Resin composition, resin coating film, dry film, and cured resin product

Abstract

A resin composition capable of forming a cured resin product having a relative dielectric constant of 2.5 or less at 10 GHz and a dielectric loss tangent of 0.005 or less at 10 GHz by thermal curing, the resin composition comprising (A) a polymer having a silicon phenylene skeleton, an isocyanuric acid skeleton containing an epoxy group, and a norbornane skeleton in the main chain, and (B) an epoxy curing accelerator.

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin film, a dry film and a resin cured product. Background Art

[0002] In recent years, in the semiconductor industry, to cope with the high frequencies of mobile devices such as smartphones, there is a need for semiconductor sealing materials with low dielectric loss. Until now, epoxy resins have been frequently used as semiconductor sealing materials. Epoxy resins can be used to seal substrates with uneven portions such as chips and wiring flatly without introducing voids. A semiconductor sealing material in the form of a dry film using a silicone resin has been proposed, comprising a support film and a resin film on the support film (Patent Document 1).

[0003] However, the speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, network infrastructure equipment such as servers and routers, and electronic equipment such as mainframe computers are increasing year by year. This has led to a need for further reductions in transmission losses, and for semiconductor sealing materials, a need for further reductions in dielectric loss.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-95524 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a resin composition, a resin film, and a dry film including a support film and the resin film on the support film that can form a cured resin product having high adhesion to substrates, electronic components, semiconductor elements, and particularly base materials used in circuit boards, excellent reliability as a protective film for electrical and electronic components, etc., low relative dielectric constant and dielectric loss tangent, and small warpage.

[0009] Means for solving problems

[0010] The present inventors have conducted extensive research to achieve the above-mentioned objectives and have discovered that a resin composition comprising (A) a polymer containing a silphenylene skeleton, an isocyanuric acid skeleton containing an epoxy group, and a norbornane skeleton in its main chain, and (B) an epoxy curing accelerator, can achieve the above-mentioned objectives, thereby completing the present invention.

[0011] That is, the present invention provides the following resin composition, resin film, dry film, and resin cured product.

[0012] 1. A resin composition comprising:

[0013] (A) a polymer comprising a silphenylene skeleton, an isocyanuric acid skeleton containing an epoxy group, and a norbornane skeleton in the main chain, and

[0014] (B) epoxy curing accelerator,

[0015] The resin composition can form a cured resin having a relative dielectric constant of 2.5 or less at 10 GHz and a dielectric loss tangent of 0.005 or less at 10 GHz by thermal curing.

[0016] 2. The resin composition according to 1, wherein the polymer (A) comprises a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2).

[0017] [Chemistry 1]

[0018]

[0019] (Wherein, a and b are positive numbers satisfying 0<a<1, 0<b<1 and a+b=1. 1 is a divalent group represented by the following formula (X1). 2 is a divalent group represented by the following formula (X2).

[0020] [Chemistry 2]

[0021]

[0022] (Where R 11 and R 12 R are each independently a hydrogen atom or a methyl group. 13 It is a hydrocarbon group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be inserted between its carbon-carbon bonds. x and y are each independently an integer from 0 to 7. The dotted line represents the bonding end.

[0023] [Chemistry 3]

[0024]

[0025] (Where R 21 and R 22 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. z is an integer from 0 to 10, and the dotted line represents the bonding end.

[0026] 3. The resin composition according to 1 or 2, further comprising 0.01 to 10 parts by mass of the (B) epoxy curing accelerator relative to 100 parts by mass of the (A) polymer.

[0027] 4. The resin composition according to any one of 1 to 3, further comprising (C) a solvent.

[0028] 5. The resin composition according to any one of 1 to 4, wherein the curing temperature of the resin composition during thermal curing is 100 to 250°C.

[0029] 6. The resin composition according to any one of 1 to 5, which is a material for a protective film for electric and electronic components.

[0030] 7. A resin film obtained from the resin composition according to any one of 1 to 6.

[0031] 8. A dry film comprising: a support film; and the resin film according to 7 on the support film.

