TW202030238A - Dry film, cured product, and electronic component resulting in no bulging of the protective film or cracking of the resin - Google Patents

Abstract

A subject of the present invention is to provide a dry film, which does not cause resin to adhere to a blade even if a cutting process is continuously performed, resulting no cracks or bulging of the resin at the end and no bulging of the protective film. The solution of the present invention is a dry film provided with a carrier film, a resin layer and a protective film, which is characterized in that: the peel strength of the protective film relative to the resin layer is 0.010kgf/cm or more, and the peel strength of the protective film relative to the resin layer is greater than the peel strength of the carrier film relative to the resin layer.

Description

Dry film, hardened material and electronic parts

The present invention relates to dry films, hardened products and electronic parts.

Conventionally, as one of the means for forming protective films or insulating layers such as solder resists or interlayer insulating layers that are provided on printed wiring boards used in electronic equipment, etc., dry films (laminated films) have been used (for example, Patent Document 1). The dry film has a resin layer obtained by coating a resin composition with desired characteristics on the carrier film and then undergoing a drying step. Generally speaking, it is a layer for protecting the side opposite to the carrier film. The state of the protective film is circulating in the market. After the resin layer of the dry film is attached (hereinafter also referred to as "laminating") on the substrate, patterning or hardening is applied to produce a printed wiring board with the above-mentioned protective film or insulating layer.

The protective film is removed from the resin layer when the dry film is adhered to the substrate. At that time, in order to prevent the resin composition from being transferred to the protective film (hereinafter also referred to as "resin separation"), it was used in the dry film manufacturing process. , Adjust the conditions so that the peel strength of the protective film with respect to the resin composition becomes small. Patent Document 2 discloses an adhesive sheet with a protective film that does not peel off the resin when the protective film is peeled off, and an adhesive sheet with a protective film whose peel strength of the protective film is lower than the peel strength of the carrier film by 0.0020 kgf/cm or more. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-010179 [Patent Document 2] Japanese Invention Patent No. 6353184

[The problem to be solved by the invention]

The aforementioned three-layer dry film with a protective film and a carrier film is usually made by first adjusting the viscosity of the curable resin composition by the amount of solvent, then coating it on the carrier film, and then drying it in a drying oven, and then the carrier film A resin layer is formed on the surface, and then a protective film is attached to the surface of the dry film to produce a long dry film. The shape of the long dry film is, for example, a roll shape with a width of 1 m and a length of 1000 m.

The aforementioned long dry film is cut (cut) according to the required length and width, for example, to become a dry film whose width is adjusted to 50 cm, but for example, as mentioned above, the cutting process is continuously performed in a length of 1000 m At this time, in the conventional dry film, the resin adheres to the blade and the sharpness deteriorates. As a result, the resin at the end may be broken or floated, and the protective film may float.

Therefore, the object of the present invention is to provide a dry film, a cured product of the resin layer of the dry film, and an electronic component having the cured product. Even if the dry film is continuously cut, the resin does not adhere to the blade and is sharp. As a result, the resin at the end will not be broken or floated, and the protective film will not float. [Means to solve the problem]

The inventors intensively reviewed and found that by fully adhering the protective film to the resin layer, a dry film whose peel strength relative to the resin layer’s protective film satisfies a certain condition can solve the above-mentioned problems, and in this case, also The transfer of the resin composition to the protective film when the protective film was removed from the resin layer was not initially concerned, and finally completed the present invention. That is, the dry film of the present invention is a dry film provided with a carrier film, a resin layer, and a protective film, and is characterized in that the peel strength of the protective film relative to the resin layer is 0.010 kgf/cm or more, and is relative to the resin layer. The peel strength of the protective film of the layer is greater than the peel strength of the carrier film of the resin layer.

The peel strength of the dry film-based protective film of the present invention is preferably greater than the peel strength of the carrier film relative to the resin layer by 0.005 kgf/cm or more.

The thickness of the dry film of the present invention is preferably 60 μm or more.

The above-mentioned protective film of the dry film system of the present invention preferably has adhesiveness.

The cured product of the present invention is characterized by curing the resin layer of the aforementioned dry film.

The electronic component of the present invention is characterized by having the aforementioned hardened substance. [Effects of the invention]

According to the present invention, it is possible to provide a dry film, a cured product of the resin layer of the dry film, and an electronic component having the cured product. Even if the dry film is continuously cut, the resin does not adhere to the blade and the sharpness is deteriorated. , As a result, no cracking or floating of the resin at the end and floating of the protective film occurred.

[The form of implementing the invention] ＜Dry film＞

Fig. 1 shows a schematic cross-sectional view of the dry film of the present invention. The dry film 11 of the three-layer structure of the present invention has a structure in which a resin layer 12 is formed on a carrier film 13 and a protective film 14 is laminated. The dry film of the present invention is characterized in that in such a three-layered dry film, the peel strength of the protective film relative to the resin layer is 0.010kgf/cm or more, and the peel strength of the protective film relative to the resin layer is greater than The peel strength of the carrier film of the resin layer. Here, as the upper limit of the peel strength of the protective film with respect to the resin layer, for example, if it is 0.150 kgf/cm or less, it is possible to well prevent the resin composition from being transferred to the protective film. Furthermore, in the dry film of the present invention, the peel strength of the protective film with respect to the resin layer is preferably greater than the peel strength of the carrier film with respect to the resin layer by 0.005 kgf/cm or more. Here, as the upper limit of the difference in peel strength, for example, if it is 0.150 kgf/cm or less, it is possible to well prevent the resin composition from being transferred to the protective film.

