraft, etc.) and the like.

[Example]

Hereinafter, the present invention will be described in detail by showing examples. However, this invention is not limited to the Example shown below. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, temperature conditions and pressure conditions in the case where there is no designation in particular were room temperature (25 degreeC) and atmospheric pressure (1 atm).

[Description of Inorganic Fillers]

The inorganic filler used in the following Examples and Comparative Examples is as follows.

Inorganic filler 1: Spherical silica particles (average particle diameter: 1 μm, specific surface area: 4.5 m 2 /g) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.).

Inorganic filler 2: Spherical alumina particles (average particle diameter: 1.5 μm, specific surface area: 1.6 m 2 /g) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.).

[Production Example 1. Preparation of Elastomer 1]

In the reaction vessel, bifunctional hydroxyl group terminal polybutadiene (number average molecular weight = 5,047 (GPC method), hydroxyl group equivalent = 1,800 g / eq., solid content 100 mass%, Nippon Soda Co., Ltd. "G-3000") 69 g, 40 g of an aromatic hydrocarbon-based mixed solvent (“Ipsol 150” manufactured by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 8 g of isophorone diisocyanate (made by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq) was added while further stirring, and the reaction was performed for about 3 hours. Then, after cooling the reaction product to room temperature, 23 g of cresol novolak resin ("KA-1160" manufactured by DIC, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyldiglycol acetate (produced by Daicel) are added thereto. was added, the temperature was raised to 80°C while stirring, and the reaction was performed for about 4 hours. Disappearance of the NCO peak at 2,250 cm ⁻¹ was confirmed from FT-IR. The disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain Elastomer 1 having a polybutadiene structure and phenolic hydroxyl groups (50% by mass of non-volatile content). The number average molecular weight was 5,500.

[Production Example 2. Production of Elastomer 2]

In the reaction vessel, bifunctional hydroxyl group terminal polybutadiene (number average molecular weight = 5,047 (GPC method), hydroxyl group equivalent = 1,800 g / eq., 100 mass% of solid content: Nippon Soda Co., Ltd. "G-3000") 50 g, 23.5 g of an aromatic hydrocarbon-based mixed solvent (“Ipsol 150” by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added while further stirring, and the mixture was reacted for about 3 hours. Then, after cooling the reactant to room temperature, 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyldiglycol acetate (Dicell Co., Ltd.) Production) 40.4g was added, and the temperature was raised to 130°C while stirring, and the reaction was performed for about 4 hours. Disappearance of the NCO peak at 2,250 cm ⁻¹ was confirmed from FT-IR. After confirming the disappearance of the NCO peak, it was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered with a 100 mesh filter cloth to obtain an elastomer 2 having an imide structure, a urethane structure, and a polybutadiene structure (50% by mass of non-volatile matter) got The number average molecular weight was 13,700.

[Production Example 3. Preparation of Elastomer 3]

In a reaction vessel, 80 g of polycarbonate diol (number average molecular weight: about 1,000, hydroxyl equivalent: 500 g/eq., non-volatile content: 100%, "C-1015N" manufactured by Kuraray) and 0.01 g of dibutyltin dilaurate were mixed, It was uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate (“Ethyl Diglycol Acetate” by Daicel Co., Ltd.). Then, the temperature of the mixture was raised to 50°C, and 27.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08) was added while further stirring, followed by reaction for about 3 hours. After cooling the reaction product to room temperature, 14.3 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g/eq.), 0.12 g of triethylenediamine and diethylene glycol monoethyl ether acetate (manufactured by Daicel Co., Ltd. "Ethyl 84.0 g of "diglycol acetate") was added, the temperature was raised to 130°C while stirring, and the reaction was conducted for about 4 hours. Disappearance of the NCO peak at 2,250 cm ⁻¹ was confirmed from FT-IR. The disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered with a 100 mesh filter cloth to obtain Elastomer 3 (50% by mass of non-volatile matter) having an imide structure, a urethane structure and a polycarbonate structure. Got it. The number average molecular weight was 8,500.

