JP7259913B2 - Adhesive sheet with support - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive sheet with a support; a circuit board using the adhesive sheet with a support.

2. Description of the Related Art As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is formed by, for example, laminating a resin composition layer on a circuit board using an adhesive sheet having a layer structure of a resin composition layer/support, and then curing the resin composition layer. (Patent Document 1).

Japanese Patent Application Laid-Open No. 2016-20480

As a method of efficiently forming an insulating layer on a printed wiring board using an adhesive sheet, a method of forming an insulating layer on a circuit board using a vacuum laminator has been proposed.

In order to meet the recent demand for miniaturization, the present inventors have studied forming an insulating layer on a component built-in circuit board in which a component such as a capacitor is built. When forming an insulating layer on a circuit board with a built-in component using a vacuum laminator, a resin composition layer may be embedded in recesses of the circuit board with a built-in component where components are arranged. However, for example, in a resin composition containing a large amount of inorganic filler, the resin composition layer has low fluidity (part embedding property), and a gap is likely to occur between the circuit board and the resin composition layer. I got some insight. Therefore, it is required to improve the fluidity (part embedding property) of the resin composition layer in order to sufficiently embed the parts arranged in the recess, and for this reason, a device to lower the melt viscosity of the resin composition layer is required. .

On the other hand, when the melt viscosity of the resin composition layer is lowered in order to sufficiently embed the recessed portions where the parts are arranged, the tackiness of the surface of the resin composition layer is greatly improved, and the circuit board is laminated during lamination. and the resin composition layer stick to each other. For example, if the circuit board and the resin composition layer are overlapped in a step prior to pressurization, sticking occurs at the contact portion. When this sticking occurs, air enters between the circuit board and the resin composition layer, and the air cannot escape, which may cause voids. As described above, there is a trade-off relationship between the improvement of the part-embedding property of the resin composition layer and the suppression of the generation of voids in the resin composition layer.

Accordingly, the problem to be solved by the present invention is to provide an adhesive sheet with a support that can suppress the generation of voids and has good component embedding properties; a circuit board that uses the adhesive sheet with a support; and

As a result of intensive studies on the above-mentioned problems, the present inventors have found that a resin composition layer having a specific range of arithmetic mean roughness (Ra2) and tack force on the surface opposite to the surface bonded to the support. The inventors have found that the above problems can be solved by using them, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A support-attached adhesive sheet comprising a resin composition layer having a first surface and a second surface, and a support bonded to the first surface of the resin composition layer,
The arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more,
A support-attached adhesive sheet, wherein the second surface of the resin composition layer has a tack force of 1.1 N or more and 1.5 N or less at 80°C.
[2] The adhesive sheet with a support according to [1], which is used for forming an insulating layer using a vacuum laminator.
[3] The adhesive sheet with a support according to [2], wherein the degree of vacuum in the vacuum laminator is 0.01 hPa or more and 4 hPa or less.
[4] The support-attached adhesive sheet according to any one of [1] to [3], which is used for forming an insulating layer for embedding electronic components.
[5] The support-attached adhesive sheet according to any one of [1] to [4], which is used for forming an insulating layer on a circuit board.
[6] The adhesive sheet with a support according to any one of [1] to [5], wherein the resin composition layer has a minimum melt viscosity of 2000 poise or less at 60°C to 200°C.
[7] The resin composition layer contains a resin composition, the resin composition contains an inorganic filler, and the content of the inorganic filler is 70% by mass when the non-volatile component in the resin composition is 100% by mass. The adhesive sheet with a support according to any one of the above [1] to [6].
[8] The adhesive sheet with a support according to any one of [1] to [7], wherein the resin composition layer contains a resin composition, and the resin composition contains a liquid epoxy resin and a solid epoxy resin.
[9] Further comprising a protective film having a first surface and a second surface, the first surface of the protective film is bonded to the second surface of the resin composition layer of [1] to [8] The support-attached adhesive sheet according to any one of the above.
[10] The adhesive sheet with support of [9], wherein the first surface of the protective film has an arithmetic mean roughness of 150 nm or more.
[11] A circuit board comprising an insulating layer formed from a cured resin composition layer of the adhesive sheet with a support according to any one of [1] to [10].

ADVANTAGE OF THE INVENTION According to this invention, the adhesive sheet with a support which can suppress generation|occurrence|production of a void and the component embedding property is favorable, A circuit board using the adhesive sheet with a support, The circuit board can be provided.

FIG. 1 is a schematic cross-sectional view for explaining an example of the adhesive sheet with a support of the present invention. FIG. 2 is a schematic cross-sectional view for explaining an example of the support-attached adhesive sheet of the present invention. FIG. 3 is a schematic cross-sectional view for explaining an example of a circuit board. FIG. 4 is a schematic cross-sectional view for explaining an example of a circuit board provided with a cavity. FIG. 5 is a schematic cross-sectional view for explaining an example of how a temporary attachment material is laminated on a circuit board provided with a cavity. FIG. 6 is a schematic cross-sectional view for explaining an example of temporarily attaching an electronic component to the adhesive surface of the temporary attaching material exposed through the cavity. FIG. 7 is a schematic cross-sectional view for explaining an example of laminating a resin composition layer of an adhesive sheet with a support so as to be bonded to a circuit board using a vacuum laminator. FIG. 8 is a schematic cross-sectional view for explaining an example of how an electronic component is embedded in a resin composition layer. FIG. 9 is a schematic cross-sectional view for explaining an example of how the temporary attachment material is peeled off.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Adhesive sheet with support]
A support-attached adhesive sheet of the present invention is a support-attached adhesive sheet comprising a resin composition layer having a first surface and a second surface, and a support bonded to the first surface of the resin composition layer. The arithmetic average roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more, and the tack force at 80 ° C. of the second surface of the resin composition layer is 1.1 N or more and 1.5 N It is below.

FIG. 1 shows a schematic cross-sectional view of an example of the adhesive sheet with a support of the present invention. A support-attached adhesive sheet 1 of the present invention includes a support 3 and a resin composition layer 2 having a first surface 2a and a second surface 2b. The first surface 2a and the second surface 2b are opposite to each other in the thickness direction of the resin composition layer 2 . Therefore, when the first surface 2a is viewed as the back surface, the second surface 2b is the front surface. Further, the support 3 is bonded to the first surface 2 a of the resin composition layer 2 . As an example is shown in FIG. 2, the support-attached adhesive sheet 1 may include a protective film 4 having a first surface 4a and a second surface 4b. The first surface 4a and the second surface 4b are opposite to each other in the thickness direction of the protective film 4 . Moreover, the first surface 4 a of the protective film 4 is provided so as to be bonded to the second surface 2 b of the resin composition layer 2 . The support-attached adhesive sheet 1 is usually wound into a roll so that it can be stored and transported as a roll-shaped support-attached adhesive sheet.