[0032] 9. A cured resin product obtained by thermally curing the resin film according to 7 at 100 to 250°C.

[0033] Effects of the Invention

[0034] The resin composition of the present invention, the resin film obtained from the resin composition, and the dry film comprising a support film and the resin film on the support film can form a cured resin product having high adhesion to substrates such as substrates, electronic components, and semiconductor elements, particularly substrates used in circuit boards, and excellent reliability as a protective film for electrical and electronic components, etc., and having low relative dielectric constant and dielectric loss tangent and small warpage. DETAILED DESCRIPTION

[0035] [Resin composition]

[0036] The resin composition of the present invention comprises a polymer having a silphenylene skeleton, an isocyanuric acid skeleton containing an epoxy group, and a norbornane skeleton in its main chain, and (B) an epoxy curing accelerator.

[0037] [(A) Polymer]

[0038] The polymer of the component (A) is a polymer containing a silphenylene skeleton, an epoxy group-containing isocyanuric acid skeleton, and a norbornane skeleton in the main chain.

[0039] Such a polymer preferably contains a repeating unit represented by the following formula (A1) (hereinafter also referred to as repeating unit A1) and a repeating unit represented by the following formula (A2) (hereinafter also referred to as repeating unit A2).

[0040] [Chemistry 4]

[0041]

[0042] In formulas (A1) and (A2), a and b are positive numbers satisfying 0 < a < 1, 0 < b < 1, and a + b = 1. Preferably, a is 0 < a ≤ 0.35. When a is within this range, the solubility in general organic solvents is excellent and handling is easy.

[0043] In formula (A1), X 1 It is a divalent group represented by the following formula (X1).

[0044] [Chemistry 5]

[0045]

[0046] (The dotted line is the junction end.)

[0047] In formula (X1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0048] In formula (X1), R 13 It is a hydrocarbon group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be inserted between its carbon-carbon bonds, but preferably no ester bond or ether bond exists between the carbon-carbon bonds. The hydrocarbon group may be any of linear, branched, or cyclic. Specific examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, and other alkylene groups. Among these, R 13 , preferably methylene or ethane-1,2-diyl, more preferably methylene.

[0049] In formula (X1), x and y are each independently an integer of 0-7, preferably an integer of 0-2.

[0050] In formula (A2), X 2 It is a divalent group represented by the following formula (X2).

[0051] [Chemistry 6]

[0052]

[0053] (The dotted line is the junction end.)

[0054] In formula (X2), R 21 and R 22Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain heteroatoms. The saturated hydrocarbon group may be any of linear, branched, and cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. In addition, the saturated hydrocarbon group may contain heteroatoms. Specifically, a part or all of the hydrogen atoms of the saturated hydrocarbon group may be substituted by halogen atoms, such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and carbonyl groups, ether bonds, thioether bonds, and the like may intervene between the carbon-carbon atoms. As R 21 and R 22 , preferably a hydrogen atom or a methyl group.

[0055] In formula (X2), z is an integer of 0-10, preferably an integer of 0-2.

[0056] The polymer of component (A) preferably has a weight-average molecular weight (Mw) of 3,000 to 100,000, more preferably 5,000 to 50,000. When the Mw falls within this range, a non-sticky, solid polymer with excellent flexibility can be obtained, and dry film formation with a protective film can also be achieved. It should be noted that Mw in the present invention is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran as the elution solvent.

[0057] In the polymer of the component (A), the repeating units A1 and A2 may be randomly bonded or alternately bonded, and may include a plurality of blocks of each unit.

[0058] The polymer of the component (A) contains a silphenylene skeleton as a skeleton containing silicon atoms, but preferably does not contain a siloxane skeleton from the viewpoint of dielectric properties. The skeleton containing silicon atoms is particularly preferably composed of only a silphenylene skeleton.

[0059] The polymer of the component (A) functions as a polymer that imparts dry film-forming ability.

[0060] The polymer of the component (A) may be used alone or in combination of two or more.

[0061] [Method for producing polymer]

[0062] The polymer compound can be produced by addition-polymerizing a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) in the presence of a metal catalyst.