[Example 1]

Liquid chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent 240 g/eq., chelate modified amount (phosphoric acid modified amount) 1.0% by mass) 2 parts, liquid epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. Production "ZX1059", 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq.) 4 parts and bixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation) , Epoxy equivalent 185 g/eq.) 3 parts were heated and dissolved in 10 parts of MEK while stirring. After cooling to room temperature, 16 parts of elastomer 1 (50% by mass of non-volatile matter), a phenolic curing agent having a triazine skeleton and a novolac structure (“LA-3018-50P” manufactured by DIC Corporation, active group equivalent of about 151 g/eq. , 2-methoxypropanol solution with a solid content of 50%) 10 parts, imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 5% by mass) 1 part and inorganic filler 1 were mixed with 75 parts and 10 parts of MEK, dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin varnish.

[Example 2]

The amount of chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was changed to 1.5 parts, and the amount of elastomer 1 (50% by mass of non-volatile content) was changed to 18 parts. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 3]

The amount of chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was changed to 0.7 part, and the amount of elastomer 1 (50% by mass of non-volatile content) was changed to 19 parts. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 4]

The amount of chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent of 240 g/eq.) was changed to 3 parts, and the amount of elastomer 1 (50% by mass of non-volatile content) was changed to 14 parts. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 5]

The amount of chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was changed to 4 parts, and the amount of elastomer 1 (50% by mass of non-volatile content) was changed to 12 parts. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 6]

A chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent 240 g/eq.) is mixed with a liquid chelate modified epoxy resin (“EP-49-10P2” manufactured by ADEKA, epoxy equivalent 300 g/eq., The amount of chelate modification (amount of phosphoric acid modification) was changed to 1.5% by mass). A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 7]

A chelate type epoxy resin ("EP-49-10P" manufactured by ADEKA, epoxy equivalent 240 g/eq.) was converted into a liquid chelate type epoxy resin ("EP-49-23" manufactured by ADEKA, epoxy equivalent 175 g/eq.) changed. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Example 8]

A resin varnish was prepared in the same manner as in Example 1, except that 75 parts of inorganic filler 2 was used instead of 75 parts of inorganic filler 1.

[Example 9]

A resin varnish was prepared in the same manner as in Example 1 except that 16 parts of Elastomer 2 (50% by mass of nonvolatile matter) were used instead of 16 parts of Elastomer 1 (50% by mass of nonvolatile matter).

[Example 10]

A resin varnish was prepared in the same manner as in Example 1 except that 16 parts of Elastomer 3 (50% by mass of nonvolatile matter) was used instead of 16 parts of Elastomer 1 (50% by mass of nonvolatile matter).

[Example 11]

Resin varnish was prepared in the same manner as in Example 1 except that 8 parts of hydroxyl-containing acrylic polymer ("ARUFON UH-2000" manufactured by Toagosei Co., Ltd., weight average molecular weight: 11,000) was used instead of 16 parts of elastomer 1 (50% by mass of non-volatile matter). manufactured.

[Example 12]

In place of 10 parts of a phenolic curing agent ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) having a triazine skeleton and a novolac structure, phenol furnace A resin varnish was prepared in the same manner as in Example 1 except that 7.5 parts of rockfish resin ("TD-2090-60M" manufactured by DIC, hydroxyl equivalent of about 105 g/eq., MEK solution with a solid content of 60%) was used.

[Example 13]

A phenolic curing agent having a triazine skeleton and a novolac structure ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) instead of 10 parts, naphthalene-based A resin varnish was prepared in the same manner as in Example 1, except that 10 parts of phenol resin ("SN485" manufactured by Nittetsu Chemical & Material Co., Ltd., MEK solution having a hydroxyl equivalent of 215 g/eq. and a solid content of 60% by mass) was used.

[Example 14]

A phenolic curing agent having a triazine skeleton and a novolac structure ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) instead of 10 parts, active ester A resin varnish was prepared in the same manner as in Example 1 except that 10 parts of the compound ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 g/eq., toluene solution with a solid content of 65 mass%) was used.

[Comparative Example 1]

A resin varnish was prepared in the same manner as in Example 1 except that the chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was not used.

[Comparative Example 2]

A chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was not used. Further, the amount of the liquid epoxy resin (“ZX1059” manufactured by Nippon Steel Sumikin Chemicals, Inc., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq.) is 6 changed to part. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Comparative Example 3]

A chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent: 240 g/eq.) was not used. In addition, the amount of inorganic filler 1 was changed to 82 parts. In addition, the amount of a phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, active group equivalent of about 151 g / eq., 2-methoxypropanol solution with a solid content of 50%) having a triazine skeleton and a novolac structure is 18 parts changed. A resin varnish was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 4]

A chelate type epoxy resin (“EP-49-10P” manufactured by ADEKA, epoxy equivalent 240 g/eq.) was not used. Further, the amount of liquid epoxy resin ("ZX1059" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq.) was 6 changed to part. Further, 0.3 part of a triazine functional group-containing silane coupling agent ("VD-5", 2,4-diamino-6-triethoxysilane triazine, manufactured by Shikoku Kasei Co., Ltd.) was added to the resin varnish as an adhesive imparting agent. A resin varnish was prepared in the same manner as in Example 1 except for the above.