The backing-attached adhesive sheet 1 satisfies the following conditions (I) and (II). The present inventors have found that the use of an adhesive sheet with a support containing a resin composition layer that satisfies the conditions (I) and (II) in the production of a circuit board suppresses the generation of voids and improves the embeddability of parts. found to be better.
(I) The arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more.
(II) The tack force at 80° C. of the second surface of the resin composition layer is 1.1 N or more and 1.5 N or less.

Condition (I) relates to the arithmetic mean roughness (Ra2) of the second surface of the resin composition layer being 150 nm or more. When the adhesive sheet with a support satisfies the condition (I), a passage through which air can be discharged is easily formed between the resin composition layer and the circuit board. Air can escape through the surface unevenness, and as a result, it is possible to suppress the generation of voids.

The arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more, preferably 200 nm or more, more preferably 250 nm or more. Although the upper limit is not particularly limited, it is preferably 2000 nm or less, more preferably 1500 nm or less, and still more preferably 1200 nm or less. The arithmetic mean roughness (Ra2) is a value measured within 15 minutes before laminating the second surface of the resin composition layer to the circuit board, for example, within 15 minutes after peeling off the protective film. be. Arithmetic mean roughness (Ra2) can be measured using a non-contact surface roughness meter. A specific example of the non-contact surface roughness meter is "WYKO NT3300" manufactured by Beecoinstruments. The arithmetic mean roughness (Ra2) can be measured, for example, using a non-contact surface roughness meter in VSI mode with a 50x lens and a measurement range of 121 μm×92 μm.

As a method for adjusting the arithmetic mean roughness of the second surface of the resin composition layer to 150 nm or more, for example, the surface unevenness is formed on the resin composition layer using a mold having surface unevenness, such as a support or a protective film. A method of transcription can be mentioned. The arithmetic mean roughness of the surface having surface irregularities is the same as the arithmetic mean roughness of the second surface of the resin composition layer. In detail, the surface unevenness is formed on the surface opposite to the surface bonded to the first surface of the resin composition layer of the support, and the surface unevenness formed on the support is formed by resin. A method of transferring to the second surface of the composition layer; It is a method of transferring to a surface. The support and protective film will be described later.

Condition (II) relates to the tack force at 80° C. of the second surface of the resin composition layer being 1.1 N or more and 1.5 N or less. As noted above, tack force generally increases as the minimum melt viscosity decreases. The adhesive sheet with a support of the present invention is required to have a low minimum melt viscosity in order to improve the embedding property of parts, and the tack force at 80° C. of the second surface of the resin composition layer is 1.1 N. It becomes bigger than above. As a result, voids are generally likely to occur, but since the adhesive sheet with a support of the present invention satisfies the condition (I), it is possible to suppress the generation of voids between the circuit board and the resin composition layer. It becomes possible. In addition, if the tack force is too large, the generation of voids cannot be suppressed completely, but by setting the tack force of the second surface of the resin composition layer at 80 ° C. to 1.5 N or less, the generation of voids is suppressed. It becomes possible to

The tack force of the second surface of the resin composition layer at 80° C. is 1.1 N or more, preferably 1.15 N or more, and more preferably 1.2 N or more. The upper limit is 1.5N or less, preferably 1.45N or less, more preferably 1.4N or less. The tack force at 80°C can be measured using a probe tack tester. A specific example of the probe tack tester is "TE-6002" manufactured by Tester Sangyo Co., Ltd. The tack force at 80° C. is measured, for example, using a probe tack tester with a glass probe having a diameter of 5 mm under a load of 1 kgf/cm ² , a contact speed of 0.5 mm/sec, a tensile speed of 0.5 mm/sec, and a holding time of 10 seconds. It can be measured under the measurement conditions.

The minimum melt viscosity of the resin composition layer is preferably 2000 poise or less, more preferably 1500 poise or less, and even more preferably 1000 poise or less. Although the lower limit is not particularly limited, it can be set to 10 poise or more. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity between 60°C and 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. A specific example of the dynamic viscoelasticity measuring device is "Rheosol-G3000" manufactured by UBM. For the lowest melt viscosity, for example, using a dynamic viscoelasticity measuring device, a parallel plate with a diameter of 18 mm is used for 1 g of the sample, and the starting temperature is 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min. It can be measured under the measurement conditions of a temperature interval of 2.5° C., a frequency of 1 Hz, and a strain of 1 deg.

As a method for adjusting the tack force of the second surface of the resin composition layer at 80° C. to 1.1 N or more and 1.5 N or less, for example, a resin composition containing a liquid epoxy resin and a solid epoxy resin is used. A method of forming a layer; a method of adjusting drying conditions after coating a resin varnish obtained by dissolving a resin composition in a solvent on a support in producing an adhesive sheet with a support, and the like.

<Resin composition layer>
Since the resin composition layer is a layer formed of a resin composition, it contains the resin composition. Examples of components contained in the resin composition include thermosetting resins. As the thermosetting resin, any thermosetting resin that is used when forming the insulating layer of a printed wiring board can be used, and among them, it is preferable to use an epoxy resin and a curing agent. Accordingly, in one embodiment, the resin composition comprises (A) an epoxy resin and (B) a curing agent. The resin composition may further contain (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing accelerator, (F) a flame retardant and (G) other additives, if necessary. good. Each component contained in the resin composition of the present invention will be described in detail below.

-(A) epoxy resin-
(A) Epoxy resins include, for example, 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, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. Epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. From the viewpoint of obtaining the desired effects of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin (A) is preferably 50% by mass. % or more, more preferably 60 mass % or more, and particularly preferably 70 mass % or more.