[0063] [Chemistry 7]

[0064]

[0065] [Chemistry 8]

[0066]

[0067] (Where R 11 ~R 13 , x, and y are the same as above.)

[0068] [Chemistry 9]

[0069]

[0070] (Where R 21 、R 22 and z are the same as above)

[0071] As the metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metal elements can be used; platinum chloride, chloroplatinic acid and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (wherein x is an integer from 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (e.g., U.S. Patent No. 3 220972); complexes of chloroplatinic acid and olefins (for example, the catalysts described in the specification of U.S. Patent No. 3159601, the specification of U.S. Patent No. 3159662, and the specification of U.S. Patent No. 3775452); catalysts in which platinum group metals such as platinum black and palladium are supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinates and vinyl-containing siloxanes (particularly vinyl-containing cyclic siloxanes), etc.

[0072] The amount of the catalyst used is a catalytic amount, and is generally preferably 0.001 to 0.1% by mass relative to the total of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) in terms of platinum group metal. In the polymerization reaction, a solvent can be used as needed. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferred. As the polymerization conditions, from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150° C., particularly preferably 60 to 120° C. The polymerization time also depends on the type and amount of the polymer. In order to prevent moisture from intervening in the polymerization system, it is preferably completed in about 0.5 to 100 hours, particularly 0.5 to 30 hours. After the polymerization reaction is completed in this way, if a solvent is used, it can be distilled off to obtain the polymer.

[0073] The reaction method is not particularly limited. First, the compound represented by formula (2) and the compound represented by formula (3) are mixed, heated, and then a metal catalyst is added to the mixed solution. Then, the compound represented by formula (1) is added dropwise over a period of 0.1 to 5 hours.

[0074] The raw material compounds are blended so that the molar ratio of the hydrosilyl group contained in the compound represented by formula (1) relative to the total carbon-carbon double bonds contained in the compound represented by formula (2) and the compound represented by formula (3) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of the polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

[0075] [(B) Epoxy curing accelerator]

[0076] The epoxy curing accelerator of component (B) can be widely used as long as it is used for the ring opening of epoxy groups. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxy ... Imidazoles such as 2-(4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tertiary amines such as 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo[5.4.0]undecene-7, and tris(dimethylaminomethyl)phenol; organic phosphines such as diphenylphosphine, triphenylphosphine, and tributylphosphine; tetrasubstituted phosphonium and tetrasubstituted borates such as tetraphenylphosphonium and tetraphenylborate, and tetraphenylphosphonium and ethyltriphenylborate; metal compounds such as tin octoate, etc.

[0077] The content of component (B) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, relative to 100 parts by mass of component (A). Within this range, the curing reaction proceeds without excess or deficiency. The epoxy curing accelerators of component (B) may be used alone or in combination of two or more.

[0078] [(C) Solvent]

[0079] The resin composition of the present invention may further contain a solvent as component (C). The solvent is not particularly limited as long as it can dissolve component (A) and component (B), but an organic solvent is preferred due to its excellent solubility in these components.

[0080] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pivalate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ-butyrolactone. Ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof are particularly preferred.

[0081] From the viewpoint of compatibility and viscosity, the amount of component (C) used is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and particularly preferably 50 to 100 parts by mass per 100 parts by mass of component (A). The organic solvent of component (C) may be used alone or as a mixture of two or more.

[0082] The resin composition of the present invention can be prepared by a conventional method. For example, the above-mentioned components can be stirred and mixed, and then filtered using a filter or the like to remove the solid content as needed.

[0083] [Resin film]

[0084] By coating the resin composition of the present invention on a substrate consisting of base materials such as metals and glass such as silicon, glass, iron, copper, nickel, and aluminum, and then preheating (prebaking) as needed to evaporate the solvent, a resin film can be obtained. Prebaking can, for example, be carried out at 40 to 140° C. for 1 minute to 1 hour. As a coating method, it can be a known method, and dipping, spin coating, roller coating, etc. can be listed. The coating amount of the resin composition can be appropriately selected according to the purpose, but it is preferably coated in a manner such that the thickness of the resin film obtained becomes preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0085] [Dry film]

[0086] The dry film of the present invention comprises a support film and a resin film obtained from the resin composition on the support film.

