TW202003767A - Adhesive sheet with support body capable of suppressing generation of voids and having a good component embedding property - Google Patents

Abstract

The present invention provides an adhesive sheet with a support body, which is capable of suppressing generation of voids and has a good component embedding property, and a circuit board using the adhesive sheet with the support body. The adhesive sheet with a support body of the present invention is an adhesive sheet with a support body comprising: a resin composition layer having a first surface and a second surface, and a support body bonded to the first surface of the resin composition layer, wherein the arithmetic mean roughness (Ra2) of the second surface of a resin composition layer is 150 nm or more, and the adhesion force at 80 DEG. of the second surface of the resin composition layer is 1.1 N or more and 1.5 N or less.

Description

Adhesive sheet with support

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

As a manufacturing technology of a printed circuit board, a manufacturing method of a cumulative method in which an insulating layer and a conductor layer are alternately overlapped is known. For the manufacturing method by the accumulation method, the insulating layer is, for example, a bonding sheet composed of a layer having a resin composition layer/support, and after laminating the resin composition layer on the circuit board, by making the resin composition layer It can be formed by curing (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Literature 1] JP 2016-20480

[Problems solved by the invention]

As a method for efficiently forming an insulating layer of a printed circuit board using an adhesive sheet, a method of forming an insulating layer on a circuit board by a vacuum lamination device has been proposed.

The inventors of the present invention intend to review the formation of an insulating layer on a circuit board in which components such as capacitors are built, in response to past miniaturization requirements. For forming an insulating layer on a circuit board with a built-in part using a vacuum lamination device, there is a method in which a resin composition layer is embedded in a concave portion where the circuit board with a built-in part is placed. However, for example, it is known that for a resin composition containing a large amount of inorganic filler, the fluidity (part embedability) of the resin composition layer is low, and voids are easily generated between the circuit board and the resin composition layer. Therefore, in order to allow the parts disposed in the recess to be sufficiently embedded, it is necessary to increase the fluidity of the resin composition layer (part embedding property), so the work of reducing the melt viscosity of the resin composition layer is expected.

On the other hand, it is known that when the resin composition layer is to be sufficiently embedded in the recess where the parts are arranged to reduce the melt viscosity, the adhesion of the surface of the resin composition layer will be greatly improved. The composition layer will produce a fit. For example, if the circuit board and the resin composition layer are overlapped in the step before pressurization, bonding will occur at this contact portion. When this bonding occurs, air may enter between the circuit board and the resin composition layer, and if the air cannot be discharged, it may cause a void. In this way, the improvement of the embedment of the parts of the resin composition layer has a trade-off relationship with the suppression of the voids of the resin composition layer, and there is still much room for improvement in removing this trade-off.

Then, the problem to be solved by the present invention is to provide a bonding sheet with a support that can suppress the occurrence of voids and has good part embedability; and a circuit board using the bonding sheet with a support. [Means to solve the problem]

The inventors conducted a detailed review of the above-mentioned problems and found that the above-mentioned problems can be solved by using the following resin composition layer to complete the present invention; the resin composition layer is an arithmetic that is opposite to the surface to which the support is joined The average thickness (Ra2) and adhesion are within a certain range.

That is, the present invention includes the following. [1] A support-attached adhesive sheet, which is a support-attached body comprising a resin composition layer having a first surface and a second surface, and a support body bonded to the first surface of the resin composition layer Adhesive sheet, in which the arithmetic average roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more, and the adhesive force of the second surface of the resin composition layer at 80° C. is 1.1 N or more and 1.5 N or less. [2] The adhesive-attached sheet described in [1] for forming an insulating layer using a vacuum lamination device. [3] The adhesive-attached sheet described in [2] in which the vacuum degree in the vacuum laminating apparatus is 0.01 hPa or more and 4 hPa or less. [4] The adhesive-attached sheet described in any one of [1] to [3] for forming an insulating layer in which an electronic component is embedded. [5] The adhesive-attached sheet described in any one of [1] to [4] for forming an insulating layer on a circuit board. [6] The adhesive sheet with a support according to any one of [1] to [5] described in any one of [1] to [5] whose minimum melt viscosity of the resin composition layer at 60° C. to 200° C. is 2000 poise or less. [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 or more when the nonvolatile component in the resin composition is taken as 100% by mass [1] The adhesive sheet with a support described in any one of [6]. [8] The resin composition layer contains a resin composition, and the resin composition contains a supporting sheet with a support as described in any one of [1] to [7] of liquid epoxy resin and solid epoxy resin. [9] A protective film further having a first surface and a second surface, the first surface of the protective film and the second surface of the resin composition layer are joined together according to any one of [1] to [8] Adjacent sheet with support. [10] The adhesive sheet with a support described in [9] of [9] whose arithmetic average roughness of the first surface of the protective film is 150 nm or more. [11] A circuit board containing an insulating layer formed by a cured product of a resin composition layer of a support-attached adhesive sheet as described in any one of [1] to [10]. [Effect of invention]

According to the present invention, it is possible to provide an adhesive sheet with a support that can suppress the occurrence of voids and has good part embedability; and a circuit board using the adhesive sheet with a support.

[Type of implementation of invention]

The present invention will be described in detail below by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be implemented with any changes without departing from the scope of the patent application and the equivalent scope of the present invention.

[Adhesive sheet with support] The support-attached sheet of the present invention is a support-attached adhesive containing 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 In the sheet, the arithmetic average roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more, and the adhesion of the second surface of the resin composition layer at 80° C. is 1.1 N or more and 1.5 N or less.

FIG. 1 shows a schematic cross-sectional view of an example of the adhesive-attached sheet of the present invention. The adhesive-attached sheet 1 of the present invention is a resin composition layer 2 including a support 3 and a first surface 2a and a second surface 2b. The first surface 2a and the second surface 2b are opposite sides with respect to the thickness direction of the resin composition layer 2. Therefore, when the first surface 2a is viewed from the back, the second surface 2b is the surface. In addition, the support 3 is joined to the first surface 2a of the resin composition layer 2. As an example shown in FIG. 2, the adhesive sheet 1 with a support 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 sides with respect to the thickness direction of the protective film 4. In addition, the first surface 4 a of the protective film 4 is provided to be joined to the second surface 2 b of the resin composition layer 2. The adhesive sheet 1 with a support is usually wound into a roll shape, and can be stored and transported as a roller-shaped adhesive sheet with a support.

The adhesive sheet 1 with a support satisfies the following conditions (I) and (II). The present inventors found that by using a supporting sheet with a support containing a resin composition layer that satisfies the conditions (I) and (II) when producing a circuit board, the generation of voids can be suppressed, and the part embedability becomes good . (I) The arithmetic average roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more. (II) The adhesive 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.

The condition (I) relates to the arithmetic average roughness (Ra2) of the second surface of the resin composition layer being 150 nm or more. Since the adhesive sheet with the support satisfies the condition (I), it is easy to form a passage through which the air between the resin composition layer and the circuit board can be discharged, so the second side of the resin composition layer is interposed especially during vacuum lamination The surface of the surface is uneven and can be separated from the air, and as a result, the generation of voids can be suppressed.

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

As a method for adjusting the arithmetic average roughness of the second surface of the resin composition layer to 150 nm or more, for example, a type having surface irregularities is used, for example, a support or a protective film is used, and the surface irregularities are converted in the resin composition layer The method of printing. The arithmetic average roughness of the surface having irregularities on the surface is the same as the arithmetic average roughness of the second surface of the resin composition layer. In detail, the side surface to be joined to the first surface of the resin composition layer of the support is to form the aforementioned surface irregularities on the opposite side surface, and transfer the surface irregularities formed on the support to the first side of the resin composition layer A two-sided method; a method of forming the aforementioned surface irregularities on the first surface of the protective film, and transferring the surface irregularities formed on the first surface of the protective film to the second surface of the resin composition layer. The support and the protective film will be described later.