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”). ). The resin composition may contain only a liquid epoxy resin as the (A) epoxy resin, or may contain only a solid epoxy resin. Therefore, it is preferable to include a liquid epoxy resin and a solid epoxy resin in combination. A solid epoxy resin is a concept including a crystalline epoxy resin that is crystalline at a temperature of 20°C. When the resin composition contains a crystalline epoxy resin as a solid epoxy resin, in order to keep the 80° C. tack force of the second surface of the resin composition layer within a predetermined range, in addition to the crystalline epoxy resin, It is preferable to contain other solid epoxy resins.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, cyclohexanedimethanol type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd. "EX -721" (glycidyl ester type epoxy resin); Daicel's "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600" (epoxy resin having a butadiene structure); Nippon Steel "ZX1658" and "ZX1658GS" (cyclohexane dimethanol type epoxy resin) manufactured by Sumikin Chemical Co., Ltd., and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak 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 type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and bixylenol type epoxy resin and biphenyl type epoxy resin are more preferred. .

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd. "YL7800 (fluorene type epoxy resin); Mitsubishi Chemical Corp.'s "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical Corp.'s "jER1031S" (tetraphenylethane type epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) When a combination of a liquid epoxy resin and a solid epoxy resin is used as the epoxy resin, the ratio by mass (solid epoxy resin: liquid epoxy resin) is preferably 1:0.3 to 1:0.3 to 1:0.3. :10, more preferably 1:0.35 to 1:5, particularly preferably 1:0.4 to 1:3. When the ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the resin composition layer easily satisfies the condition (II), thereby improving the part embedding property.

(A) The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. It is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit of the epoxy resin content is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

-(B) Curing agent-
(B) Curing agent usually has a function of reacting with (A) epoxy resin to cure the resin composition.

(B) Curing agents include, for example, active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, and acid anhydrides. physical curing agents, and the like. (B) As the curing agent, an active ester curing agent and a phenolic curing agent are preferable. (B) Curing agents may be used singly or in combination of two or more.

A compound having one or more active ester groups in one molecule can be used as the active ester curing agent. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity. Preferred are compounds having The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenol compounds or naphthol compounds 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, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

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 phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. 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. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC- 8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T", "EXB-8500-65T" (manufactured by DIC); "EXB9416-70BK" as an active ester curing agent containing a naphthalene structure ( DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated phenol novolak; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylated phenol novolak. "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) and "YLH1030" as an active ester curing agent that is a benzoylated product of phenol novolak. (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and the like.

From the viewpoint of heat resistance and water resistance, the phenol-based curing agent and naphthol-based curing agent preferably have a novolac structure. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei; "NHN" manufactured by Nippon Kayaku; "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500";

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resins) and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, 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-diphenylmethane Diamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)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, and the like. Commercially available amine-based curing agents may be used. Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Co., Ltd., and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic 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), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid.

Among those mentioned above, the curing agent (B) is selected from phenol-based curing agents, active ester-based curing agents, cyanate ester-based curing agents, and benzoxazine-based curing agents from the viewpoint of significantly obtaining the desired effects of the present invention. and more preferably an active ester curing agent or a phenolic curing agent.

The ratio of (A) epoxy resin to (B) curing agent is [total number of epoxy groups in component (A)]:[total number of reactive groups in component (B)], which is 1:0. A range of 01 to 1:3 is preferred, 1:0.05 to 1:2 is more preferred, and 1:0.1 to 1:1 is even more preferred. Here, the "total number of epoxy groups in the component (A)" is the sum of all the values obtained by dividing the mass of the non-volatile component of the epoxy resin (A) present in the resin composition by the epoxy equivalent. The "total number of reactive groups of component (B)" is the sum of all the values obtained by dividing the mass of the non-volatile component of the curing agent (B) present in the resin composition by the active group equivalent. By setting the ratio between (A) the epoxy resin and (B) the curing agent within such a range, the desired effect of the present invention can be significantly obtained, and moreover, usually, the cured product of the resin composition layer Heat resistance is further improved.

(B) The content of the curing agent is preferably 1% by mass or more, more preferably 3% by mass, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of significantly obtaining the desired effects of the present invention. Above, more preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

-(C) Inorganic filler-
Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, 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, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (C) Inorganic fillers may be used singly or in combination of two or more.

(C) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatechs. ”, “YA010C”; “UFP-30” manufactured by Denka; "SO-C4", "SO-C2", "SO-C1";

(C) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, from the viewpoint of significantly obtaining the desired effects of the present invention, It is preferably 5 µm or less, more preferably 2 µm or less, and still more preferably 1 µm or less.

(C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, and the volume-based particle size distribution of the inorganic filler (C) is measured by the flow cell method. The average particle size was calculated as the median size from the size distribution. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(C) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 3 m ² /g or more, and particularly preferably 5 m ² /g or more, from the viewpoint of significantly obtaining the desired effects of the present invention. be. Although there is no particular upper limit, it 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 is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.

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 more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

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

(C) The content of the inorganic filler is 70% by mass or more, preferably 71% by mass or more, more preferably 71% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of reducing the tackiness. is 72% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less from the viewpoint of improving part embedding properties.

-(D) thermoplastic resin-
Examples of thermoplastic resins as component (D) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins. , polycarbonate resins, polyetheretherketone resins, polyester resins, and the like. Among them, the phenoxy resin is preferable from the viewpoint of obtaining the desired effects of the present invention remarkably and from the viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. In addition, (D) the thermoplastic resin may be used alone or in combination of two or more.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", "YL7482BH30";

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

(D) The content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.5% by mass or more, more preferably 1% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

-(E) Curing accelerator-
Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are preferred, and amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are more preferred. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 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-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-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, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(E) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less .

-(F) flame retardant-
In one embodiment, the resin composition may contain (F) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As the flame retardant, a commercially available product may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is difficult to hydrolyze is preferable, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable.

(F) The content of the flame retardant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass, when the non-volatile component in the resin composition is 100% by mass. or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

-(G) Other additives-
The resin composition may further contain other additives as optional components in addition to the components described above. Such additives include, for example, organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents; and the like. These additives may be used singly or in combination of two or more.

The thickness of the resin composition layer is preferably 1 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more, from the viewpoint of improving part embedding properties. From the viewpoint of suppressing the tack force, the thickness is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 50 μm or less, 40 μm or less, and 30 μm or less. In one preferred embodiment, the thickness of the resin composition layer is in the range of 10-40 μm.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In one preferred embodiment, the thickness of the support is in the range of 20-50 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

The arithmetic mean roughness (Ra) of the surface of the support that is not bonded to the resin composition layer is preferably 150 nm or more, more preferably 200 nm or more, and even more preferably 250 nm or more. The upper limit is preferably 2000 nm or less, more preferably 1500 nm or less, still more preferably 1200 nm or less. The arithmetic mean roughness can be measured by the same method as described for the arithmetic mean roughness (Ra2) of the second surface of the resin composition layer.