[0087] The dry films (support film and resin film) are solid, and since the resin film does not contain a solvent, there is no risk of bubbles generated by the solvent volatilizing and remaining between the inside of the resin film and the substrate having irregularities.

[0088] The thickness of the resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm, from the viewpoints of flatness on a substrate having irregularities, coverage of step height differences, and substrate lamination intervals.

[0089] Furthermore, the viscosity of the resin film is closely related to its fluidity. Within an appropriate viscosity range, the resin film exhibits adequate fluidity, allowing it to penetrate narrow gaps or soften, thereby enhancing adhesion to the substrate. Therefore, from the perspective of fluidity, the viscosity of the resin film is preferably 10 to 5000 Pa·s at 80 to 120°C, more preferably 30 to 2000 Pa·s, and even more preferably 50 to 300 Pa·s. In the present invention, viscosity is measured using a rotational viscometer.

[0090] When the dry film of the present invention is adhered to a substrate having irregularities, the resin coating follows the irregularities and covers them, achieving high flatness. In particular, the resin coating is characterized by low viscoelasticity, thus achieving even higher flatness. Furthermore, by adhering the resin coating to the substrate under a vacuum environment, gaps can be more effectively prevented.

[0091] The dry film of the present invention can be produced by coating a resin composition dissolved in the solvent onto a support film and drying to form a resin film. As an apparatus for producing the dry film, a film coater generally used for producing pressure-sensitive adhesive products can be used. Examples of the film coater include a notch wheel coater, a notch wheel reverse coater, a multipurpose coater, a die coater, a lip coater, a lip reverse coater, a direct gravure roll coater, an offset gravure roll coater, a three-roller bottom reverse coater, and a four-roller bottom reverse coater.

[0092] The supporting film is unwound from the unwinding shaft of the film coater, and when it passes through the coater head of the film coater, the resin composition is applied to the supporting film at a specified thickness, and then passed through a hot air circulation oven at a specified temperature and time to dry on the supporting film to form a resin film, thereby making it possible to manufacture a dry film. In addition, as needed, the dry film and the protective film unwound from another unwinding shaft of the film coater are passed through a laminating roller at a specified pressure, and after the resin film on the supporting film and the protective film are bonded, they are wound on the winding shaft of the film coater, thereby making it possible to manufacture a dry film with a protective film. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5MPa.

[0093] The supporting film may be a single-layer film consisting of a single film, or a multilayer film formed by laminating a plurality of films. As the material of the film, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate can be listed. Among these, polyethylene terephthalate is preferred from the perspective of having appropriate flexibility, mechanical strength, and heat resistance. These films may be films subjected to various treatments such as corona treatment and release agent coating. They can use commercially available products, for example, Cerapeel WZ (RX), Cerapeel BX8 (R) (above are made by Toray Film Processing (Co., Ltd.)), E7302, E7304 (above are made by Toyobo (Co., Ltd.)), Purex G31, Purex G71T1 (above are made by Teijin DuPont Film (Co., Ltd.)), PET38×1-A3, PET38×1-V8, PET38×1-X08 (above are made by Nippa Co., Ltd.), etc.

[0094] As the protective film, the same protective film as the supporting film described above can be used. Polyethylene terephthalate and polyethylene are preferred because of their moderate flexibility. Commercially available products can be used. Examples of polyethylene terephthalate include those listed above, and examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE Film Type 0 (manufactured by Nippa Co., Ltd.).

[0095] From the viewpoint of stability in dry film production and prevention of so-called winding around the core, the thickness of both the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm.

[0096] The lamination method using the dry film of the present invention on a flat or uneven substrate is not particularly limited. For example, the following method can be used: the protective film attached to the dry film is peeled off, and a vacuum laminator (product name: TEAM-300) manufactured by Takatori Corporation is used to set the vacuum degree in the vacuum chamber to 50 to 1000 Pa, preferably 50 to 500 Pa, for example, 100 Pa. The resin film attached to the support film is simultaneously bonded to the substrate at 80 to 200°C, preferably 80 to 130°C, for example, 100°C. After returning to normal pressure, the substrate is cooled to room temperature, removed from the vacuum laminator, and the support film is peeled off.