Since the dry film of the present invention satisfies the aforementioned requirements, even if the cutting process is continuously performed, the resin will not adhere to the blade and the sharpness will not deteriorate. As a result, the resin at the end will not break or float, and the protective film will not float. . Such an effect is significant in dry films having a thickness of 60 μm or more, more significant in dry films having a thickness of 100 μm or more, and particularly significant in dry films having a thickness of 150 μm or more. The upper limit of the thickness of the dry film is 500 μm.

[Protective Film] The so-called protective film is to prevent dust etc. from adhering to the surface of the resin layer of the dry film, or to prevent physical damage to the surface of the resin layer when the dry film is cut and process the dry film, and to improve the workability. It is installed on the resin layer. It is the opposite side of the carrier film. Examples of materials used for the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, polycarbonate, and polyimide.

As the protective film of the present invention, as long as it satisfies: the peel strength of the protective film relative to the resin layer is 0.010kgf/cm or more, and the peel strength of the protective film relative to the resin layer is greater than the peel strength of the carrier film relative to the resin layer For the requirements of the present invention, any commercially available protective film can be used. For example, conventional films such as biaxially stretched polypropylene films MA-411, MA-420, and MAM-430 manufactured by Oji F-TEX Co., Ltd. can also adjust the pressure or temperature during bonding to improve the peel strength of the protective film. Suitable films for use include self-adhesive biaxially stretched polypropylene films 100M, 150M, 300M manufactured by Fukumura Chemical Co., Ltd., heat-resistant micro-adhesive special polyester film T-APN10 manufactured by Nitto Shinko Co., and Somatac WA series manufactured by Somar Co. (PS-105WA, PS-1080WA, PS-503WA, etc.), Teraoka Manufacturing Co., Ltd. film masking tape (465 #40, etc.), PEEK film adhesive tape (4920 0.012, etc.), silicone rubber double-sided adhesive tape (9030W) , LINTEC's adhesives (MF, MA, Ntac, REPOP polysiloxane micro-adhesive, etc.) are formed on PET or OPP film, Hitachi Chemical's adhesive film "Hitalex", A-2400 series, D- 5700 series, GS-1000 series, L-1200 series, L-3300 series, BN-1000, Lioelm LE950 series (LE951, LE957L) manufactured by Toyo Chemical Company, Panaprotect (HP, CT, ET, MK, etc.) manufactured by PANAC ), adhesive films made by Bachuan Company (CA01, CA22, CA91, CA31, CA32, Clearvisible, etc.), DNP heat-resistant adhesive films made by DNP, etc.

Here, in the present invention, the peel strength of the protective film relative to the resin layer refers to the peel strength (90° peel strength) when the protective film is torn off the resin layer in the vertical direction (90° direction). The peel strength when the film is torn to the resin layer at a tear angle of 90° can be determined by a tensile testing machine. As a tensile tester, for example, the universal tensile tester AG-X manufactured by Shimadzu Corporation can be mentioned.

When bonding the protective film to the resin layer, it is preferable to laminate the protective film to the resin layer by a roll or pressure bonding under a temperature condition around the lowest melting temperature of the curable resin composition. The crimping pressure of the lamination process is preferably 0.01 kgf/cm ² to 20 kgf/cm ² . Here, the definition of the minimum melting temperature is as follows. <Definition of the minimum melting temperature> Use a vacuum laminator MVLP-500 (manufactured by Meiji Corporation) to produce a dry film (40μm) under the conditions (temperature 50℃, time 120sec, pressure 0.5MPa, peeling off the protective film surface ), prepare a sample for melt viscosity measurement with a thickness of 200 μm and a size of 50×50 mm. Next, it was processed into a circle with a measurement size of φ20 mm, and the PET film on the front and back was peeled off to prepare a sample for measurement. Then, using a rheometer HAAKE MARS40 (manufactured by Thermo Fisher), it was defined by the viscosity when the melt viscosity was measured under the following conditions. The measurement is performed with a sensor parallel plate φ20mm, strain 2%, frequency 1Hz vibration mode, measurement sample gap 180μm, 5°C/min from room temperature, and the temperature rise is defined by the temperature when the viscosity of the material becomes the lowest.

Here, while using a protective film that does not have micro-adhesive properties, in order to expand the peel strength of the protective film with respect to the resin layer to the scope of the present invention, the bonding temperature must be higher than the conventional bonding temperature. When the bonding temperature is uneven, or when the bonding temperature becomes too high, the problem of elongation of the protective film may occur, or it may become curled due to the difference in the shrinkage rate of the protective film and the resin layer or carrier film during shrinkage after bonding. The question of status. Therefore, for the reason that the peel strength of the protective film can be improved without increasing the bonding temperature in the present invention, it is preferable to use an adhesive protective film such as a micro-adhesive protective film. As the constituent material of the adhesive layer of the adhesive protective film, a styrene-based polymer or a styrene-isoprene-based polymer is preferable.

In addition, as the protective film, it is preferable to use a biaxially stretched polypropylene film from the viewpoint of reducing cooling shrinkage after lamination to the resin layer.