The condition (II) relates to the second surface of the resin composition layer having an adhesive force at 80° C. of 1.1 N or more and 1.5 N or less. As mentioned above, the adhesive force usually increases when the minimum melt viscosity decreases. The adhesive sheet with a support of the present invention is intended to improve the embedability of parts, so it is required to reduce the minimum melt viscosity, and the adhesive force of the second surface of the resin composition layer at 80°C becomes a larger value such as 1.1 N or more . As a result, voids are generally easy to generate, but the adhesive sheet with a support of the present invention satisfies the condition (I), so that the voids between the circuit board and the resin composition layer can be suppressed. Also, if the adhesive force is too large, the occurrence of voids cannot be suppressed, but by setting the adhesive force at 80°C of the second surface of the resin composition layer to 1.5 N or less, the occurrence of voids can be suppressed.

The adhesive force at 80°C of the second surface as the resin composition layer is 1.1 N or more, preferably 1.15 N or more, and preferably 1.2 N or more. The upper limit is 1.5N or less, preferably 1.45N or less, preferably 1.4N or less. The adhesion at 80°C can be measured using a probe adhesion tester. As a specific example of the probe adhesion tester, "TE-6002" manufactured by Tester Industries Co., Ltd. can be cited. For adhesion at 80°C, for example, a probe adhesion tester can be used. A glass probe with a diameter of 5 mm is loaded with 1 kgf/cm ² , a contact speed of 0.5 mm/second, a stretching speed of 0.5 mm/second, and a holding time of 10 seconds. The measurement is performed under measurement conditions.

The minimum melt viscosity of the resin composition layer is preferably 2000 poise or less, preferably 1500 poise or less, and more preferably 1000 poise or less. Although the lower limit value is not particularly limited, it may be 10 poise or more. Among them, the term "minimum melt viscosity" refers to the lowest melt viscosity at 60 ℃ ~ 200 ℃. The lowest melt viscosity can be determined by using a dynamic viscoelasticity measuring device. As a specific example of the dynamic viscoelasticity measuring device, "Rheosol-G3000" manufactured by You BM Corporation can be cited. For the lowest melt viscosity, for example, a dynamic viscoelasticity measuring device can be used. For a sample of 1 g, a parallel plate with a diameter of 18 mm is used. The temperature rise from 60° C. to 200° C. is carried out at a rate of 5° C./min with a temperature interval of 2.5° C. , Vibration number 1Hz, strain 1deg measurement conditions were measured.

As a method of adjusting the adhesive 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 can be used. A method of forming a resin composition layer; a method of adjusting the drying conditions after coating the resin of the resin composition dissolved in the solvent when the support-attached sheet is manufactured, and the like.

<Resin composition layer> The resin composition layer is a layer formed on the resin composition, and therefore contains the resin composition. Examples of components contained in the resin composition include thermosetting resins. As the thermosetting resin, any thermosetting resin used when forming the insulating layer of the printed circuit board can be used, and among them, an epoxy resin and a hardener are also preferably used. Therefore, in one embodiment, the resin composition contains (A) epoxy resin and (B) hardener. The resin composition may further contain (C) inorganic filler, (D) thermoplastic resin, (E) hardening accelerator, (F) flame retardant, and (G) other additives as necessary. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

-(A) Epoxy resin- (A) Examples of the epoxy resin include bis-cresol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and bisphenol AF-type ring Oxygen resin, dicyclopentadiene epoxy resin, phenolic epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin , Naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane epoxy resin Resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

As the (A) epoxy resin in the resin composition, an epoxy resin having two or more epoxy groups in one molecule is preferable. From the viewpoint that the desired effect of the present invention can be made more remarkable, for (A) 100% by mass of the non-volatile content of the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule The proportion of the resin is preferably 50% by mass or more, preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”), and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”). Solid epoxy resin"). In the resin composition, (A) the epoxy resin may contain only liquid epoxy resin or solid epoxy resin, but from the viewpoint of forming a resin composition layer satisfying the condition (II), The liquid epoxy resin and the solid epoxy resin are preferably combined and contained. The solid epoxy resin is a concept containing a crystalline epoxy resin at a temperature of 20°C. When the resin composition contains a crystalline epoxy resin as a solid epoxy resin, from the viewpoint of setting the adhesive force of the second surface of the resin composition layer at 80°C within a predetermined range, except for the crystalline epoxy resin In addition to the resin, those containing other solid epoxy resins are preferred.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

As the liquid epoxy resin, 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 group Amine epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, glycidylamine epoxy resin The resin and the epoxy resin having a butadiene structure are preferred, and bisphenol A epoxy resin, bisphenol F epoxy resin, and cyclohexanedimethanol epoxy resin are preferred.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "" manufactured by Mitsubishi Chemical Corporation. "825", "EPICOAT828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac varnish) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and double Phenol F type epoxy resin mixed product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex; "CELLOXIDE2021P" (alicyclic ring with ester skeleton) manufactured by Daicel Chemical Industries, Ltd. Epoxy resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Chemical Industries, Ltd.; "ZX1658", "ZX1658GS" (cyclohexane) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Dimethanol epoxy resin), etc. One of these may be used alone, or two or more types may be used in combination.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Is better.

As the solid epoxy resin, bis-cresol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type 4-functional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, Phenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF ring Oxygen resins and tetraphenylethane-type epoxy resins are preferred, and bis-cresol-type epoxy resins and biphenyl-type epoxy resins are preferred.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy) manufactured by DIC. Resin); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolac epoxy resin) made by DIC; "HP-" made by DIC "7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (Japanese phenol type epoxy resin) manufactured by Nippon Kayaku; manufactured by Nippon Chemical Co., Ltd. "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Chemical "ESN475V" (naphthol epoxy resin) manufactured by the company; "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "YX4000H", "YX4000" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Company; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. One of these may be used alone, or two or more types may be used in combination.

When (A) an epoxy resin is used in combination with a liquid epoxy resin and a solid epoxy resin, the mass ratio of this equivalent ratio (solid epoxy resin: liquid epoxy resin) is 1: 0.3 to 1. : 10 is better, preferably 1:0.35 to 1:5, particularly preferably 1:0.4 to 1:3. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within this range, the resin composition layer can easily meet the condition (II), and the part embedding property can become good.

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq. to 5000g/eq., preferably 50g/eq. to 3000g/eq., more preferably 80g/eq. to 2000g/eq., more It is preferably 110 g/eq. to 1000 g/eq. With this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, preferably from 250 to 3000, and more preferably from 400 to 1500, from the viewpoint that the desired effect of the present invention can be obtained remarkably. The weight average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC).

(A) The content of the epoxy resin, from the viewpoint of obtaining an insulating layer with good mechanical strength and showing insulation reliability, when the non-volatile component in the resin composition is taken as 100% by mass, 1% by mass or more Preferably, it is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, preferably 25% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, 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 taken as 100% by mass unless specifically stated otherwise.

-(B) Hardener- (B) The hardener usually has a function of reacting with A) the epoxy resin to harden the resin composition.

Examples of the (B) hardener include active ester-based hardeners, phenol-based hardeners, naphthol-based hardeners, benzoxazine-based hardeners, cyanate-based hardeners, and carbodiimide-based hardeners. , Amine hardener, anhydride hardener, etc. As the (B) hardener, active ester-based hardeners and phenol-based hardeners are preferred. (B) One type of hardener may be used alone, or two or more types may be used in combination.