[0097] [cured material]

[0098] For the resin film formed by applying the solution of the resin composition and drying on substrate or the resin film formed by pasting the dry film, use baking oven, hot plate, preferably at 100~250 ℃, more preferably at 150~230 ℃ thermosetting, thereby can obtain cured product.In addition, the thermosetting time is preferably 10 minutes~10 hours, more preferably 10 minutes~4 hours.If the curing temperature is 100~250 ℃, then can obtain for substrate, electronic component, semiconductor element etc., the adhesion of the base material used in circuit substrate is high, as the reliability of electric and electronic component protection film etc. is excellent, relative dielectric constant, dielectric loss tangent are low, the resin cured product with little warping.

[0099] The resin film and dry film obtained from the resin composition are preferably used as sealing materials such as protective films for semiconductor elements.

[0100] Example

[0101] The following synthesis examples, examples, and comparative examples illustrate the present invention in more detail, but the present invention is not limited to the following examples. Mw was measured by GPC using a TSKgelSuper HZM-H (manufactured by Tosoh Corporation) as a column, at a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40°C, with monodisperse polystyrene as the standard.

[0102] [1] Synthesis of polymers

[0103] The compounds used in the synthesis of the polymer are shown below.

[0104] [Chemistry 10]

[0105]

[0106] [Chemistry 11]

[0107]

[0108] [Chemistry 12]

[0109]

[0110] [Synthesis Example 1] Synthesis of Polymer P-1

[0111] In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 92.8g (0.35 mol) of compound (S-4a) and 105.3g (0.65 mol) of compound (S-3b) were added, and then 2000g of toluene was added and heated to 70°C. Then, 1.0g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 194.0g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 2 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain polymer P-1. In addition, for polymer P-1, 1 H-NMR (manufactured by Bruker) did not detect a peak near 4.5 ppm indicating the presence of SiH groups. FT-IR (manufactured by Shimadzu Corporation) did not detect a peak at 2200 cm-1 indicating the presence of SiH groups. -1 The peak near the alkyl group was also measured by GPC, and its Mw was 4000, thereby confirming that it was a polymer containing repeating units A1 and A2.

[0112] [Synthesis Example 2] Synthesis of Polymer P-2

[0113] After adding 53.0 g (0.20 mol) of compound (S-4a) and 96.8 g (0.80 mol) of compound (S-3a) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2000 g of toluene was added and heated to 70°C. Then, 1.5 g of chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 194.0 g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 8 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain polymer P-2. In addition, for polymer P-2, 1 H-NMR (manufactured by Bruker) did not detect a peak near 4.5 ppm indicating the presence of SiH groups. FT-IR (manufactured by Shimadzu Corporation) did not detect a peak at 2200 cm-1 indicating the presence of SiH groups. -1 The peak near the alkylene group was also measured by GPC, and Mw was 41,000, thereby confirming that it was a polymer containing repeating units A1 and A2.

[0114] [Synthesis Example 3] Synthesis of Polymer P-3

[0115] In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 13.3g (0.05 mol) of compound (S-4a) and 115.0g (0.95 mol) of compound (S-3a) were added, and then 2000g of toluene was added and heated to 70°C. Then, 2.0g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 194.0g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 20 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain polymer P-3. In addition, as for polymer P-3, 1 H-NMR (manufactured by Bruker) did not detect a peak near 4.5 ppm indicating the presence of SiH groups. FT-IR (manufactured by Shimadzu Corporation) did not detect a peak at 2200 cm-1 indicating the presence of SiH groups. -1 The peak near the alkylene group was also measured by GPC, and Mw was 83,000, thereby confirming that it was a polymer containing repeating units A1 and A2.