The thickness of the protective film is not particularly limited, and can be appropriately selected in the range of about 10-100 μm according to the application. The surface where the resin layer is provided on the protective film is preferably subjected to embossing processing, corona processing, micro-adhesion processing, or other processing to improve adhesion or release processing.

[Resin layer] The resin layer of the dry film of the present invention is generally referred to as the state of the B-stage state, and is obtained from the curable resin composition, specifically, the curable resin composition is applied to the film and then dried. The thickness of the resin layer is not particularly limited. For example, the thickness may be 1 to 200 μm. In the present invention, when the thickness is large, the flatness is excellent. Therefore, for example, the thickness is 30 μm or more, especially 50 μm or more, and further 100 μm or more. In addition, by stacking plural resin layers of the dry film of the present invention, a resin layer having a thickness of more than 200 μm may be formed. At that time, a roll laminator or a vacuum laminator was sufficient.

The aforementioned resin layer preferably contains a curable resin, for example, an epoxy resin. The epoxy resin is a resin having an epoxy group, and any known ones can be used. Examples include bifunctional epoxy resins having two epoxy groups in the molecule, and multifunctional epoxy resins having three or more epoxy groups in the molecule. In addition, it may be a hydrogenated epoxy resin. The resin layer contains at least any one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin. Semi-solid epoxy resin and crystalline epoxy resin can be used individually by 1 type or in combination of 2 or more types. In addition, the aforementioned resin layer may contain a solid epoxy resin or a liquid epoxy resin. In this specification, solid epoxy resin means solid epoxy resin at 40°C, semi-solid epoxy resin means solid epoxy resin at 20°C, liquid epoxy resin at 40°C, liquid ring Oxygen resin refers to epoxy resin that is liquid at 20°C. The determination of the liquid state is based on the "Method of Confirming Liquid State" in Annex No. 2 of the Provincial Order concerning the test and the nature and shape of hazardous materials (Japan Autonomous Ministry Order No. 1). For example, it is performed by the method described in paragraphs 23 to 25 of JP 2016-079384 A. In addition, crystalline epoxy resin means an epoxy resin with strong crystallinity. At a temperature below the melting point, the polymer chains are regularly arranged. Although it is a solid resin, it has the same low viscosity as a liquid resin during melting. Thermosetting epoxy resin.

Examples of semi-solid epoxy resins include EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822 manufactured by DIC, Epotohto YD-134 manufactured by Toto Kasei Co., Ltd., jER834 and jER872 manufactured by Mitsubishi Chemical Corporation, and Sumitomo Chemical Bisphenol A type epoxy resin such as ELA-134 manufactured by the company; naphthalene type epoxy resin such as EPICLON HP-4032 manufactured by DIC company; phenol novolac type epoxy resin such as EPICLON N-740 manufactured by DIC company. The semisolid epoxy resin preferably contains at least one selected from the group consisting of bisphenol A epoxy resin, naphthalene epoxy resin, and phenol novolak epoxy resin. By including semi-solid epoxy resin, the glass transition temperature (Tg) of the hardened product is high, the CTE is low, and the crack resistance is excellent.

As the crystalline epoxy resin, for example, a crystalline epoxy resin having a biphenyl structure, a sulfide structure, a phenylene structure, a naphthalene structure, or the like can be used. Biphenyl type epoxy resins can be provided, for example, by Mitsubishi Chemical Corporation jER YX4000, jER YX4000H, jER YL6121H, jER YL6640, jER YL6677, and diphenyl sulfide type epoxy resins can be provided, for example, by Totoh Kasei Co., Ltd. Epotohto YSLV-120TE, The phenylene type epoxy resin can be provided, for example, by Tohto Kasei Co., Ltd. Epotohto YDC-1312, and the naphthalene type epoxy resin can be provided, for example, by DIC Co., Ltd. EPICLON HP-4032, EPICLON HP-4032D, and EPICLON HP-4700. In addition, as the crystalline epoxy resin, Epotohto YSLV-90C manufactured by Totoh Chemical Co., Ltd. and TEPIC-S (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd. can also be used.

Examples of solid epoxy resins include HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (4-functional naphthalene epoxy resin) manufactured by DIC, and NC-7000 (containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Multifunctional solid epoxy resin) and other naphthalene type epoxy resins; EPPN-502H (triphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. Epoxides of condensation products of phenols and aromatic aldehydes with phenolic hydroxyl groups (Triphenol type epoxy resin); Dicyclopentadiene aralkyl type epoxy resin such as EPICLON HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC; Nippon Kayaku Biphenyl aralkyl type epoxy resin such as NC-3000H (multifunctional solid epoxy resin containing biphenyl skeleton) manufactured by the company; Biphenyl/phenol novolac type epoxy resin such as NC-3000L manufactured by Nippon Kayaku Co., Ltd. ; EPICLON N660, EPICLON N690, N770 manufactured by DIC Corporation, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Novolac epoxy resin; Nippon Steel & Sumikin Chemical Corporation TX0712, etc. phosphorous epoxy resin; TEPIC manufactured by Nissan Chemical Co., Ltd. Etc. (2,3-epoxypropyl) isocyanurate, etc. Since it contains a solid epoxy resin, the glass transition temperature of the cured product becomes high, and the heat resistance is excellent.