As an active ester hardener, it can be used for compounds having one or more active ester groups in one molecule. Among them, as active ester-based hardeners, phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compound esters are equal to compounds having two or more highly reactive ester groups in one molecule Better. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, the active ester hardener obtained from the carboxylic acid compound and the hydroxy compound is preferred, and the active ester hardener obtained from the carboxylic acid compound and the phenol compound and/or naphthol compound is preferred good.

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, methyl alcohol 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, phloroglucinol, pyrogallol, dicyclopentadiene diphenol Compounds, phenolic novolac, etc. The so-called "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensation of 1 molecule of dicyclopentadiene and 2 molecules of phenol.

As preferred specific examples of the active ester-based hardeners, there may be mentioned active ester-based hardeners containing a dicyclopentadiene-type diphenol structure, active ester-based hardeners containing a naphthalene structure, and acetylated compounds containing phenol novolac. Active ester-based hardener, active ester-based hardener containing phenol novolac benzoyl compound. Among them, active ester hardeners containing a naphthalene structure and active ester hardeners containing a dicyclopentadiene diphenol structure are also preferred. The so-called "dicyclopentadiene diphenol structure" means a divalent structural unit formed by phenylene-dicyclopentylene-phenylene.

As a sales product of an active ester hardener, examples of active ester hardeners containing a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" ", "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T", "EXB-8500-65T" (manufactured by DIC); as an active ester hardener containing naphthalene structure "EXB9416-70BK" (manufactured by DIC); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener containing phenol novolac acetoxylate; activity as benzoyl benzoate containing phenol novolac "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an ester hardener; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener of phenol novolak; benzoyl compound as a phenol novolak The active ester-based hardeners include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, those having a novolac structure are preferred. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is preferred.

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

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylidene-1,5-phenylenecyanate), and 4,4′. -Methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) thioether, and bis(4-cyanate phenyl) ether And other bifunctional cyanate resins; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; etc.; a part of these cyanate trees is pre-triazineized and so on. Specific examples of the cyanate ester hardener include "PT30" and "PT60" (phenol novolak type multifunctional cyanate resin) manufactured by Lonza Japan, and "ULL-950S" (multifunctional cyanate Resin), "BA230", "BA230S75" (a part or all of bisphenol A dicyanate triazine is converted into a prepolymer prepolymer), etc.

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

Examples of the amine-based hardener include hardeners having one or more amine groups in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effect of the present invention. The amine-based hardener is preferably a first-level amine or a second-level amine, and preferably a first-level amine. As specific examples of the amine-based hardener, 4,4'-methylidene bis(2,6-dimethylaniline), diphenyl diamino sulfone, 4,4'-diamino diphenyl Methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, m-phenylenediamine, m-xylene diamine, diethyltoluene Amine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl -4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-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) phenanthrene, bis(4-(3-aminophenoxy)phenyl ) 碸 and so on. Amine-based hardeners can be used for sale, for example, "KAYABOND C-200S", "KAYABOND C-100", "KayahardA-A", "KayahardA-B", "KayahardA-S" manufactured by Nippon Kayaku Co., Ltd. ", "EpicureW" manufactured by Mitsubishi Chemical Corporation, etc.

Examples of the acid anhydride hardener include hardeners having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic acid. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- (Furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetra Carboxylic dianhydride, oxodiphthalic dianhydride, 3,3'-4,4'-diphenylbenzene tetracarboxylic 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(dehydro trimellitate) ). Polymeric anhydrides such as styrene and maleic acid copolymerized with styrene and maleic acid.

Among the above-mentioned (B) hardeners, from the viewpoint that the desired effect of the present invention can be obtained remarkably, they are selected from phenol-based hardeners, active ester-based hardeners, cyanate-based hardeners, and benzoxazine-based One or more hardeners are preferred, and active ester hardeners or phenol hardeners are preferred.

The ratio of (A) epoxy resin to (B) hardener is at the ratio of [total of epoxy groups of (A) component]: [total of reactive groups of (B) component], at 1: The range of 0.01 to 1:3 is preferred, preferably 1:0.05 to 1:2, and more preferably 1:0.1 to 1:1. Among them, the so-called "total count of epoxy groups of (A) component" means that the value obtained by dividing the mass of the non-volatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent is the total total value . In addition, the "total count of reactive groups of (B) component" means that the value obtained by dividing the mass of the non-volatile components of the (B) hardener present in the resin composition by the equivalent of active groups is the total total value. By setting the amount ratio of (A) epoxy resin to (B) hardener within this range, the desired effect of the present invention can be remarkably obtained, and generally the heat resistance of the hardened product of the resin composition layer can be further improved .

(B) The content of the curing agent is preferably 1% by mass or more, preferably 3% for the 100% by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. The mass% or more, more preferably 5 mass% or more, preferably 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less.

-(C)Inorganic filler- Examples of the material of the inorganic filler include silicon dioxide, alumina, glass, cordierite, silicate, 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, titanic acid Bismuth, titanium oxide, acid zirconium, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly preferred. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. As the silica, spherical silica is preferred. (C) One type of inorganic filler may be used alone, or two or more types may be used in combination.

Examples of (C) inorganic fillers sold include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Materials Co., Ltd.; "YC100C", "YA050C" and "YA050C" manufactured by Admatechs. -MJE", "YA010C"; "UFP-30" made by Denka; "SilfirNSS-3N", "SilfirNSS-4N", "SilfirNSS-5N" made by Tokuyama; "SC2500SQ", "SO" made by Admatechs -C4", "SO-C2", "SO-C1", etc.

(C) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. , Is preferably 2 μm or less, and more preferably 1 μm or less.

(C) The average particle size of the inorganic filler can be measured by laser diffraction/scattering method according to Mie scattering theory. Specifically, with a laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the inorganic filler is made on a volume basis, and the median diameter can be measured as the average particle size. For measuring the sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed in a sample bottle, and the latter can be applied with ultrasound for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device, using the light source wavelength as blue and red, and the flow cell method was used to measure (C) the volume-based particle size distribution of the inorganic filler, and calculated from the obtained particle size distribution As the average diameter of the median diameter. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by HORIBA, Ltd. can be cited.

(C) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, preferably 3 m ² /g or more, and particularly preferably 5 m ² /g or more from the viewpoint that the desired effect of the present invention can be remarkably obtained. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area was obtained by calculating the specific surface area using a BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas on the surface of the sample, and using the BET multipoint method.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organic silazane. Compounds, titanate-based coupling agents, etc. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available products for surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) made by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyl trimethyl) made by Shin-Etsu Chemical Co., Ltd. Oxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler by the surface treatment degree of the surface treatment agent, it is preferable to suppress it within a predetermined range. Specifically, among 100 parts by mass of the inorganic filler, 0.2 to 5 parts by mass of the surface treatment agent is preferred for surface treatment, and 0.2 to 3 parts by mass is preferred for surface treatment to 0.3 mass 1 to 2 parts by mass is preferred for 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, preferably 0.1 mg/m ² or more, and 0.2 mg/m from the viewpoint of improving the dispersibility of the inorganic filler. ² or more is better. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin coating and the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, preferably 0.8 mg/m ² or less, and 0.5 mg/m ² or less is better.

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

(C) The content of the inorganic filler is preferably from 70% by mass or more, preferably from 71% by mass or more, when the nonvolatile component in the resin composition is taken as 100% by mass from the viewpoint of reducing adhesion. It is preferably 72% by mass or more. From the viewpoint of improving the embeddability of the parts, 90% by mass or less is preferable, 85% by mass or less is preferable, and 80% by mass or less is more preferable.