[Preparation of Resin Sheet]

As a support, a polyethylene terephthalate film ("Lumira R80" manufactured by Toray Corporation, thickness: 38 µm, softening point: 130°C) subjected to release treatment with an alkyd resin release agent ("AL-5" manufactured by Lintec) was prepared. On the support, the resin varnish prepared in Examples and Comparative Examples was applied with a die coater so that the thickness of the resin composition layer after drying was 50 μm, and dried at 85 ° C. to 100 ° C. for 4 minutes to obtain a resin sheet.

[Evaluation of Copper Foil Adhesion Strength]

<Substrate Treatment of Copper Clad Laminate>

A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate thickness of 0.8 mm, manufactured by Panasonic Corporation “R-1766”) having copper foil on the surface was prepared. Using a microetching agent (“CZ8101” manufactured by Mack Corporation), it was etched so that the amount of copper etching was 2 μm, and both surfaces were roughened. A copper clad laminated board obtained in this way may be referred to as a "roughened copper clad laminated board".

<Laminating of Resin Sheets>

The resin sheets produced in Examples and Comparative Examples are bonded to the roughened copper-clad laminate using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials), so that the resin composition layer is bonded to the roughened copper-clad laminate. Laminated on one side. The lamination was performed by reducing the pressure for 30 seconds to set the air pressure to 13 hPa or less, and then compressing the layer at 100°C and a pressure of 0.74 MPa for 30 seconds.

<Treatment of copper foil base>

Copper foil (electrolytic copper foil “3EC-III” manufactured by Mitsui Kinzokukozan Co., Ltd., thickness 35 μm) is immersed in a microetching agent (“Mac Etchbond CZ-8100” manufactured by Mack Corporation), and the glossy surface of the copper foil is roughened ( 1 μm etching) was performed.

<Copper foil lamination and curing>

The support of the resin sheet laminated on the roughened copper clad laminate was peeled off to expose the resin composition layer. A resin composition layer and copper foil were laminated to the resin composition layer so that the roughened glossy surface was bonded to the resin composition layer. The lamination was performed by reducing the pressure for 30 seconds to set the air pressure to 13 hPa or less, and then compressing the layer at 100°C and a pressure of 0.74 MPa for 30 seconds. Then, it was hot-pressed for 60 seconds under atmospheric pressure at 100°C and a pressure of 0.5 MPa to smooth the resin composition layer. Further, by curing the resin composition under curing conditions of 100°C, 30 minutes, and then 190°C, 90 minutes, a sample having a layer structure of "cured product layer/copper foil of roughened copper-clad laminate/resin composition" was obtained.

<Measurement and evaluation of peel strength (peel strength) of copper foil>

A sheath was placed in the copper foil to enclose a portion having a width of 10 mm and a length of 100 mm. The load (kgf/cm) when peeling off one end of this part and holding it with a clamp (Autocomb type tester "AC-50C-SL" manufactured by TSE) and peeling 20 mm in the vertical direction at a speed of 50 mm/min at room temperature ) was measured, and the peel strength as copper foil adhesion strength was obtained.

[Evaluation of Si adhesion strength]

<Laminate to Silicon Wafer and Curing>

The resin sheets produced in Examples and Comparative Examples were bonded to a 12-inch silicon wafer ( 775 μm thick) was laminated on one side. The lamination was carried out by reducing the pressure for 30 seconds to reduce the air pressure to 13 hPa or less, and then compressing at 100°C and a pressure of 0.74 MPa for 30 seconds. After lamination, the support of the resin sheet was peeled off. The resin composition was cured under curing conditions of 100° C. for 30 minutes, followed by 190° C. for 90 minutes to obtain a laminate having a layer configuration of “silicone wafer/cured product layer of resin composition”.