Examples of liquid epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, phenol novolac epoxy resins, and tertiary butyl catechol Type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin, alicyclic epoxy resin, etc. Since it contains liquid epoxy resin, the dry film has excellent flexibility.

The total blending amount of the semi-solid epoxy resin and the crystalline epoxy resin is based on the total amount of the epoxy resin, preferably 5-40% by mass, more preferably 10-30% by mass. If it is within the above range, the resin layer of the dry film has excellent viscosity and flexibility.

[Inorganic Filler] The aforementioned resin layer preferably contains an inorganic filler. By blending inorganic fillers, the hardening shrinkage of the obtained hardened material is suppressed, and the adhesion, hardness, and thermal characteristics of the conductive layer such as copper and the like around the insulating layer and the thermal resistance due to the thermal strength are improved. . As the inorganic filler, conventional inorganic fillers can be used, and they are not specified, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, etc. Of silicon dioxide, talc, clay, Neuburg silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate Extender pigments such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, platinum and other metal powders. The inorganic filler is preferably spherical particles. Among them, silicon dioxide is preferred, which suppresses the curing shrinkage of the cured product of the curable composition, becomes lower CTE, and improves the properties such as adhesion and hardness. In addition, as for alumina, inorganic fillers with a high specific gravity generally have a faster sedimentation rate, but they are applicable because sedimentation can be suppressed in the present invention. The average particle diameter (median particle diameter, D50) of the inorganic filler is preferably 0.01 to 10 μm. As the inorganic filler, from the viewpoint of cutting processability, silica having an average particle diameter of 0.01 to 3 μm is preferred. In this specification, the average particle diameter of the inorganic filler is not only the particle diameter of the primary particles, but also the average particle diameter of the secondary particles (aggregates). The average particle size can be determined by a laser diffraction particle size distribution measuring device. As a measuring device of the laser diffraction method, the Nanotrac wave manufactured by Microtrac Bel, etc. can be mentioned.

The aforementioned inorganic filler system may be surface-treated. As the surface treatment, the surface treatment of the coupling agent or the surface treatment such as alumina treatment without introducing organic groups is performed. The surface treatment method of the inorganic filler is not particularly limited, as long as the well-known and commonly used method is used, as long as the surface treatment agent with a curable reactive group, for example, a coupling agent with a curable reactive group as an organic group, is used to treat the inorganic The surface of the filler is sufficient.

The inorganic filler system may be blended with epoxy resin or the like in a powder or solid state, or may be blended with epoxy resin or the like after being mixed with a solvent or dispersant to form a slurry.

The inorganic filler system may be used alone or as a mixture of two or more types. The blending amount of the inorganic filler is based on the total solid content of the resin layer of the dry film, and is preferably 10 to 90% by mass, more preferably 50 to 90% by mass, and particularly preferably 60 to 90% by mass. When the blending amount of the inorganic filler is 10% by mass or more, thermal expansion can be suppressed and heat resistance can be improved. On the other hand, when the amount is less than 90% by mass, the occurrence of cracks can be suppressed.

[hardener] The aforementioned resin layer preferably contains a curing agent. Examples of hardeners include compounds having phenolic hydroxyl groups, polycarboxylic acids and their anhydrides, compounds having cyanate ester groups, compounds having active ester groups, compounds having maleimide groups, and alicyclic compounds. Olefin polymers, etc. The hardening agent system can be used individually by 1 type or in combination of 2 or more types.

In the present invention, the resin layer preferably contains at least any one of a compound having a phenolic hydroxyl group, a compound having an active ester group, a compound having a cyanate group, and a compound having a maleimide group. By using a compound having a phenolic hydroxyl group and a compound having an active ester group, a cured product having a low-thickness substrate or excellent adhesion to a circuit can be obtained. In addition, by using cyanate ester, the Tg of the cured product becomes higher, and the heat resistance is increased. By using a compound having a maleimide group, the Tg of the cured product becomes higher, the heat resistance is increased, and the CTE can be reduced. .

As the aforementioned compound having a phenolic hydroxyl group, phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene can be used Modified phenol resin, cresol/naphthol resin, polyvinyl phenols, phenol/naphthol resin, phenol resin containing α-naphthol skeleton, cresol novolak resin containing tri-skeleton, biphenylarane Those who are familiar with basic phenol resin, new phenol phenol novolak resin, etc. Among the aforementioned compounds having a phenolic hydroxyl group, those having a hydroxyl equivalent of 100 g/eq. or more are preferred. Examples of compounds having a phenolic hydroxyl group with a hydroxyl equivalent of 100 g/eq. or more include dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Kunei Chemical Co., Ltd.), and novel phenol novolac resin (MEH- 7800, made by Meiwa Chemical Co., Ltd.), biphenyl aralkyl type novolac resin (MEH-7851, made by Meiwa Chemical Co., Ltd.), naphthol aralkyl type hardener (SN series, manufactured by Nippon Steel & Sumikin Co.), containing Tri-skeleton cresol novolac resin (LA-3018-50P, manufactured by DIC Corporation), tri-skeleton-containing phenol novolac resin (LA-705N, DIC Corporation), etc.