-(D) Thermoplastic resin- Examples of the thermoplastic resin of the component (D) include phenoxy resin, polyethylene acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide amide imide resin, and polyimide resin. Ether imine resin, poly satin resin, polyether satin resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Among them, the phenoxy resin is preferred from the viewpoint of remarkably obtaining the desired effect of the present invention, and from the viewpoint of obtaining an insulating layer having excellent adhesion to a conductor layer having a small surface roughness. In addition, (D) the thermoplastic resin may be used alone or in combination of two or more kinds.

Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and dicyclopentane. A phenoxy resin of at least one type of group consisting of alkene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group or epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (including double Phenoxy resin with phenol S skeleton); "YX6954" (phenoxy resin with bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", "YL7482BH30" manufactured by the Chemical Company.

Examples of polyvinyl acetal resins include polyethylene formaldehyde resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "Electronic Butyral 4000-2", "Electronic Butyral 5000-A", "Electronic Butyral 6000-C", " Electro-Butyral 6000-EP"; S-LECBH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Corporation.

As specific examples of the polyimide resin, "RIKACOATSN20" and "RIKACOATPN20" manufactured by New Japan Physical and Chemical Corporation can be cited. As a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) Modified polyimide such as polyimide described in Japanese Patent No. 6), polyimide containing polysiloxane skeleton (polyimide described in JP 2002-12667 and 2000-319386, etc.) Imine.

As specific examples of the polyamide amide imide resin, "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Co., Ltd. can be cited. As specific examples of the polyimide amide imine resin, there may be mentioned modified polyamide amide imide such as "KS9100" and "KS9300" (polyamide amide imide containing polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. .

As a specific example of the polyether resin, the "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

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

As specific examples of the poly-resin resin, poly-resin "P1700", "P3500" manufactured by Solvay Advanced Polymers, etc. may be mentioned.

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, preferably 10,000 or more, particularly preferably 20,000 or more, and 70,000 or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. Preferably, it is preferably 60,000 or less, and particularly preferably 50,000 or less.

(D) The content of the thermoplastic resin is from the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 0.1% by mass or more, preferably 0.5 The mass% or more, more preferably 1 mass% or more, preferably 5 mass% or less, preferably 4 mass% or less, more preferably 3 mass% or less.

-(E) Hardening accelerator- Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonium decanate. , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutyl The phosphonium decanoate is preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diaza Heterobicyclic (5,4,0)-undecene is preferred.

Examples of the imidazole hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl -2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(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 adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 -Methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resin, with 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole Better.

As the imidazole-based hardening accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-toluene)guanidine, diacetyl Methylguanidine, 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecane Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-toluene) biguanide, etc., Dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

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

(E) The content of the hardening accelerator, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less.

-(F) Flame retardant- In one embodiment, the resin composition contains (F) flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, and the like. One kind of flame retardant can be used alone, or two or more kinds can be used together.

As the flame retardant, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Chemical Co., Ltd., and "PX-200" manufactured by Daiichi Chemical Industry Corporation. As the flame retardant, those that are not easily hydrolyzed are preferred, for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferred.

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

-(G)Other additives- The resin composition may contain other additives as optional components in addition to the above components. Examples of such additives include organic fillers; resin additives such as tackifiers, defoamers, leveling agents, and adhesion-imparting agents. One type of these additives may be used alone, or two or more types may be used in combination.

The thickness of the resin composition layer is preferably 1 μm or more, preferably 10 μm or more, and more preferably 15 μm or more from the viewpoint of improving the embeddability of parts. From the viewpoint of suppressing the adhesive force, it is preferably 100 μm or less, preferably 80 μm or less, more preferably 50 μm or less, 40 μm or less, and 30 μm or less. In a preferred embodiment, the thickness of the resin composition layer is in the range of 10 μm to 40 μm.

<Support> Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials 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 simply referred to as "PET") and polyethylene naphthalate ( Acrylic acid, cyclic polyolefin, triacetyl cellulose such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), polymethyl methacrylate (PMMA), etc. TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are also preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The surface on which the support and the resin composition layer are joined may be subjected to matting treatment, corona treatment, and electrification prevention treatment.

In addition, as the support, a support with a release layer having a release layer for bonding to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include, for example, 1 selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than one release agent. For the support with a release layer, commercially available products can be used, for example, "SK-1" and "AL-5" manufactured by Lintec, a PET film having a release layer with an alkyd resin-based release agent as the main component. , "AL-7", "LumirrorT60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. For a preferred embodiment, the thickness of the support is in the range of 20 μm to 50 μm. Furthermore, when using a support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.

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

<Protection film> According to the protective film, the second surface of the resin composition layer can be protected from physical damage, and the adhesion of foreign materials such as garbage can be suppressed. Further in the present invention, since a resin composition layer that satisfies the above condition (I) is formed, it is preferable to use a protective film having an arithmetic average roughness on the first surface of the protective film in a specific range. By transferring the surface unevenness of the first surface of the protective film of the resin composition layer, it can be adjusted that the arithmetic average roughness of the second surface of the resin composition layer satisfies the condition (I).

The arithmetic average roughness of the surface of the protective film bonded to the resin composition layer, that is, the first surface of the protective film is preferably 150 nm or more, preferably 200 nm or more, and more preferably 250 nm or more. The upper limit value is preferably 2000 nm or less, preferably 1500 nm or less, and more preferably 1200 nm or less. The arithmetic average roughness can be measured by the same method as described for the arithmetic average 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, the plastic material can be used for the same material as described for the support. In addition, when a metal foil is used as the protective film, the same metal foil as described for the support can be used as the metal foil.

Examples of the protective film for sale include "MA430" and "MA411" (biaxially stretched polypropylene film) manufactured by Oji F-Tex Corporation.

The thickness of the protective film is preferably 5 μm or more, preferably 10 μm or more. The upper limit of the thickness of the protective film is preferably 75 μm or less, preferably 50 μm or less, and more preferably 40 μm or less. For a preferred embodiment, the thickness of the protective film is in the range of 10-30 μm. Moreover, when using the protective film with a mold release layer, it is preferable that the whole thickness of the protective film with a mold release layer is in the said range.

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

In the step (i), the resin composition layer may be provided such that the second surface of the resin composition layer is bonded to the support by a known method. For example, a resin coating of a resin composition dissolved in a solvent is prepared, the resin coating is coated, and the surface of the support is coated using a coating device such as die coating. The resin coating layer may be provided after drying the resin coating.

Examples of solvents used for the preparation of resin coatings include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether. Acetates such as acetate and carbitol acetate, cellosolve and carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl Acetamide-based solvents such as acetamide and N-methylpyrrolidone. Solvent can be used alone or in combination of two or more.

The drying of the resin coating can be carried out by a known drying method such as heating and hot air blowing. From the viewpoint of meeting the above condition (II), the amount of residual solvent in the resin composition layer is usually 10% by mass or less, preferably dried to 5% by mass or less. Although it differs depending on the boiling point of the solvent in the resin coating, for example, when using a resin coating containing 30% by mass to 60% by mass of the solvent, it can be dried for 3 minutes to 10 minutes at 50°C to 150°C Instead, a resin composition layer is provided.

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

The step (ii) can be carried out by laminating the first surface of the protective film on the resin composition layer with a roller or pressure. The conditions of the lamination process are not particularly limited, and for example, they can be the same as those described in the method of manufacturing a printed circuit board described later.

In the method of manufacturing the above-mentioned support-attached sheet, the support can be continuously transported by rolling the support into a roll shape, and after the resin composition layer is formed on the support by coating and drying with resin coating, A protective film (using a protective film wound into a roll shape) is provided to be bonded to the resin composition layer, and can be continuously implemented.