<Protective film>
The protective film can protect the second surface of the resin composition layer from physical damage, and can suppress adhesion of foreign matter such as dust. Furthermore, in the present invention, in order to form a resin composition layer that satisfies the above condition (I), it is preferable to use a protective film whose first surface has an arithmetic mean roughness within a specific range. By transferring the surface unevenness of the first surface of the protective film to the resin composition layer, the arithmetic mean roughness of the second surface of the resin composition layer can be adjusted so as to satisfy the condition (I).

The surface of the protective film that joins the resin composition layer, that is, the first surface of the protective film preferably has an arithmetic mean roughness of 150 nm or more, more preferably 200 nm or more, and still more preferably 250 nm or more. The upper limit is preferably 2000 nm or less, more preferably 1500 nm or less, still more preferably 1200 nm or less. The arithmetic mean roughness can be measured by the same method as described for the arithmetic mean roughness (Ra2) of the second surface of the resin composition layer.

When a film made of a plastic material is used as the protective film, as the plastic material, the same materials as those described for the support can be used. Moreover, when a metal foil is used as the protective film, the same metal foil as that described for the support can be used as the metal foil.

Examples of commercially available protective films include "MA430" and "MA411" (biaxially stretched polypropylene film) manufactured by Oji F-Tex.

The thickness of the protective film is preferably 5 μm or more, more preferably 10 μm or more. The upper limit of the thickness of the protective film is preferably 75 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less. In one preferred embodiment, the thickness of the protective film is in the range of 10-30 μm. When using a release layer-attached protective film, the overall thickness of the release layer-attached protective film is preferably within the above range.

<Method for manufacturing adhesive sheet with support>
The adhesive sheet with a support of the present invention can be produced, for example, by a production method including the following step (i). In addition, the support-attached adhesive sheet may further include the following step (ii).
(i) Step of providing a resin composition layer so as to be bonded to the support (ii) Step of providing a protective film so as to be bonded to the first surface of the resin composition layer

In step (i), the resin composition layer can be provided by a known method so as to bond the second surface of the resin composition layer to the support. For example, a resin varnish is prepared by dissolving a resin composition in a solvent, the resin varnish is applied to the surface of a support using a coating device such as a die coater, and the resin varnish is dried to provide a resin composition layer. can be done.

Solvents used for the preparation of resin varnish include, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Examples include carbitols such as toll, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. A solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

Drying of the resin varnish may be carried out by a known drying method such as heating or blowing hot air. From the viewpoint of satisfying the above condition (II), drying is performed so that the amount of residual solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of solvent, the resin composition layer is provided by drying at 50 to 150° C. for 3 to 10 minutes. be able to.

In step (ii), a protective film is provided so as to be bonded to the first surface of the resin composition layer.

Step (ii) may be carried out by laminating the first surface of the protective film to the resin composition layer by rolls, press crimping, or the like. Conditions for the lamination process are not particularly limited, and may be, for example, the same as the conditions described later for the method of manufacturing a printed wiring board.

In the above method for producing a support-attached adhesive sheet, the support is continuously conveyed from the support wound into a roll, and a resin varnish is applied and dried to form a resin composition layer on the support. , by providing a protective film (a protective film wound into a roll can be used) so as to join with the resin composition layer.

By winding the obtained adhesive sheet with a support into a roll, a roll-shaped adhesive sheet with a support can be produced.

<Application of Adhesive Sheet with Support>
The support-attached adhesive sheet of the present invention can suppress the generation of voids and has good part-embedding properties. Therefore, the adhesive sheet with a support of the present invention can be suitably used as an adhesive sheet with a support for forming an insulating layer using a vacuum laminator. At this time, the degree of vacuum in the vacuum laminator is preferably 0.01 hPa or more, more preferably 0.1 hPa or more, still more preferably 0.3 hPa or more, preferably 4 hPa or less, more preferably 3 hPa or less, and still more preferably. It is 1 hPa or less. The support-attached adhesive sheet of the present invention can also be suitably used as a support-attached adhesive sheet for forming an insulating layer for embedding electronic components. That is, for forming an adhesive sheet with a support used for forming an insulating layer for embedding an electronic component in a component-embedded circuit board in which the electronic component is built-in, or an insulating layer for sealing the electronic component. It can also be suitably used as an adhesive sheet with a support. Examples of electronic components include passive components such as capacitors, inductors and resistors, and active components such as semiconductor chips.

Further, the adhesive sheet with a support of the present invention can be suitably used as an adhesive sheet with a support for forming an insulating layer on a circuit board. Specifically, it can be suitably used as an adhesive sheet with a support used for forming an insulating layer of a multilayer printed wiring board and an adhesive sheet with a support used for forming an interlayer insulating layer of a printed wiring board. can be done.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed from the cured resin composition layer of the resin sheet with the support of the present invention. The support-attached adhesive sheet of the present invention is suitable for use in the production of circuit boards. In particular, the support-attached adhesive sheet of the present invention can suppress the generation of voids when the resin composition layer is laminated on a circuit board or the like, and has good component embedding properties. It is preferably used.

<Manufacturing method of component-embedded circuit board>
The method for manufacturing a component-embedded circuit board of the present invention comprises:
(1) A circuit board having first and second principal surfaces and having a cavity penetrating between the first and second principal surfaces, and a circuit board bonded to the second principal surface of the circuit board and an electronic component temporarily attached by the temporary attaching material inside the cavity of the circuit board, the adhesive sheet with the support of the present invention is applied to the circuit board to which the electronic component is temporarily attached, A lamination step of laminating using a vacuum laminator so that the second surface of the resin composition layer is bonded to the first main surface of the circuit board;
(2) a peeling step of peeling the temporary attachment material from the second main surface of the circuit board, in this order.

Before describing each step, the "circuit board to which electronic components are temporarily attached" using the adhesive sheet with support of the present invention will be described.

- Circuit board with electronic parts temporarily attached -
A circuit board to which electronic components are temporarily attached (hereinafter also referred to as "electronic component temporarily attached circuit board" or "cavity substrate") has first and second main surfaces, and the first and second main surfaces are A circuit board in which a cavity penetrating between main surfaces is formed, a tacking material bonded to a second main surface of the circuit board, and a tacking material tacked inside the cavity of the circuit board by the tacking material. including electronic components.