The aforementioned compound having a cyanate group is preferably a compound having two or more cyanate groups (-OCN) in one molecule. Any conventional compound can be used for the compound having a cyanate ester group. Examples of the compound having a cyanate group include phenol novolac type cyanate resin, alkylphenol novolac type cyanate resin, dicyclopentadiene type cyanate resin, and bisphenol A type cyanate resin. Ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin. In addition, it can also be a part of the prepolymer that has undergone a triad.

Examples of commercially available compounds having cyanate groups include phenol novolac type polyfunctional cyanate resin (manufactured by LONZA Japan, PT30S), and bisphenol A dicyanate in which a part or all of it has been trioxidized Prepolymer of trimer (made by LONZA Japan, BA230S75), cyanate ester resin containing dicyclopentadiene structure (made by LONZA Japan, DT-4000, DT-7000), etc.

The aforementioned compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. Compounds with active ester groups can generally be obtained by the condensation reaction of carboxylic acid compounds and hydroxyl compounds. Among them, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as the hydroxyl compound is preferred. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac Wait. In addition, as a compound having an active ester group, a naphthalenediol alkyl/benzoic acid type may be used.

Examples of commercially available compounds having active ester groups include dicyclopentadiene-type diphenol compounds, such as HPC8000-65T (manufactured by DIC Corporation), HPC8100-65T (manufactured by DIC Corporation), HPC8150-65T (Dic company system).

The aforementioned compound having a maleimine group is a compound having a maleimine skeleton, and any conventionally known compound can be used. The compound having a maleimide group preferably has a maleimide skeleton of 2 or more, more preferably N,N'-1,3-phenylene dimaleimide, N,N'- 1,4-Phenyldimaleimide, N,N'-4,4-diphenylmethane bismaleimide, 1,2-bis(maleimide)ethane, 1 ,6-Bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,2'-bis-(4-(4- (Maleimide phenoxy) phenyl) propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4- Methyl-1,3-phenylene bismaleimide, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, bisphenol A diphenyl ether bismarine Leximine, polyphenylmethane maleimide, and at least any one of these oligomers, and diamine condensates having a maleimine skeleton. The aforementioned oligomer is an oligomer obtained by condensing a compound having a maleimide group among monomers among the above-mentioned maleimide group-containing compounds.

Examples of commercially available compounds having a maleimide group include BMI-1000 (4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-2300 (phenyl Methane bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd., BMI-3000 (m-phenylene bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-5100 (3,3'-dimethyl -5,5'-Dimethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd., BMI-7000 (4-methyl-1,3,-phenylene Bismaleimide, manufactured by Daiwa Chemical Co., Ltd.), BMI-TMH ((1,6-Bismaleimide-2,2,4-trimethyl)hexane, manufactured by Daiwa Chemical Co., Ltd.), etc. .

The blending amount of the hardener is preferably 20-100 parts by mass, more preferably 25-90 parts by mass relative to 100 parts by mass of epoxy resin.

Specific examples of the curable resin composition forming the aforementioned resin layer include thermosetting resin composition, photocuring thermosetting resin composition, and photocuring thermosetting resin composition containing a photopolymerization initiator. Photocurable thermosetting resin composition containing photoalkali generator, photocurable thermosetting resin composition containing photoacid generator, negative photocuring thermosetting resin composition and positive photosensitive Thermosetting resin composition, alkali-developing photo-curing thermosetting resin composition, solvent-developing photo-curing thermosetting resin composition, swelling peeling type thermosetting resin composition, dissolving peeling type thermosetting The resin composition is not limited by these.

Hereinafter, as an example, regarding a case where the resin layer is formed from a thermosetting resin composition that does not contain a photocurable component, components that may be contained in addition to the above-mentioned components will be described.

The aforementioned resin layer may contain thermosetting resins other than epoxy resins. For example, isocyanate compounds, blocked isocyanate compounds, amino resins, benzodiazepine resins, carbodiimide resins, cyclic carbonate compounds, and polyfunctional oxygen can be used. Well-known and commonly used thermosetting resins such as ethidium compounds and episulfide resins.

The aforementioned resin layer may further contain a thermoplastic resin in order to increase the mechanical strength of the cured film obtained. The thermoplastic resin is preferably one that is soluble in a solvent. When it is soluble in solvents, it can improve the softness of the dry film and inhibit the occurrence of cracks or powder falling. Examples of thermoplastic resins include thermoplastic polyhydroxy polyether resins, or phenoxy resins of condensates of epichlorohydrin and various bifunctional phenol compounds, or hydroxy ethers existing in the skeleton. Various acid anhydrides or phenols are used for the hydroxyl group. Chlorine esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyimide imine resin, block copolymer, etc. The thermoplastic resin system can be used individually by 1 type or in combination of 2 or more types.

The aforementioned resin layer contains a polymer resin. The glass transition point of the aforementioned polymer resin is preferably -40 to 20°C, more preferably -15 to 15°C, particularly preferably -5 to 15°C. If it is -5 to 15°C, the warpage of the hardened product can be suppressed well. In addition, the higher the weight average molecular weight of the aforementioned polymer resin, the greater the effect of preventing sedimentation of the inorganic filler, so it is preferably 100,000 or more, and more preferably 200,000 or more. The upper limit is, for example, 1 million or less.