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

<Use of adhesive sheet with support> The adhesive sheet with a support of the present invention can suppress the occurrence of voids, and the embedment of parts is also good. However, the supporting sheet with a support of the present invention can be suitably used as the supporting sheet with a support when forming an insulating layer using a vacuum laminating device. At this time, the vacuum degree in the vacuum laminating apparatus is preferably 0.01hPa or more, preferably 0.1hPa or more, more preferably 0.3hPa or more, preferably 4hPa or less, preferably 3hPa or less, more preferably 1hPa or less . The adhesive sheet with a support of the present invention can be suitably used as the adhesive sheet with a support to be used for forming an insulating layer in which an electronic component is to be embedded. In other words, it can be suitably used as the following two types of adhesive-attached films, which are used to form an insulating layer for embedding an electronic component in a circuit substrate embedded in a component containing an electronic component, or used for Those who form an insulating layer to seal electronic parts. Examples of electronic components include passive components such as capacitors, inductors, and resistors, and active components such as semiconductor chips.

In addition, the adhesive-attached adhesive sheet of the present invention can be suitably used as an adhesive-attached adhesive sheet to form an insulating layer on a circuit board. Specifically, it can be used as a support-attached adhesive sheet used for forming an insulating layer of a multilayer printed circuit board, and can be suitably used as a support-attached adhesive sheet used for forming an interlayer insulating layer of a printed circuit board .

[Circuit board] The circuit board of the present invention is an insulating layer formed by a cured product of the resin composition layer of the resin sheet with a support of the present invention. The adhesive sheet with a support of the present invention can be suitably used for the manufacture of circuit boards. In particular, the adhesive sheet with a support of the present invention can suppress the occurrence of voids when the resin composition layer is laminated on a circuit board and the like, and the embedding of parts is also good, so it can be applied to the circuit board with built-in parts manufacture.

<Manufacturing method of circuit board with built-in parts> The manufacturing method of the circuit board with built-in parts of the present invention includes the following steps; (1) Containing a circuit substrate having first and second main surfaces penetrating between the first and second main surfaces to form a cavity, a point material that is bonded to the second main surface of the circuit substrate, and For the electronic parts that are ignited by the ignited materials inside the cavity of the circuit board, on the circuit board where the electronic parts are ignited, the adhesive sheet with a support of the present invention and the resin composition The second surface of the layer is the first main surface of the circuit board, and the lamination step of lamination is performed using a vacuum lamination device; (2) Peeling step of peeling the point material from the second main surface of the circuit board.

Before describing each step, a description will be given of the "circuit board for electronic parts via tack weld" using the adhesive-attached sheet of the present invention.

-Electronic parts pass through the circuit board of Dianhu- The electronic parts are contained through the circuit board of the point (hereinafter also referred to as "circuit board of the point of electronic parts", "cavity substrate"): it has the first and second main surfaces, and penetrates between the first and second main surfaces The circuit board forming the cavity, the point-hard material joined to the second main surface of the circuit board, and the electronic parts that are point-hardened by the point-hard material for the inside of the cavity of the circuit board.

The circuit board of the electronic component ignition circuit board can be prepared according to any procedure known in the past when manufacturing the circuit board with built-in parts. The following describes an example of a procedure for preparing a circuit board for the electronic component ignition circuit with reference to FIGS. 3 to 6, but it is not limited to the following procedure.

First, as an example shown in FIG. 3, the circuit board 10 is prepared. The "circuit board" is a plate-like substrate having first and second main faces, and having patterned circuit wiring on one or both sides of the first and second main faces. The first main surface and the second main surface are opposite sides. With reference to FIG. 3, the end surface of the circuit board 10 is schematically shown. The circuit board 10 is a circuit wiring 30 including a substrate 20 and through wiring, surface wiring, and the like. For the following description, for simplicity, the first main surface of the circuit board represents the upper main surface of the circuit board shown, and the second main surface of the circuit board represents the lower main surface of the circuit board shown.

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, and glass epoxy substrates are preferred. In addition, when manufacturing a printed circuit board, an inner layer circuit board that further needs to form an intermediate product of an insulating layer and/or a conductor layer is also included in the so-called "circuit board" in the present invention.

The thickness of the substrate 20 is preferably less than 400 μm, preferably 350 μm or less, more preferably 300 μm or less, more preferably 250 μm or less, and particularly preferably 200 μm or less from the viewpoint of thinning the circuit board with built-in parts. 180 μm or less, 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, preferably 80 μm or more, and more preferably 100 μm or more from the viewpoint of improvement in handling during transport.

The size of the loop wiring 30 can be determined according to the desired characteristics. For example, the thickness of the surface wiring is preferably 40 μm or less, preferably 35 μm or less, more preferably 30 μm or less, more preferably 25 μm or less, and particularly preferably 20 μm or less from the viewpoint of thinning the circuit board embedded in the component. 19 μm 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, 5 μm or more, or the like.

As an example shown in FIG. 4, a cavity (recess) to accommodate electronic components is provided on the circuit board. As shown in the pattern shown in FIG. 4, a cavity 20 a penetrating between the first and second main surfaces of the circuit substrate is provided at a predetermined position on the substrate 20. The cavity 20a can be formed by using a well-known method such as a drill, laser, plasma, or etching medium in consideration of the characteristics of the substrate 20.

Although only one cavity 20a is shown in FIG. 4, the cavity 20a may be provided in plural at a predetermined interval. Although the distance between the cavities 20a varies depending on the opening size of the cavities 20a itself, from the viewpoint of miniaturization of the circuit board embedded in the parts, it is preferably 10 mm or less, preferably 9 mm or less, and more preferably 8 mm or less, more preferably 7 mm or less, and particularly preferably 6 mm or less. The lower limit is usually 1 mm or more and 2 mm or more. The pitches between the cavities 20a do not have to be the same on 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 rectangular, circular, slightly rectangular, and slightly circular. The opening shape and opening size of the cavity 20a are not necessarily the same on the circuit board, and may be different.

As an example shown in FIG. 5, a point material 40 is laminated on the second main surface of the circuit board 10 provided with the cavity 20 a. As the point material 40, it is only necessary to have an adhesive surface that exhibits sufficient adhesiveness when the electronic parts are point-fired, and there is no particular limitation, and any point-known material known in the past can be used in the manufacture of the circuit board with built-in parts . In the mode shown in FIG. 5, the film-like point material 40 is synthesized into an adhesive surface of the point material 40 and the second main surface of the circuit board is joined. Thereby, through the cavity 20a, the sticky surface of the hard material 40 may be exposed.

Examples of thin film-shaped materials include “PFDKE-1525TT” (polyimide film with an adhesive) manufactured by Youze Manufacturing Co., Ltd., and UC series (UV tape for wafer cutting) manufactured by Furukawa Electric Co., Ltd. )Wait.

As an example shown in FIG. 6, the electronic component 50 is ignited on the adhesive surface of the igniting material 40 exposed through the cavity 20a, and a circuit board 10A temporarily attached with the electronic component is manufactured. In the mode shown in FIG. 6, the electronic component 50 is ignited by the adhesive surface of the igniting material 40 exposed through the cavity 20 a.

As the electronic component 50, suitable electrical components can 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 can be used in all cavities, or different electronic components 50 can be used in each cavity.

-(1)Step- (1) In the step, as shown in FIG. 7 as an example, the supporting sheet 1 with a support of the present invention is laminated on the circuit board 10A through which the electronic parts pass through. In detail, the adhesive sheet 1 with a support is bonded to the first main surface of the circuit board 10A using a vacuum laminator on the circuit board 10A where the electronic parts have passed through. In the case where the adhesive sheet 1 with a support is provided with a protective film (not shown), the circuit board is laminated after the protective film is peeled off.