The electronic component temporary attachment circuit board can be prepared according to any conventionally known procedure in manufacturing the component-embedded circuit board. An example of the procedure for preparing the circuit board for temporarily attaching electronic components will be described below with reference to FIGS. 3 to 6, but the procedure is not limited to the following procedure.

First, a circuit board 10 is prepared as shown in FIG. The term "circuit board" refers to a plate-like substrate having first and second main surfaces and circuit wiring patterned on one or both of the first and second main surfaces. The first major surface and the second major surface are opposite each other. FIG. 3 schematically shows an end surface of the circuit board 10, and the circuit board 10 includes a substrate 20 and circuit wiring 30 such as via wiring and surface wiring. In the following description, for convenience, the first principal surface of the circuit board represents the upper principal surface of the illustrated circuit board, and the second principal surface of the circuit board refers to the lower surface of the illustrated circuit board. It is assumed that the main surface is represented.

Examples of the substrate 20 include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like, with glass epoxy substrates being preferred. The term "circuit board" as used in the present invention also includes an inner-layer circuit board, which is an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board.

The thickness of the substrate 20 is preferably less than 400 μm, more preferably 350 μm or less, even more preferably 300 μm or less, even more preferably 250 μm or less, particularly preferably 200 μm or less, 180 μm or less, from the viewpoint of thinning the component-embedded circuit board. 170 μm or less, 160 μm or less, or 150 μm or less. The lower limit of the thickness of the substrate 20 is preferably 50 μm or more, more preferably 80 μm or more, and even more preferably 100 μm or more, from the viewpoint of improving handling during transportation.

The dimensions of the circuit traces 30 may be determined according to the desired properties. For example, the thickness of the surface wiring is preferably 40 μm or less, more preferably 35 μm or less, even more preferably 30 μm or less, even more preferably 25 μm or less, particularly preferably 20 μm or less, or 19 μm, from the viewpoint of thinning the component-embedded circuit board. or less, or 18 μm or less. The lower limit of the thickness of the surface wiring is usually 1 μm or more, 3 μm or more, or 5 μm or more.

A cavity (recess) for accommodating an electronic component is provided in the circuit board as shown in an example in FIG. As schematically shown in FIG. 4, a cavity 20a is provided at a predetermined position of the substrate 20 so as to penetrate between the first and second main surfaces of the circuit board. The cavity 20a can be formed by a known method using, for example, a drill, laser, plasma, etching medium, etc., taking into consideration the properties of the substrate 20. FIG.

Although only one cavity 20a is shown in FIG. 4, a plurality of cavities 20a can be provided at predetermined intervals from each other. The pitch between the cavities 20a is preferably 10 mm or less, more preferably 9 mm or less, still more preferably 8 mm or less, still more preferably 8 mm or less, from the viewpoint of miniaturization of the component-embedded circuit board, although it depends on the opening size of the cavities 20a themselves. 7 mm or less, particularly preferably 6 mm or less. The lower limit is usually 1 mm or more, 2 mm or more, and the like. Each pitch between cavities 20a need not be the same across the circuit board and may be different.

The opening shape of the cavity 20a is not particularly limited, and may be any shape such as a rectangle, a circle, a substantially rectangle, and a substantially circle. The opening shape and opening size of the cavity 20a need not be the same across the circuit board and may be different.

As an example is shown in FIG. 5, a tacking material 40 is laminated on the second main surface of the circuit board 10 provided with the cavity 20a. The temporary attachment material 40 is not particularly limited as long as it has an adhesive surface exhibiting sufficient adhesiveness to temporarily attach the electronic component, and any conventionally known temporary attachment material can be used in manufacturing the component-embedded circuit board. good. In the embodiment schematically shown in FIG. 5, a film-like temporary attachment material 40 is laminated such that the adhesive surface of the temporary attachment material 40 is bonded to the second main surface of the circuit board. As a result, the adhesive surface of the temporary attachment material 40 is exposed through the cavity 20a.

Examples of the film-like temporary attachment material include "PFDKE-1525TT" (polyimide film with adhesive) manufactured by Arisawa Seisakusho Co., Ltd., UC series (UV tape for wafer dicing) manufactured by Furukawa Electric Co., Ltd., and the like.

As an example is shown in FIG. 6, the electronic component 50 is temporarily attached to the adhesive surface of the temporary attachment material 40 exposed through the cavity 20a to fabricate the circuit board 10A to which the electronic component is temporarily attached. In the embodiment schematically shown in FIG. 6, the electronic component 50 is temporarily attached to the adhesive surface of the temporary attachment material 40 exposed through the cavity 20a.

As the electronic component 50, an appropriate electrical component may be selected according to desired characteristics, and examples include passive components such as capacitors, inductors, and resistors, and active components such as semiconductor chips. The same electronic component 50 may be used for all cavities, or a different electronic component 50 may be used for each cavity.

-(1) Process-
In the step (1), as shown in FIG. 7, the adhesive sheet 1 with a support of the present invention is laminated on a circuit board 10A to which electronic components are temporarily attached. Specifically, the adhesive sheet 1 with support is laminated on the circuit board 10A to which the electronic components are temporarily attached using a vacuum laminator so that the resin composition layer 2 is bonded to the first main surface of the circuit board 10A. do. Here, when the adhesive sheet 1 with a support is provided with a protective film (not shown), the protective film is peeled off before lamination on the circuit board.

Lamination of the adhesive sheet 1 with the support onto the circuit board 10A for temporary attachment of electronic components using a vacuum laminator is performed, for example, by placing the adhesive sheet 1 with the support from the side of the support 3 under reduced pressure conditions. It can be performed by thermocompression bonding to the substrate 10A. As a member (not shown; hereinafter also referred to as a "thermocompression member") for thermocompression bonding the adhesive sheet 1 with a support to the circuit board 10A for temporary attachment of electronic components, for example, a heated metal plate (SUS panel, etc.) Alternatively, a metal roll (SUS roll) or the like may be used. The thermocompression bonding member is not directly pressed onto the adhesive sheet 1 with the support, but the adhesive sheet 1 with the support sufficiently follows the unevenness caused by the circuit wiring 30 and the cavity 20a of the circuit board 10A for temporary attachment of electronic components. Therefore, it is preferable to press through an elastic material such as heat-resistant rubber.