<Production of test piece>

The resulting laminate was cut into 1 cm squares and placed on a ceramic backing plate (11.4 cm square, P/N901450) with an epoxy adhesive so that the cured product layer faces upward. Further, on the cured product layer, stud pins (tack-shaped jig; adhesive surface diameter 2.7 mm; P/N 901106) were fixed with an epoxy adhesive, and heated at 150° C. for 1 hour to adhere the stud pins to the cured product layer. .

<Stud pull test>

Using a Stud pull tester (ROMULUS, manufactured by Quad Group Inc.), a stud pin is pulled at a rate of 2 kgf/sec in a direction perpendicular to the main surface of the cured material layer, and the load value at the time when the cured material layer is peeled off ( kgf/cm 2 ) was measured as Si adhesion strength.

[Evaluation of warpage]

The resin sheets produced in Examples and Comparative Examples were bonded to a 12-inch silicon wafer using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials) so that the resin composition layer and the silicon wafer were bonded. (thickness 775 μm) was laminated on the entire surface. The support of the resin sheet was peeled off to expose the resin composition layer, and a resin sheet was further laminated on the surface of the resin composition layer in the same manner to peel off the support. By the above lamination, two resin composition layers (total thickness of 100 μm) were formed on one side of a 12-inch silicon wafer. On the other hand, lamination was carried out under the same conditions as in [Evaluation of Si adhesion strength].

The resin composition layer was cured by heating in an oven at 100°C for 30 minutes and then at 190°C for 90 minutes to obtain a laminate having a layer configuration of "silicone wafer/cured resin composition layer". The edge of the obtained laminate was pressed against a horizontal platform. The distance between the end of the wafer on the opposite side to the end pressed and the table was measured as the amount of warpage. And the warpage was evaluated according to the following criteria.

Criteria for evaluating warpage:

"○": The amount of warpage is 0 mm or more and 1.5 mm (1500 µm) or less.

"x": The amount of warpage is greater than 1.5 mm.

[Measurement of modulus of elasticity]

The resin sheets produced in Examples and Comparative Examples were thermally cured at 190°C for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. In accordance with Japanese Industrial Standards (JIS K7127), a tensile test of the cured product was performed using a Tensilon universal testing machine (manufactured by A&D), and the modulus of elasticity (tensile modulus of elasticity) of the cured product at room temperature was measured.

[Measurement of Melt Viscosity]

A resin composition layer was obtained by peeling the support from the resin sheet prepared in Examples and Comparative Examples. Pellets for measurement (diameter 18 mm, 1.0 g to 1.1 g) were produced by compressing the resin composition layer with a mold. After that, the minimum melt viscosity was measured for the pellet for measurement using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). Specifically, with respect to 1 g of pellets for measurement, using a parallel plate with a diameter of 18 mm, 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 value thereof was obtained. The measurement conditions were a heating rate of 5°C/min, a measurement temperature interval of 2.5°C, a frequency of 1Hz, and a strain of 5deg.

[result]

The results of the above Examples and Comparative Examples are shown in the table below. In the table below, the meaning of the abbreviation is as follows.

(B) Content rate: (B) Content rate of inorganic filler.

Active group ratio: (A) The number of active groups in the curing agent (D) when the number of epoxy groups in the epoxy resin is 1.

100 Semiconductor Chip Package
110 semiconductor chips
120 sealing layer
130 rewiring cambium
140 redistribution layer
150 solder resist layer
160 bump

Claims (13)

(A) an epoxy resin, (B) an inorganic filler and (C) an elastomer;
(A) The resin composition in which the epoxy resin contains the epoxy resin containing the structure which has (A-1) epoxy group and chelate formation ability. The resin composition according to claim 1, wherein the amount of chelate modification of component (A-1) is 0.3% by mass to 10% by mass. The method of claim 1, wherein the ratio W (A-1) / W (C) of the mass W (A-1) of component (A-1) and the mass W (C) of component (C) is 0.01 to 1.0, resin composition. The resin composition according to claim 1, wherein the amount of the component (B) is 40% by mass or more with respect to 100% by mass of the non-volatile component of the resin composition. The resin composition according to claim 1, wherein component (C) has a number average molecular weight of 1,000 or more. The resin composition according to claim 1, further comprising (D) a curing agent. The resin composition according to claim 1, further comprising (E) a curing accelerator. The resin composition according to claim 1, which is for a sealing layer. A cured product of the resin composition according to any one of claims 1 to 8. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 8 formed on the support. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the circuit board according to claim 11 or the semiconductor chip package according to claim 12.

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