The bonding sheet 1 with a support using a vacuum laminating device can be used for laminating the electronic component point circuit board 10A. For example, the bonding sheet 1 with a support can be attached to the electron from the support 3 side under reduced pressure. The parts are tack welded on the circuit board 10A by heating and pressing. Examples of the member (not shown; hereinafter also referred to as "heating and pressing member") that heat-presses the adhesive sheet 1 with a support on the electronic component point circuit board 10A are exemplified by a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller), etc. Moreover, instead of directly pressing the heating and pressing member to the adhesive sheet 1 with a support, the adhesive sheet 1 with a support is intended to sufficiently follow the circuit of the circuit board 10A due to the tack weld of electronic parts The irregularities caused by the wiring 30 or the cavity 20a are preferably pressed through an elastic material such as heat-resistant rubber.

The heating and pressing temperature is preferably from 80°C to 160°C, preferably from 100°C to 140°C, the heating and pressing pressure is from 0.098MPa to 1.77MPa, preferably from 0.29MPa to 1.47MPa, and the heating pressure The time is preferably 20 seconds to 400 seconds, preferably 30 seconds to 300 seconds. The vacuum degree of the vacuum lamination device is preferably 0.01 hPa or more, preferably 0.1 hPa or more, more preferably 0.3 hPa or more, preferably 4 hPa or less, preferably 3 hPa or less, more preferably 1 hPa or less.

The vacuum lamination device can be performed by a commercially available vacuum lamination device. Examples of vacuum laminate devices that are sold include vacuum pressurized laminates made by famous machine manufacturers, vacuum applicators made by Nikko･Materials Co., Ltd., and second-level accumulation laminates "CVP700" made by Nikko･Materials Co., Ltd., etc. .

(1) After the step, the circuit substrate laminated with the support-attached sheet 1 may be subjected to a heat treatment step of heat treatment. The heating temperature in this step is preferably 155°C or lower, preferably 150°C or lower, 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, preferably 115°C or higher, more preferably 120°C or higher, and even more preferably 125°C or higher.

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

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

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

Further, after step (1), under normal pressure (at atmospheric pressure), for example, by pressing the heating and pressing member from the support 3 side, smoothing of the laminated adhesive sheet 1 with support is performed The smoothing step of the chemical processing is preferable. The pressurization conditions in the smoothing step may be the same conditions as the heat-pressing conditions for lamination using the vacuum lamination device described above.

After the step (1), as shown in an example shown in FIG. 8, the resin composition layer 2 is filled with the electronic component 50 filled in the cavity 20 a and ignited in the cavity 20 a is embedded in the resin composition layer 2.

-(2)Step- (2) Step As shown in FIG. 9 as an example, the tack weld material 40 is peeled from the second main surface of the circuit board, and the second main surface of the circuit board is exposed.

The peeling of the tack weld material 40 can correspond to the type of the tack weld material 40, and is carried out according to a conventionally known method. For example, when using "PFDKE-1525TT" (polyimide film with an adhesive) manufactured by Aizawa Manufacturing Co., Ltd. as the flameproof material 40, the flameproof material 40 can be peeled off by cooling to room temperature. In addition, when using UV tape for wafer cutting such as UC series manufactured by Furukawa Electric Industries Co., Ltd., the spot-hard material 40 can be peeled off after irradiating the spot-hard material 40 with UV. Conditions such as the amount of UV radiation are well-known conditions commonly used in the manufacture of circuit boards with built-in parts.

-Other steps- In the manufacture of the circuit board with built-in parts of the present invention, it may further include (3) a step of thermosetting the resin composition layer to form an insulating layer, (4) a step of opening the insulating layer, (5) insulating The step of roughening the surface of the layer, (6) the step of forming a conductor layer on the surface of the roughened insulating layer. In addition, after the step (1), the step (3) may be performed before the step (2), and the step (2) may further include a step of laminating an adhesive sheet with a support on the second main surface of the circuit board.

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

Before heat curing, the adhesive sheet 1 with a support can be preheated at a temperature lower than the curing temperature. For example, before heat curing, at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, preferably 70°C or more and 100°C or less), the supporting sheet 1 can be attached The preliminary heating is performed for 5 minutes or more (preferably 5 minutes to 150 minutes, preferably 15 minutes to 120 minutes). When preliminary heating is performed, the preliminary heating is also included in the hardening step.

(4) The step is a step of making holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. (4) The step corresponds to the composition of the resin composition used for the formation of the insulating layer, and can be performed using a drill, laser, plasma, etc., for example. The size or shape of the hole can be appropriately determined according to the design of the circuit board embedded in the part.

(5) The step is a step of roughening the insulating layer. For this step (5), stain removal is also usually performed. The procedure and conditions of the roughening treatment are not particularly limited, and when forming the insulating layer of the circuit board in which the part is built, a commonly known procedure and conditions can be adopted. For example, the roughening treatment of the insulating layer is to perform the roughening treatment of the insulating layer by sequentially performing the swelling treatment by the swelling liquid, the roughening treatment by the oxidizing agent, and the neutralization treatment by the neutralizing solution. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and the alkaline solution is preferable. The alkaline solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of the swelling liquid to be sold include Swing Dip Securigant P and Swinging Dip Securigant SBU manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in the swelling liquid at 30 to 90°C for 1 to 20 minutes. From the viewpoint that the swelling of the resin of the insulating layer can be controlled to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40 to 80°C for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment of an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing solution heated at 60° C. to 80° C. for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of the oxidizing agent sold include alkaline permanganate solutions such as Concentrate Compact P and Dosing Solution Securigant P manufactured by Atotech Japan. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercial products include Reduction Sholyshin Securigant P manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent solution in a neutralizing solution at 30 to 80°C for 5 to 30 minutes. From the viewpoint of workability and the like, the method of immersing the object roughened with the oxidant solution in a neutralizing liquid at 40 to 70° C. for 5 to 20 minutes is preferable.

(6) The step is a step of forming a conductor layer (loop 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 metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above group (eg, nickel, chromium alloy, copper, nickel alloy, and copper, titanium alloy) ) The formed layer. Among them, from the perspective of universality, cost, and ease of patterning of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel･chromium alloy, The alloy layer of copper, nickel alloy, copper and titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel and chromium alloy is preferred. A single metal layer of copper is better.

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

Although the thickness of the conductor layer depends on the design of the circuit board inside the desired part, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, by a well-known technique such as a semi-additive method and a full-additive method, the surface of the insulating layer can be plated to form a conductor layer having a desired wiring pattern. From the viewpoint of simplicity of manufacturing, the semi-additive method Formers are better. The following shows an example of forming a conductor layer by a semi-additive method.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a part of the plating seed layer is exposed corresponding to the desired wiring pattern to form a mask pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, 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] The semiconductor device of the present invention includes the circuit substrate manufactured by the above method.

Examples of the semiconductor device include various semiconductor devices provided in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as automatic bicycles, automobiles, trams, ships, and aircraft). [Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to those examples. In addition, the "parts" indicating the quantity indicates the mass parts unless otherwise specified.