The thermocompression temperature is preferably in the range of 80° C. to 160° C., more preferably 100° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.5 MPa. It is in the range of 47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The degree of vacuum of the vacuum laminator is preferably 0.01 hPa or more, more preferably 0.1 hPa or more, still more preferably 0.3 hPa or more, preferably 4 hPa or less, more preferably 3 hPa or less, and still more preferably 1 hPa or less. be.

Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminator devices include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a two-stage build-up laminator “CVP700” manufactured by Nikko Materials.

(1) After the step, a heat treatment step of heat-treating the circuit board on which the adhesive sheet 1 with support is laminated may be performed. The heating temperature in this step is preferably 155° C. or lower, more preferably 150° C. or lower, still more preferably 145° C. or lower, and even more preferably 140° C. or lower. The lower limit of the heating temperature is preferably 110° C. or higher, more preferably 115° C. or higher, still more preferably 120° C. or higher, and even more preferably 125° C. or higher.

The heating time in the heat treatment step depends on the heating temperature, but is preferably 10 minutes or longer, more preferably 15 minutes or longer, and still more preferably 20 minutes or longer. Although the upper limit of the heating time is not particularly limited, it can usually be 60 minutes or less.

The heat treatment of the support-attached adhesive sheet 1 in the heat treatment step is preferably performed under atmospheric pressure (normal pressure).

The heat treatment of the support-attached adhesive sheet 1 in the heat treatment step may be performed before the support 3 is peeled off, or may be performed after the support 3 is peeled off.

Further, after the step (1), the laminated adhesive sheet 1 with support is smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support 3 side. It is preferred to carry out the steps. The press conditions in the smoothing step can be the same conditions as the thermocompression bonding conditions for lamination using the vacuum laminator.

(1) After the step, as shown in an example in FIG. Embedded.

-(2) Process-
In the step (2), as an example is shown in FIG. 9, the temporary attachment material 40 is removed from the second main surface of the circuit board to expose the second main surface of the circuit board.

The temporary attachment material 40 may be peeled off according to a conventionally known method depending on the type of the temporary attachment material 40 . For example, when "PFDKE-1525TT" (polyimide film with adhesive) manufactured by Arisawa Seisakusho Co., Ltd. is used as the temporary attachment material 40, the temporary attachment material 40 can be peeled off by cooling to room temperature. Further, when using a wafer dicing UV tape such as the UC series manufactured by Furukawa Electric Co., Ltd., the temporary bonding material 40 can be peeled off after the temporary bonding material 40 is irradiated with UV. The conditions such as the amount of UV irradiation can be known conditions that are usually employed in the manufacture of component-embedded circuit boards.

-Other processes-
When manufacturing the component-embedded circuit board of the present invention, the steps of (3) thermosetting the resin composition layer to form an insulating layer, (4) forming holes in the insulating layer, and (5) removing the surface of the insulating layer It may further include a step of roughening, and (6) a step of forming a conductor layer on the roughened surface of the insulating layer. Further, the step (3) may be performed after the step (1) and before the step (2) is performed, and after the step (2), a step of laminating an adhesive sheet with a support on the second main surface of the circuit board. may further include

The conditions for thermosetting the resin composition layer in the step (3) vary depending on the composition of the resin composition used in the resin composition layer, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably 150 ° C. to 210 ° C. ° C. range, more preferably 170° C. to 190° C. range), and the curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

Prior to thermal curing, the adhesive sheet 1 with support may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing, the adhesive sheet 1 with a support is heated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) may be preheated. When preheating is performed, such preheating is also included in the curing step.

The step (4) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (4) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the hole may be appropriately determined according to the design of the component-embedded circuit board.

The step (5) is a step of roughening the insulating layer. In this step (5), smear is usually removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used for forming an insulating layer of a component-embedded circuit board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. The swelling liquid is not particularly limited, but may be an alkaline solution, a surfactant solution, or the like, preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 to 90° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 to 80° C. for 5 seconds to 15 minutes. Examples of the oxidizing agent include, but are not limited to, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact P and Dosing Solution Securigans P manufactured by Atotech Japan. Moreover, as a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Shoryusin Securigant P manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidant solution in the neutralizing solution at 30 to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent solution in a neutralizing solution at 40 to 70° C. for 5 to 20 minutes is preferable.

The step (6) is a step of forming a conductor layer (circuit wiring) on the surface of the roughened insulating layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired component-embedded circuit board.

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]
A semiconductor device of the present invention includes a circuit board manufactured by the above method.

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

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the "part" showing an amount means a mass part.

<Preparation Example 1: Preparation of resin varnish (composition 1)>
Bisphenol type epoxy resin (epoxy equivalent about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) 10 parts, bixylenol type epoxy resin (epoxy equivalent about 185, Mitsubishi Chemical Co., Ltd.) "YX4000HK" manufactured by Nippon Kayaku Co., Ltd.) and 10 parts of a biphenyl type epoxy resin (epoxy equivalent of about 271, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) were heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7482BH30", solid content 30% by mass methyl ethyl ketone (MEK) solution), triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 151, DIC Company "LA-3018-50P", 2-methoxypropanol solution with a solid content of 50%) 8 parts, active ester curing agent (DIC "EXB-8500-65T", active group equivalent about 223, non-volatile components 65 mass% toluene solution) 10 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 2% by mass MEK solution) 4 parts, flame retardant (manufactured by Sanko Co., Ltd. "HCA-HQ", 10-(2 ,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) 2 parts, aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 130 parts of spherical silica (“SC2050SQ” manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.9 m ² /g, carbon amount per unit surface area 0.38 mg/m ² ) surface-treated with , and dispersed uniformly with a high-speed rotating mixer to prepare a resin varnish (composition 1).

<Preparation Example 2: Preparation of resin varnish (composition 2)>
In Preparation Example 1,
1) Change the amount of bisphenol type epoxy resin (epoxy equivalent about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) from 10 parts to 5 parts,
2) Change the amount of bixylenol type epoxy resin (epoxy equivalent of about 185, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) from 10 parts to 5 parts,
3) Change the amount of biphenyl type epoxy resin (epoxy equivalent of about 271, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) from 10 parts to 15 parts,
4) Furthermore, 5 parts of cyclohexanedimethanol-type epoxy resin (epoxy equivalent: 130, "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added to the resin varnish material.
A resin varnish (composition 2) was obtained in the same manner as in Preparation Example 1 except for the above matters.