Examples of polymer resins include butadiene skeletons, amide skeletons, amide skeletons, acetal skeletons, carbonate skeletons, ester skeletons, urethane skeletons, acrylic skeletons, and silicone skeletons. Selected one or more kinds of polymer resins with a skeleton, etc. For example, a polymer resin having a butadiene skeleton ("G-1000", "G-3000", "GI-1000", "GI-3000", "GI-3000" manufactured by Soda Corporation, and "R -45EPI", "PB3600", "Epofriend AT501" manufactured by DAICEL, "Ricon130", "Ricon142", "Ricon150", "Ricon657", "Ricon130MA" manufactured by CRAY VALLEY), with butadiene skeleton and polyamide Amine skeleton polymer resin (described in JP 2006-37083 A), polymer resin with acrylic skeleton ("SG-P3", "SG-600LB", "SG-280", "SG-790", "SG-K2", "SN-50", "AS-3000E", "ME-2000" manufactured by Nejo Industrial Co., Ltd.), etc.

Based on the total solid content of the resin layer, the blending amount of the thermoplastic resin is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass. If the blending amount of the thermoplastic resin is within the above range, it is easy to obtain a uniform roughened surface state.

Furthermore, the aforementioned resin layer may contain rubber-like particles as necessary. Examples of such rubbery particles include polybutadiene rubber, polyisopropylene rubber, urethane modified polybutadiene rubber, epoxy modified polybutadiene rubber, and acrylonitrile modified polybutadiene rubber. Diene rubber, carboxyl modified polybutadiene rubber, carboxyl or hydroxyl modified acrylonitrile butadiene rubber, and their cross-linked rubber particles, core-shell rubber particles, etc., can be one type alone or two in combination More than one kind of use. These rubber-like particles are added in order to increase the flexibility of the cured film obtained, or to increase the crack resistance, to enable surface roughening treatment with an oxidizing agent, and to increase the adhesion strength with copper foil.

The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle size of the rubber-like particles in the present invention can be determined by a laser diffraction particle size distribution measuring device. For example, the rubber-like particles can be more uniformly dispersed in a suitable organic solvent by ultrasonic waves. The Nanotrac wave manufactured by Nikkiso Co., Ltd. is used to create the particle size distribution of the rubber-like particles on a mass basis, and the median diameter is taken as The average particle size is measured.

Based on the total solid content of the resin layer, the blending amount of the rubber-like particles is preferably 0.5-10% by mass, more preferably 1-5% by mass. At 0.5% by mass or more, crack resistance is obtained and the adhesion strength with conductor patterns can be improved. At 10% by mass or less, the coefficient of thermal expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the hardening characteristics increase.

The aforementioned resin layer may contain a hardening accelerator. The hardening accelerator is one that promotes the thermal hardening reaction, and is used to further improve the characteristics such as adhesion, chemical resistance, and heat resistance. Specific examples of such hardening accelerators include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, metaphenylene diamine, and Polyamines such as xylene diamine, diamino diphenyl sulfide, dicyandiamine, urea, urea derivatives, melamine, polybasic hydrazine, etc.; these organic acid salts and/or epoxy adducts ; Amine complexes of boron trifluoride; ethyldiamino-S-tris, 2,4-diamino-S-tris, 2,4-diamino-6-xylyl-S -Three derivatives such as three; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa( N-Methyl) melamine, 2,4,6-ginseng (dimethylaminophenol), tetramethylguanidine, m-aminophenol and other amines; polyvinylphenol, polyvinylphenol bromide, phenol Polyphenols such as novolac and alkylphenol novolac; organic phosphines such as tributyl phosphine, triphenyl phosphine, ginseng-2-cyanoethyl phosphine; tri-n-butyl (2,5-dihydroxy (Phenyl) phosphonium bromide, hexadecyl tributyl phosphonium chloride and other phosphonium salts; benzyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride and other quaternary ammonium salts; the aforementioned polybasic acid anhydride ；Diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate and other photocationic polymerization catalysts; Styrene-Male Acid anhydride resin; Moore reactants such as phenyl isocyanate and dimethylamine, or organic polyisocyanates such as toluene diisocyanate, isophorone diisocyanate, and dimethylamine mole reactants, metal catalysts, etc. Known hardening accelerator. Among the hardening accelerators, phosphonium salts are preferred from the viewpoint of obtaining BHAST (Biased Highly Accelerated Stress Test) resistance.

The hardening accelerator system can be used individually by 1 type or in mixture of 2 or more types. The use of a hardening accelerator is not essential, but especially when it is desired to accelerate hardening, it is preferably used in the range of 0.01-5 parts by mass relative to 100 parts by mass of epoxy resin. In the case of a metal catalyst, it is preferably 10 to 550 ppm in terms of metal, and more preferably 25 to 200 ppm based on 100 parts by mass of the compound having a cyanate ester group.

The organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. Specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Glycol ethers such as butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, butyl acetate, isobutyl acetate Esters, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; Alcohols such as ethanol, propanol, 2-methoxypropanol, n-butanol, isobutanol, isoamyl alcohol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum Petroleum solvents such as naphtha, hydrogenated naphtha, solvent naphtha, etc., as well as N,N-dimethylformamide (DMF), perchloroethylene, turpentine, etc. In addition, Swazole 1000, Swazole 1500 manufactured by Maruzen Petrochemical Company, Solvent #100, Solvent #150 manufactured by Sankyo Chemical Co., Ltd., Shellsol A100 and Shellsol A150 manufactured by Shell Chemical Japan Co., Ltd., Ipsol No. 100 and Ipsol No. 150 manufactured by Idemitsu Kosan Co., Ltd. can be used. And other organic solvents. The organic solvent system may be used alone or as a mixture of two or more types.