<Preparation Example 1: Preparation of resin coating (Composition 1)> Bisphenol-type epoxy resin (epoxy equivalent of about 165g/eq., manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "ZX1059", bisphenol A type and bisphenol 10 parts of F type 1:1 mixed product), 10 parts of bis-cresol type epoxy resin (epoxy equivalent of about 185g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation), and biphenyl type epoxy resin ( Epoxy equivalent is about 271g/eq., 10 parts of "NC3000L" manufactured by Nippon Kayaku Co., Ltd., and dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of a phenoxy resin ("YX7482BH30" manufactured by Mitsubishi Chemical Corporation, a solid content of 30% by mass of methyl ethyl ketone (MEK) solution), a phenol novolak system containing a triazine skeleton are mixed here Hardener (hydroxyl equivalent 151, "LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution with 50% solid content) 8 parts, active ester-based hardener ("EXB-8500-65T manufactured by DIC Corporation"'', active group equivalent of about 223, nonvolatile content 65% by mass in toluene solution) 10 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 2% by mass in MEK solution) 4 parts, difficult Combustion agent ("HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) 2 Parts, spherical silica ("SC2050SQ" manufactured by Admatechs), surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, specific surface area 5.9 m ² /g, per The amount of carbon per unit surface area (0.38 mg/m ² ) was 130 parts, and the resin coating (Composition 1) was prepared by uniformly dispersing with a high-speed rotating mixer.

<Preparation example 2: Preparation of resin coating (Composition 2)> For modulation example 1, 1) The amount of bisphenol-type epoxy resin (epoxy equivalent of about 165g/eq., "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixed product of bisphenol A and bisphenol F) from 10 Changed to 5 copies, 2) Change the amount of bis-xylenol type epoxy resin (epoxy equivalent of about 185g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation) from 10 to 5 parts. 3) Change the amount of biphenyl type epoxy resin (epoxy equivalent of about 271g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) from 10 to 15 parts. 4) Add 5 parts of cyclohexanedimethanol type epoxy resin (epoxy equivalent 130g/eq., Nippon Steel & Sumitomo Chemical Co., Ltd. product "ZX1658GS") to the resin-painted material. Except for the above matters, a resin coating (Composition 2) was obtained in the same manner as in Preparation Example 1.

<Preparation Example 3: Preparation of Resin Paint (Composition 3)> For modulation example 1, 1) 10 parts of bisphenol type epoxy resin (epoxy equivalent of about 165g/eq., "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) were changed to 10 parts 10 parts of cyclohexane dimethanol type epoxy resin (epoxy equivalent 130g/eq., "ZX1658GS" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), 2) Change 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) to biphenyl type epoxy resin (epoxy equivalent of about 291g/eq., 10 copies of "NC3000H" manufactured by Nippon Kayaku Co., Ltd. Except for the above matters, a resin coating (composition 3) was obtained in the same manner as in Preparation Example 1.

<Preparation Example 4: Preparation of resin coating (Composition 4)> For modulation example 1, 1) The amount of bisphenol-type epoxy resin (epoxy equivalent of about 165g/eq., "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixed product of bisphenol A and bisphenol F) from 10 Changed to 20 copies, 2) Change 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) to biphenyl type epoxy resin (epoxy equivalent of about 291g/eq., 10 copies of "NC3000H" manufactured by Nippon Kayaku, 3) 10 parts of bis-xylenol type epoxy resin (epoxy equivalent of about 185g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation) are not used. Except for the above matters, a resin coating (Composition 4) was obtained in the same manner as in Preparation Example 1.

<Preparation Example 5: Preparation of Resin Paint (Composition 5)> For modulation example 1, 1) The amount of bis-cresol epoxy resin (epoxy equivalent of about 185g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation) was changed from 10 to 15 parts. 2) Change 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) to biphenyl type epoxy resin (epoxy equivalent of about 291g/eq., 5 copies of "NC3000H" manufactured by Nippon Kayaku Co., Ltd. Except for the above matters, a resin coating (Composition 5) was obtained in the same manner as in Preparation Example 1.

<Preparation Example 6: Preparation of Resin Paint (Composition 6)> For modulation example 1, 1) The amount of bisphenol-type epoxy resin (epoxy equivalent of about 165g/eq., "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixed product of bisphenol A and bisphenol F) from 10 Changed to 5 copies, 2) Change 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) to biphenyl type epoxy resin (epoxy equivalent of about 291g/eq., 25 copies of "NC3000H" manufactured by Nippon Kayaku, 3) 10 parts of bis-xylenol type epoxy resin (epoxy equivalent of about 185g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation) are not used. Except for the above matters, a resin coating (Composition 6) was obtained in the same manner as in Preparation Example 1.

<Preparation Example 7: Preparation of resin coating (Composition 7)> For modulation example 1, 1) The amount of bisphenol-type epoxy resin (epoxy equivalent of about 165g/eq., "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixed product of bisphenol A and bisphenol F) from 10 Changed to 20 copies, 2) 10 parts of biphenyl type epoxy resin (epoxy equivalent of about 271 g/eq., "NC3000L" manufactured by Nippon Kayaku Co., Ltd.) are not used. Except for the above matters, a resin coating (Composition 7) was obtained in the same manner as in Preparation Example 1.

The components used for the preparation of Compositions 1 to 7 and the blending amount (parts by mass) are shown in the following table.

<Example 1: Preparation of adhesive sheet with support> As a support, on the release surface of a PET film ("LumirrorT6AM" manufactured by Toray Corporation, thickness 38 μm) that was released with a non-silicone mold release agent ("AL-5" manufactured by Lintec), a mold was used. The resin coating (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 is 20 μm. Next, a protective film is provided so as to be bonded to the resin composition layer. As the protective film, a polypropylene film ("Biaxially stretched polypropylene film, "MA430" manufactured by Oji F-Tex Co., Ltd., thickness 20 μm, arithmetic average roughness 1000 nm) was used.

<Example 2: Fabrication of adhesive sheet with support> For Example 1, as the protective film, the roughened surface (arithmetic average roughness 250 nm) of a polypropylene film ("Biaxially stretched polypropylene film, product name: MA411" manufactured by Oji F-Tex Corporation, thickness 15 μm) was set to Join with the resin composition layer. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Example 3: Fabrication of adhesive sheet with support> For Example 1, composition 1 was changed to composition 2. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Example 4: Fabrication of adhesive sheet with support> For Example 1, composition 1 was changed to composition 3. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Example 5: Production of adhesive sheet with support> For Example 1, composition 1 was changed to composition 4. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Example 6: Production of adhesive sheet with support> For Example 1, composition 1 was changed to composition 5. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Comparative Example 1: Fabrication of Adhesive Sheet with Support> For Example 1, composition 1 was changed to composition 6. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Comparative Example 2: Fabrication of Adhesive Sheet with Support> For Example 1, as a protective film, the smooth surface (arithmetic average thickness 50nm) of a polypropylene film ("Biaxially stretched polypropylene film, product name: MA411" manufactured by Oji F-Tex Corporation, thickness 15 μm) was set to The resin composition layer is joined. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Comparative Example 3: Fabrication of Adhesive Sheet with Support> For Example 1, composition 1 was changed to composition 7. Except for the above matters, an adhesive sheet with a support was produced in the same manner as in Example 1.

<Measurement of the arithmetic average roughness (Ra2) of the second surface of the resin composition layer> The adhesive sheet with a support obtained in Examples and Comparative Examples peeled off the protective film. Within 15 minutes after peeling off the protective film, the arithmetic average roughness of the surface of the resin composition layer is obtained from the following value, which is a non-contact surface roughness meter ("WYKO NT3300" manufactured by VICO INSTRUMENTS), by VSI Mode, 50x lens, and set the measurement range to 121μm × 92μm. For each sample, it was measured by averaging 10 points without selection.