<Preparation Example 3: Preparation of resin varnish (composition 3)>
In Preparation Example 1,
1) 10 parts of a bisphenol type epoxy resin (epoxy equivalent of about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a 1:1 mixture of bisphenol A type and bisphenol F type) was added to cyclohexanedimethanol type epoxy resin (epoxy equivalent of 130, "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) changed to 10 copies,
2) 10 parts of biphenyl type epoxy resin (epoxy equivalent about 271, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) was changed to 10 parts of biphenyl type epoxy resin (epoxy equivalent about 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.).
A resin varnish (composition 3) was obtained in the same manner as in Preparation Example 1 except for the above matters.

<Preparation Example 4: Preparation of resin varnish (composition 4)>
In Preparation Example 1,
1) Change the amount of bisphenol type epoxy resin (epoxy equivalent about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) from 10 parts to 20 parts,
2) 10 parts of biphenyl-type epoxy resin (epoxy equivalent of about 271, Nippon Kayaku "NC3000L") was changed to 10 parts of biphenyl-type epoxy resin (epoxy equivalent of about 291, Nippon Kayaku "NC3000H"),
3) 10 parts of bixylenol-type epoxy resin (epoxy equivalent: about 185, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) was not used.
A resin varnish (composition 4) was obtained in the same manner as in Preparation Example 1 except for the above matters.

<Preparation Example 5: Preparation of resin varnish (composition 5)>
In Preparation Example 1,
1) Change the amount of bixylenol type epoxy resin (epoxy equivalent of about 185, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) from 10 parts to 15 parts,
2) 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) was changed to 5 parts of biphenyl type epoxy resin (epoxy equivalent of about 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.).
A resin varnish (composition 5) was obtained in the same manner as in Preparation Example 1 except for the above matters.

<Preparation Example 6: Preparation of resin varnish (composition 6)>
In Preparation Example 1,
1) Change the amount of bisphenol type epoxy resin (epoxy equivalent about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) from 10 parts to 5 parts,
2) 10 parts of biphenyl-type epoxy resin (epoxy equivalent of about 271, Nippon Kayaku "NC3000L") was changed to 25 parts of biphenyl-type epoxy resin (epoxy equivalent of about 291, Nippon Kayaku "NC3000H"),
3) 10 parts of bixylenol-type epoxy resin (epoxy equivalent: about 185, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) was not used.
A resin varnish (composition 6) was obtained in the same manner as in Preparation Example 1 except for the above matters.

<Preparation Example 7: Preparation of resin varnish (composition 7)>
In Preparation Example 1,
1) Change the amount of bisphenol type epoxy resin (epoxy equivalent about 165, "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) from 10 parts to 20 parts,
2) 10 parts of a biphenyl-type epoxy resin (epoxy equivalent: about 271, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) was not used.
A resin varnish (composition 7) was obtained in the same manner as in Preparation Example 1 except for the above matters.

The components used in the preparation of Compositions 1 to 7 and their blending amounts (parts by mass) are shown in the table below.

<Example 1: Preparation of adhesive sheet with support>
As a support, on the release surface of a PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., thickness 38 μm) that has been release-treated with a non-silicone release agent ("AL-5" manufactured by Lintec), a die coater was used. A resin varnish (composition 1) was applied and dried at 80° C. to 110° C. (average 100° C.) for 3 minutes to form a resin composition layer. The thickness of the resin composition layer was 20 μm. Then, a protective film was provided so as to join with the resin composition layer. As the protective film, a polypropylene film (manufactured by Oji F-Tex Co., Ltd., “biaxially stretched polypropylene film, “MA430”, thickness: 20 μm, arithmetic mean roughness: 1000 nm) was used.

<Example 2: Preparation of adhesive sheet with support>
In Example 1, as a protective film, the roughened surface (arithmetic average roughness 250 nm) of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Biaxially oriented polypropylene film, product name: MA411", thickness 15 μm) was used as a resin composition. It was provided so as to join with the layer. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Example 3: Preparation of adhesive sheet with support>
In Example 1, composition 1 was changed to composition 2. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Example 4: Preparation of adhesive sheet with support>
In Example 1, composition 1 was changed to composition 3. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Example 5: Preparation of adhesive sheet with support>
In Example 1, Composition 1 was changed to Composition 4. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Example 6: Preparation of adhesive sheet with support>
In Example 1, Composition 1 was changed to Composition 5. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Comparative Example 1: Production of Adhesive Sheet with Support>
In Example 1, composition 1 was changed to composition 6. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Comparative Example 2: Production of Adhesive Sheet with Support>
In Example 1, as a protective film, a smooth surface (arithmetic mean roughness 50 nm) of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Biaxially oriented polypropylene film, product name: MA411", thickness 15 μm) was used as a resin composition layer. It was provided so as to join with. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Comparative Example 3: Production of Adhesive Sheet with Support>
In Example 1, Composition 1 was changed to Composition 7. An adhesive sheet with a support was produced in the same manner as in Example 1 except for the above items.

<Measurement of arithmetic mean roughness (Ra2) of second surface of resin composition layer>
The protective film was peeled off from the adhesive sheets with a support obtained in Examples and Comparative Examples. Within 15 minutes after peeling off the protective film, the arithmetic mean roughness of the surface of the resin composition layer was measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Bcoinstruments) in VSI mode with a 50x lens. It was obtained from a numerical value obtained with a measurement range of 121 μm×92 μm. Each sample was measured by averaging 10 randomly selected points.

<Measurement of minimum melt viscosity of resin composition layer>
The minimum melt viscosity of the resin composition layer of the adhesive sheet with support was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM). Using a parallel plate with a diameter of 18 mm, 1 g of a sample resin composition sampled from the resin composition layer was heated from a starting temperature of 60° C. to 200° C. at a heating rate of 5° C./min. The dynamic viscoelastic modulus was measured under the measurement conditions of 5° C., frequency of 1 Hz, and strain of 1 deg, and the lowest melt viscosity (poise) was measured.

<Measurement of tack force at 80°C of the second surface of the resin composition layer>
The protective film was peeled off from the support-attached adhesive sheets obtained in Examples and Comparative Examples, and the resin composition layer was measured using a probe tack tester (manufactured by Tester Sangyo Co., Ltd., "TE-6002") using a glass probe with a diameter of 5 mm. The tack force was measured at a load of 1 kgf/cm ² , a contact speed of 0.5 mm/sec, a tensile speed of 0.5 mm/sec, a holding time of 10 seconds, and a temperature of 80°C.