[0116] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer CP-1

[0117] In a 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser, 26.5 g (0.10 mol) of compound (S-4a) and 108.9 g (0.90 mol) of compound (S-3a) were added, followed by 2000 g of toluene and heating to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 184.3 g (0.95 mol) of compound (S-1) and 9.3 g (0.05 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to yield comparative polymer CP-1. The Mw of comparative polymer CP-1 was 15,000.

[0118] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer CP-2

[0119] A 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 238.5 g (0.90 mol) of compound (S-4a) and 16.2 g (0.10 mol) of compound (S-3b). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 184.3 g (0.95 mol) of compound (S-1) and 79.3 g (0.05 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer CP-2. Comparative polymer CP-2 had an Mw of 7000.

[0120] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer CP-3

[0121] In a 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser, 79.5 g (0.30 mol) of compound (S-4a) and 377.3 g (0.70 mol) of compound (S-3c) were added, followed by 2000 g of toluene and heating to 70°C. Subsequently, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to yield comparative polymer CP-3. Comparative polymer CP-3 had an Mw of 83,000.

[0122] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer CP-4

[0123] A 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 132.5 g (0.50 mol) of compound (S-4a) and 409.0 g (0.50 mol) of compound (S-3d). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer CP-4. The Mw of comparative polymer CP-4 was 103,000.

[0124] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer CP-5

[0125] A 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 26.5 g (0.10 mol) of compound (S-4a), 163.6 g (0.20 mol) of compound (S-3d), and 84.7 g (0.70 mol) of compound (S-3a). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 194.0 g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer CP-5. The Mw of comparative polymer CP-5 was 11,000.

[0126] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer CP-6

[0127] After adding 392.0 g (1.00 mol) of compound (S-4b) to a 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser, 2000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 194.0 g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 10 hours. The toluene was then distilled off under reduced pressure from the reaction solution to obtain comparative polymer CP-6. Comparative polymer CP-6 had an Mw of 6000.

[0128] [Comparative Synthesis Example 7] Synthesis of Comparative Polymer CP-7

[0129] After adding 392.0 g (1.00 mol) of compound (S-4b) to a 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser, 2000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer CP-7. The Mw of comparative polymer CP-7 was 36,000.

[0130] [Comparative Synthesis Example 8] Synthesis of Comparative Polymer CP-8

[0131] A 10L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 117.6 g (0.30 mol) of compound (S-4b) and 377.3 g (0.70 mol) of compound (S-3c). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 194.0 g (1.00 mol) of compound (S-1) was added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 12 hours. The toluene was then removed from the reaction solution under reduced pressure to yield comparative polymer CP-8. The Mw of comparative polymer CP-8 was 16,000.

[0132] [Comparative Synthesis Example 9] Synthesis of Comparative Polymer CP-9

[0133] A 10L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 196.0 g (0.50 mol) of compound (S-4b) and 60.5 g (0.50 mol) of compound (S-3a). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 1585.0 g (1.00 mol) of compound (S-2b) was added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 10 hours. The toluene was then removed from the reaction solution under reduced pressure to yield comparative polymer CP-9. The Mw of comparative polymer CP-9 was 81,000.

[0134] [Comparative Synthesis Example 10] Synthesis of Comparative Polymer CP-10

[0135] A 10L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 196.0 g (0.50 mol) of compound (S-4b) and 269.5 g (0.50 mol) of compound (S-3c). Then, 2000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 1585.0 g (1.00 mol) of compound (S-2b) was added dropwise over 1 hour (total hydrosilyl group / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 10 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer CP-10. The Mw of comparative polymer CP-10 was 52,000.

[0136] [2] Preparation of resin composition

[0137] [Examples 1 to 6 and Comparative Examples 1 to 10]

[0138] The components were blended according to the compositions shown in Tables 1 and 2, stirred at room temperature, dissolved, and then microfiltered using a 1.0 μm Teflon (registered trademark) filter to prepare resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10.

[0139] [Table 1]

[0140]

[0141] [Table 2]

[0142]

[0143] In Tables 1 and 2, the epoxy curing accelerator B-1 is Curezol 2P4MHZ (manufactured by Shikoku Chemicals Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole), and B-2 is PURECAT TX-1 (manufactured by San-Apro Ltd., 1,8-diazabicyclo[5.4.0]undecene-7).