<Measurement of minimum melt viscosity of resin composition layer> For the resin composition layer of the attached sheet with the support, a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by You BM Corporation) was used to measure the minimum melt viscosity. For 1 g of the sample resin composition taken from the resin composition layer, a parallel plate with a diameter of 18 mm was used, and the temperature was raised from a starting temperature of 60° C. to a temperature of 200° C. at a heating rate of 5° C./min. The dynamic viscoelasticity and the lowest melt viscosity (poise) were measured under the measurement condition of strain 1deg.

<Measurement of Adhesion of the Second Surface of the Resin Composition Layer at 80°C> The protective film is peeled off from the supporting sheet obtained in Examples and Comparative Examples, and the resin composition layer is probed with a probe adhesion tester ("TE-6002" manufactured by Tester Industries Co., Ltd.), measured with a glass probe with a diameter of 5 mm under a load of 1 kgf/cm ² , a contact speed of 0.5 mm/second, a stretching speed of 0.5 mm/second, a holding time of 10 seconds, and a temperature Adhesion at 80℃.

<Evaluation of part embedment> Using the support sheet with the support obtained in Examples and Comparative Examples, a circuit board temporarily attached with electronic parts was manufactured according to the following procedure to evaluate the embeddability.

(1) Preparation of electronic parts point circuit board (cavity board) On the both sides of the glass cloth substrate BT resin, copper laminates (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA") 255mm × 340mm, a cavity of 0.7mm × 1.1mm Formed at a pitch of 3mm. Next, the both surfaces were etched with a micro-etching agent ("CZ8101" manufactured by MEC Corporation) at 1 [mu]m, and then roughened on the copper surface, and further subjected to anti-rust treatment ("CL8300" manufactured by MEC Corporation), and then dried at 190°C for 30 minutes.

(2) Fabrication of electronic components circuit board On one side of the substrate obtained in (1), a polyimide film with a thickness of 25 μm with an adhesive (polyimide, thickness 38 μm, manufactured by Aizawa Manufacturing Co., Ltd., “PFDKE-1525TT”) is used in batches A vacuum-pressed laminate (second-level accumulation laminate "CVP700" manufactured by Nikko Material Co., Ltd.) is provided with an adhesive to be bonded to the substrate and laminated on one side. Lamination was carried out by depressurizing for 30 seconds to make the air pressure below 13 hPa, and then pressing at 80° C. and a pressure of 0.74 MPa for 30 seconds. Next, each of the laminated ceramic capacitor parts (1005=1mm×0.5mm size, thickness 0.14mm) was separately fired in the cavity to produce a circuit board (cavity substrate) for electronic parts.

(3) Evaluation of parts embeddability Using a test batch-type vacuum pressurized laminate (second-level accumulation laminate "CVP700" manufactured by Nikko･Materials Co., Ltd.), the protective sheet with the support prepared in the examples and comparative examples was peeled off and the protective film was exposed. The resin composition layer is laminated and bonded to the polyimide film-attached surface of the adhesive-attached circuit board (cavity substrate) of the electronic component manufactured in (2) on the reverse side. The lamination is carried out within 15 minutes after the peeling of the protective film, and after 30 seconds of depressurization to reduce the pressure to 13 hPa or less (the degree of vacuum at the time of lamination is 0.5 hPa), it is carried out by pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds. . Next, the laminated support sheet with the support was hot-pressed at 100° C. and a pressure of 0.5 MPa under atmospheric pressure for 60 seconds to smooth it. After the circuit board temporarily attached with the electronic parts cooled to room temperature, the polyimide film with the adhesive was peeled off, and the evaluation board A was produced. From the surface of the polyimide film on the evaluation substrate A, the resin flow in the cavity was observed with an optical microscope (150 times). This observation was made for 10 cavities, and the part embeddability was evaluated by the following criteria. ○: For all the cavities, the peripheral part of the laminated ceramic capacitor part is covered with the resin composition layer. ×: Even if there is only one cavity, a gap is generated, or a resin composition layer is not embedded in the peripheral portion of the laminated ceramic capacitor component.

＜Empty evaluation＞ For the evaluation substrate A, observe the portion other than the cavity portion with an optical microscope (150 times), and evaluate whether a void is generated between the resin composition layer and the electronic component point circuit board, and evaluate based on the following criteria. ○: There is no void. ×: There is a void.

1‧‧‧ Adhesive sheet with support 2‧‧‧Resin composition layer 2a‧‧‧The first side of the resin composition layer 2b‧‧‧The second side of the resin composition layer 3‧‧‧Support 4‧‧‧Protection film 4a‧‧‧Protect the first side of the film 4b‧‧‧Protect the second side of the film 10‧‧‧ circuit board 10A‧‧‧Electronic parts point circuit board 20‧‧‧ substrate 20a‧‧‧ Cavity 30‧‧‧Loop wiring 40‧‧‧ point material 50‧‧‧Electronic parts

[FIG. 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a support-attached adhesive sheet of the present invention. [FIG. 2] FIG. 2 is a schematic cross-sectional view for explaining an example of a support-attached sheet of the present invention. [Fig. 3] Fig. 3 shows a schematic cross-sectional view for explaining an example of a circuit board. [FIG. 4] FIG. 4 is a schematic cross-sectional view for explaining an example of a circuit board provided with a cavity. [Fig. 5] Fig. 5 is a schematic cross-sectional view for explaining an example of a state in which a tack weld material is laminated on a circuit board provided with a cavity. [Fig. 6] Fig. 6 is a schematic cross-sectional view for explaining an example of how a tack weld of an electronic component is performed on an adhesive surface of a spotted material exposed through a cavity. [Fig. 7] Fig. 7 is a schematic cross-sectional view for explaining an example of a state in which a resin composition layer of an adhesive sheet with a support is bonded to a circuit board by lamination using a vacuum lamination device. [FIG. 8] 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] Fig. 9 is a schematic cross-sectional view for explaining an example of a state in which a spot material is peeled off.

1‧‧‧ Adhesive sheet with support

2‧‧‧Resin composition layer

2a‧‧‧The first side of the resin composition layer

2b‧‧‧The second side of the resin composition layer

3‧‧‧Support

Claims (11)

A support-attached adhesive sheet, which 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 It is characterized in that the arithmetic mean roughness (Ra2) of the second surface of the resin composition layer is 150 nm or more, and the adhesive force of the second surface of the resin composition layer at 80° C. is 1.1 N or more and 1.5 N or less. The adhesive-attached sheet as claimed in claim 1, which is used to form an insulating layer when a vacuum laminating device is to be used. The adhesive-attached sheet as claimed in claim 2, wherein the vacuum degree in the vacuum lamination device is 0.01 hPa or more and 4 hPa or less. The adhesive-attached sheet as in claim 1, which is used to form an insulating layer for embedding electronic parts. The adhesive-attached sheet as claimed in claim 1, which is used to form an insulating layer on a circuit board. The adhesive sheet with a support according to claim 1, wherein the minimum melt viscosity of the resin composition layer at 60°C to 200°C is 2000 poise or less. As in the adhesive-attached sheet of claim 1, wherein the resin composition layer contains the resin composition, the resin composition contains the inorganic filler, and the content of the inorganic filler, when the nonvolatile component in the resin composition is taken as 100 At mass%, it is 70 mass% or more. The adhesive-attached sheet as claimed in claim 1, wherein the resin composition layer contains a resin composition, and the resin composition contains a liquid epoxy resin and a solid epoxy resin. The adhesive-attached sheet of claim 1 further contains a protective film having a first surface and a second surface, and the first surface of the protective film is bonded to the second surface of the resin composition layer. An adhesive sheet with a support as claimed in claim 9, wherein the arithmetic average roughness of the first surface of the protective film is 150 nm or more. A circuit board characterized by including an insulating layer formed by a hardened product of a resin composition layer of a support attached adhesive sheet according to any one of claims 1 to 10.

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