<Evaluation of component embeddability>
Using the adhesive sheets with supports obtained in Examples and Comparative Examples, circuit boards with temporarily attached electronic components were produced according to the following procedure, and embedding properties were evaluated.

(1) Preparation of electronic component temporary mounting circuit board (cavity board) Glass cloth base BT resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Ltd. “HL832NSF LCA”) 255 mm Cavities of 0.7 mm×1.1 mm were formed at a pitch of 3 mm on the entire surface of a size of 340 mm×340 mm. Next, both sides were etched with a micro-etching agent (“CZ8101” manufactured by MEC Co., Ltd.) to a thickness of 1 μm to roughen the copper surface. Dried.

(2) Preparation of electronic component temporary attachment circuit board On one side of the substrate obtained in (1), a 25 μm thick adhesive-attached polyimide film (polyimide, 38 μm thick, manufactured by Arisawa Seisakusho Co., Ltd., “PFDKE-1525TT”). Using a batch-type vacuum pressurized laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the adhesive was arranged so as to be bonded to the substrate and laminated on one side. Lamination was carried out by pressure bonding for 30 seconds at 80° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. Next, laminated ceramic capacitor parts (1005=1 mm×0.5 mm size, thickness 0.14 mm) were temporarily mounted one by one in the cavity to prepare a circuit board (cavity board) for temporarily mounting electronic parts.

(3) Evaluation of part embedding properties Using a test batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), protected from the adhesive sheet with support prepared in Examples and Comparative Examples The resin composition layer exposed by peeling the film was laminated so as to be bonded to the surface of the electronic component temporary attachment circuit board (cavity substrate) prepared in (2) opposite to the surface on which the polyimide film with adhesive was arranged. . Lamination is performed within 15 minutes after peeling of the protective film, and after reducing the pressure for 30 seconds to 13 hPa or less (degree of vacuum during lamination: 0.5 hPa), pressure bonding is performed for 30 seconds at 100 ° C. and a pressure of 0.74 MPa. It was implemented by Then, the laminated adhesive sheet with a support was hot-pressed for 60 seconds at 100° C. under atmospheric pressure and a pressure of 0.5 MPa to smoothen. An evaluation substrate A was prepared by peeling off the adhesive-attached polyimide film from the circuit board with the electronic parts temporarily attached, which had been cooled to room temperature. The resin flow in the cavity was observed with an optical microscope (150x magnification) from the surface of the substrate for evaluation A from which the polyimide film was peeled off. This observation was performed for 10 cavities, and the component embedding properties were evaluated according to the following criteria.
○: In all the cavities, the outer periphery of the multilayer ceramic capacitor component was covered with the resin composition layer.
x: Even one of the cavities has a gap or the resin composition layer is not embedded in the outer peripheral portion of the multilayer ceramic capacitor part.

<Void evaluation>
In the substrate for evaluation A, the portion other than the cavity portion was observed with an optical microscope (150x magnification) to evaluate the presence or absence of voids between the resin composition layer and the circuit board for temporary attachment of electronic components, and evaluated according to the following criteria.
◯: No voids exist.
x: Voids are present.

REFERENCE SIGNS LIST 1 support-attached adhesive sheet 2 resin composition layer 2a first surface of resin composition layer 2b second surface of resin composition layer 3 support 4 protective film 4a first surface of protective film 4b second surface of protective film 10 Circuit board 10A Electronic component temporary attachment circuit board 20 Board 20a Cavity 30 Circuit wiring 40 Temporary attachment material 50 Electronic component

Claims (10)

a resin composition layer having a first surface and a second surface; a support bonded to the first surface of the resin composition layer; A support-attached adhesive sheet comprising a protective film bonded to the second surface of the composition layer,
The resin composition layer contains an inorganic filler,
The content of the inorganic filler is 70% by mass or more and 90% by mass or less when the non-volatile component in the resin composition is 100% by mass,
The arithmetic mean roughness of the first surface of the protective film is 150 nm or more,
The arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more,
A support-attached adhesive sheet, wherein the second surface of the resin composition layer has a tack force of 1.1 N or more and 1.5 N or less at 80°C. a resin composition layer having a first surface and a second surface; a support bonded to the first surface of the resin composition layer; A support-attached adhesive sheet comprising a protective film bonded to the second surface of the composition layer,
The resin composition layer contains an epoxy resin, an active ester curing agent, and an inorganic filler,
The arithmetic mean roughness of the first surface of the protective film is 150 nm or more,
The arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more,
A support-attached adhesive sheet, wherein the second surface of the resin composition layer has a tack force of 1.1 N or more and 1.5 N or less at 80°C. 3. The adhesive sheet with a support according to claim 1, which is used for forming an insulating layer using a vacuum laminator. 4. The adhesive sheet with a support according to claim 3, wherein the degree of vacuum in the vacuum laminator is 0.01 hPa or more and 4 hPa or less. The support-attached adhesive sheet according to any one of claims 1 to 4, which is used for forming an insulating layer for embedding electronic parts. The support-attached adhesive sheet according to any one of claims 1 to 5, which is used for forming an insulating layer on a circuit board. The adhesive sheet with a support according to any one of claims 1 to 6, wherein the resin composition layer has a minimum melt viscosity of 2000 poise or less at 60°C to 200°C. The adhesive sheet with a support according to any one of claims 1 to 7, wherein the resin composition layer contains a resin composition, and the resin composition contains a liquid epoxy resin and a solid epoxy resin. 9. The resin sheet with a support according to claim 8, wherein the ratio of liquid epoxy resin to solid epoxy resin (solid epoxy resin:liquid epoxy resin) is 1:0.3 to 1:10. A circuit board having first and second principal surfaces and having a cavity penetrating between the first and second principal surfaces, and a temporary attachment bonded to the second principal surface of the circuit board. A circuit board to which an electronic component is tacked, comprising a material and an electronic component tacked by the tacking material inside a cavity of the circuit board, according to any one of claims 1 to 9. a lamination step of laminating the adhesive sheet with a support using a vacuum laminator so that the second surface of the resin composition layer is bonded to the first main surface of the circuit board;
A method of manufacturing a component-embedded circuit board, comprising, in this order, a peeling step of peeling the temporary attachment material from the second main surface of the circuit board.

Images