The amount of residual solvent in the aforementioned resin layer is preferably 0.5 to 7.0% by mass. If the residual solvent is 7.0% by mass or less, sudden boiling during thermal hardening is suppressed, and the flatness of the surface changes well. In addition, it is possible to prevent the resin from flowing due to excessive drop in melt viscosity and to improve flatness. If the residual solvent is 0.5% by mass or more, the fluidity at the time of lamination will be good, and the flatness and embedment will be improved.

The aforementioned resin layer system can also use conventional coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc., asbestos, oruben ( Orben), Benton, Weifen silica and other conventional tackifiers, silicone, fluorine, polymer and other defoamers and/or leveling agents, thiazole, three Adhesion imparting agents such as azole-based and silane coupling agents, flame retardants, titanate-based, and aluminum-based additives.

[Carrier Film] The carrier film has a function of supporting the resin layer of the dry film, and when the resin layer is formed, a film coated with a curable resin composition is applied. As the carrier film, for example, polyester film such as polyethylene terephthalate or polyethylene naphthalate, polyimide film, polyimide film, polyethylene film, and polytetrafluoroethylene can be used. Films made of thermoplastic resins such as vinyl film, polypropylene film, and polystyrene film, and surface-treated paper. Among these, from the viewpoint of heat resistance, mechanical strength, handleability, etc., a polyester film can be preferably used. The thickness of the carrier film is not particularly limited, but is appropriately selected in the range of about 10 to 150 μm according to the application. The surface of the carrier film where the resin layer is provided can also be subjected to mold release treatment. In addition, it is also possible to sputter or form an ultra-thin copper foil on the surface of the carrier film where the resin layer is provided.

As a manufacturing method of the printed wiring board using the dry film of this invention, what is necessary is just to use a conventional method. For example, when the resin layer is composed of a thermosetting resin composition, a printed wiring board can be manufactured as follows. The protective film was peeled off from the dry film, and then heated and laminated on the circuit board on which the circuit pattern was formed, and then cured by heat. The thermal hardening system can be hardened in an oven or hardened by pressing with a hot plate. When the circuit-formed substrate and the dry film of the present invention are laminated or hot plated, a copper foil or a circuit-formed substrate may be simultaneously laminated. A printed wiring board can be manufactured by forming a pattern or a through hole with a laser or a drill at a position corresponding to a designated position on the substrate on which the circuit pattern is formed to expose the circuit wiring. At this time, when there are remaining components (smudge) that cannot be completely removed on the circuit wiring in the pattern or through hole, the desmear process is performed. The carrier film can be peeled after any one of laminating, thermal hardening, laser processing, or desmearing treatment. In addition, the connection method of the interlayer circuit can also be connected by copper pillars.

The dry film of the present invention can be suitably used in the formation of permanent protective films for electronic parts, especially printed wiring boards, and among them, it can be suitably used in the formation of solder resist layers, interlayer insulating layers, and covering layers of flexible printed wiring boards. In particular, the dry film of the present invention can be suitably used for the purpose of forming a hardened product with a large amount of inorganic filler. By using the dry film of the present invention and bonding wiring, a wiring board can also be formed. It can also be used as a sealing material for semiconductor wafers. [Example]

Hereinafter, examples and comparative examples of the present invention are shown to specifically explain the present invention, but the present invention is of course not limited by the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

<Preparation of curable resin composition> The materials and solvents described in Tables 1 and 2 were put into a container, and stirred while heating to 50°C, and then the resin and coupling agent were added separately. After confirming that the resin is dissolved, the filler component is added, and the mixture is sufficiently stirred. Then, kneading was performed with a three-roll mill to adjust curable resin compositions 1 to 4.

<Production of dry film> Adjust the amount of the solvent so that the adjusted curable resin composition has a viscosity of 0.5-20dPa·s (rotational viscometer at 5rpm, 25°C), using a standard laboratory coater manufactured by HIRANO TECSEED, After drying, the thickness of the resin layer becomes 40μm, and it is applied to a carrier film (PET film; Toyobo TN-100, thickness 38μm), and then used in a drying oven with a temperature gradient at 80°C to 100°C Drying is performed so that the residual solvent of the resin layer becomes 0.5 to 2.5% by mass, and the resin layer is formed on the carrier film. Next, on the surface of the produced dry film, the nip roll surface temperature was set at 110°C, the pressure was set at 0.1kgf/cm ² , and the protective film described in the table (OPP film MA-411, FUKUMURA manufactured by Oji F-TEX) Self-adhesive OPP film 100M manufactured by Chemical Company, or heat-resistant micro-adhesive special polyester film T-APN10 manufactured by Nitto Shinko Co., Ltd.) was laminated to produce rolls of three-layer structure of Examples 1 to 6 and Comparative Example 1 with a weight of 1000m Like dry film. Specifically, a protective film MA-411 having no adhesiveness was used, and the protective film was bonded to the curable resin composition under normal bonding temperature conditions to prepare Comparative Example 1. In contrast, the protective film MA-411, which is also non-adhesive, was used to make the bonding temperature of the protective film higher than the usual bonding temperature conditions to produce Example 1. Furthermore, instead of the non-adhesive protective film MA -411, using the adhesive protective film 100M and T-APN10 to make Examples 2-6.

＜Measurement of peel strength＞ For the obtained dry film of the three-layer structure, the peel strength of (A) the carrier film relative to the resin layer and the peel strength of (B) the protective film relative to the resin layer were measured. Using an adhesive, fix the resulting dry film on FR4 with a thickness of 1.6mm, introduce a cut with a width of 10mm and a length of 150mm in the surface of the film, and tear off one end of the film. Then, the end of the film was fixed with a jig, and the peel strength was measured using the universal tensile tester AG-X manufactured by Shimadzu Corporation. The test method is based on JIS-C-6481, with a temperature of 25°C, a tearing angle of 90°, and a speed of 50mm/min. Table 3 shows the measurement results.

＜Evaluation of resin peeling＞ For the obtained dry film in the form of a roll of three-layer structure, the automatic cutting device TS-350P (manufactured by Sakashita Iron Works) was used to perform cutting processing at a continuous 1000 m portion, and then the state of the resin end of the cut surface was evaluated. The evaluation criteria are as follows. Table 3 shows the measurement results. ○: There is no resin end cracking or peeling of the protective film even after 1000m processing. ×: After processing at 1000 m, cracking of the resin end and peeling of the protective film (floating about 3 mm) were observed.

<Evaluation of transfer of resin composition (separation of resin)> Set the produced long dry film with a three-layer structure (a roll product with a thickness of 40μm, a width of 490mm, and a length of 100m) on the automatic cutting laminator HLM-A60-T (manufactured by Hitachi Chemical Co., Ltd.), After the protective film was peeled off by the roller, a temporary attachment test of 20 sheets was continuously performed on a copper-clad plate with a size of 500×500 mm and a thickness of 0.8 mm at a lamination speed of 1 m/min, a roller temperature of 90° C., and a roller pressure of 0.2 MPa. The evaluation criteria are as follows. Table 3 shows the evaluation results. ○: Peeling of the resin layer was observed at the winding roller part of the protective film between the winding of the protective film and the temporary attachment (thermal compression bonding) part. ×: Peeling of the resin layer was observed in the take-up roller part of the protective film.

*1: EPICLON 840 manufactured by DIC (liquid epoxy resin, epoxy equivalent 185g/eq) *2: EPICLON 860 manufactured by DIC (bisphenol A type solid epoxy resin, epoxy equivalent 245g/eq) *3: EPICLON HP-5000 manufactured by DIC (Naphthalene skeleton modified multifunctional epoxy resin, epoxy equivalent 252g/eq) *4: HF-1M manufactured by Meiwa Chemicals Co., Ltd., phenol novolac resin, hydroxyl equivalent 106g/eq *5: DIC EPICLON HPC-8000 manufactured by the company, active ester resin, active equivalent 223g/eq, solid*6: dimethylaminopyridine*7: 2E4MZ manufactured by Shikoku Chemicals Corporation, 2-ethyl-4-methylimidazole*8: Phenoxy resin *9: SO-C1 manufactured by ADMATECHS Co., Ltd., spherical silica, average particle size (D ₅₀ )=200nm *10: Bisphenol F type acrylate resin, manufactured by Nippon Kayaku Co., Ltd. *11: DIC Co. Production: A carboxyl group-containing resin having an amidoimide structure *12: Tricyclic [5.2.1.0 2,6] decane dimethanol diacrylate, manufactured by Shin Nakamura Chemical Co., Ltd. *13: Mitsubishi Chemical Corporation jER828, double Phenolic A type epoxy resin, epoxy equivalent 189g/eq, liquid form *14: manufactured by DIC Corporation, dicyclopentadiene type *15: manufactured by IGM Resins BV Omnirad 369, 2-methyl-1-[4-( (Methylthio)phenyl]-2-morpholinopropane-1-one*16: Barium sulfate, manufactured by Sakai Chemical Co., Ltd.

From the results shown in the above table, it can be seen that according to the present invention, a dry film can be obtained, which does not cause the resin to adhere to the blade and deteriorate the sharpness even if the cutting process is continuously performed. As a result, the resin at the end does not occur. Cracking or floating, floating of protective film.

11: Three-layer dry film 12: Resin layer 13: carrier film 14: Protective film

[Fig. 1] A schematic cross-sectional view schematically showing an embodiment of the dry film of the present invention.

11: Three-layer dry film

12: Resin layer

13: carrier film

14: Protective film

Claims (6)

A dry film in a dry film with carrier film, resin layer and protective film, The peel strength of the protective film with respect to the resin layer is 0.010kgf/cm or more, And the peel strength of the protective film with respect to the resin layer is greater than the peel strength of the carrier film with respect to the resin layer. The dry film of claim 1, wherein the peel strength of the protective film relative to the resin layer is greater than the peel strength of the carrier film relative to the resin layer by 0.005 kgf/cm or more. For example, the dry film of claim 1 has a thickness of 60 μm or more. Such as the dry film of claim 1, wherein the aforementioned protective film is adhesive. A hardened product obtained by hardening the resin layer of the dry film as in any one of claims 1 to 4. An electronic component having a hardened product as claimed in claim 5.

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