[0144] [3] Preparation of dry film

[0145] Using a die coater as a film coater and a polyethylene terephthalate film (thickness 38 μm) as a support film, the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10 were respectively coated on the support film. Next, the resin films were formed on the support film by passing through a hot air circulation oven (length 4 m) set at 100° C. for 5 minutes to obtain dry films. The film thickness of each resin film was 100 μm. In addition, the film thickness of the resin film was measured using an optical interference film thickness measuring machine (F50-EXR manufactured by Filmetrics, Inc.).

[0146] [4] Evaluation of resin film

[0147] (1) Evaluation of warping stress

[0148] The prepared films were laminated onto an 8-inch silicon wafer using a film laminator (TEAM-100, manufactured by Takatori Corporation). The films were then cured by heating in an oven under nitrogen purge at 230°C for 2 hours for Examples 1 and 2, at 150°C for 2 hours for Examples 5 and 6, and at 190°C for 2 hours for Examples 3 and 4 and Comparative Examples 1 to 10. The warpage stress (25°C) of these films was measured using a thin film stress analyzer (FLX-2320-S, manufactured by Toho Technology Corporation). The results are shown in Tables 3 and 4.

[0149] (2) Evaluation of Adhesion

[0150] The prepared film was laminated onto an 8-inch silicon wafer using a film laminator (TEAM-100 manufactured by Takatori Corporation). A 2 mm square silicon chip was then pressed from the laminate. The film was then cured by heating in an oven under nitrogen purge at 230°C for 2 hours for Examples 1 and 2, 150°C for 2 hours for Examples 5 and 6, and 190°C for 2 hours for Examples 3 and 4 and Comparative Examples 1 to 10. The chip was then pressed laterally at 23°C at a test speed of 200 μm / sec using an adhesion tester (Universal Adhesion Tester Series 4000 (DS-100) manufactured by Nordson Advanced Technology). The adhesion strength when the chip was peeled from the substrate was measured (wafer shear test). The results are shown in Tables 3 and 4.

[0151] (3) Evaluation of relative dielectric constant and dielectric loss tangent

[0152] The prepared dry films were cured by heating in an oven at 230°C for 2 hours for Examples 1 and 2, at 150°C for 2 hours for Examples 5 and 6, and at 190°C for 2 hours for Examples 3 and 4 and Comparative Examples 1 to 10, while purging with nitrogen. The supporting film was then peeled from the cured film, and the relative dielectric constant (10 GHz, 25°C) and dielectric loss tangent (10 GHz, 25°C) were measured. Furthermore, the relative dielectric constant and dielectric loss tangent were measured using a cavity resonator method using an apparatus manufactured by AET. The results are shown in Tables 3 and 4.

[0153] (4) Evaluation of tensile strength

[0154] The prepared dry films were cured in an oven by heating under nitrogen purge at 230°C for 2 hours for Examples 1 and 2, at 150°C for 2 hours for Examples 5 and 6, and at 190°C for 2 hours for Examples 3 and 4 and Comparative Examples 1 to 10. The support film was then peeled from the cured film, and the strength was measured using a tensile strength tester (Autograph AGS-5kNG, manufactured by Shimadzu Corporation). The results are shown in Tables 3 and 4.

[0155] (5) Reliability evaluation

[0156] For the dry film produced, a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) was used, and the vacuum degree in the vacuum chamber was set to 80 Pa, so that the resin film on the supporting film was tightly adhered to the CCL substrate on which the 10 mm × 10 mm square silicon chip was stacked. The temperature condition was set to 100°C. After returning to normal pressure, the substrate was taken out of the vacuum laminator and the supporting film was peeled off. An oven was used, for Examples 1 and 2, at 230°C for 2 hours, for Examples 5 and 6, at 150°C for 2 hours, for Examples 3 and 4 and Comparative Examples 1 to 10, at 190°C for 2 hours, while heating while purging with nitrogen to cure the film. Then, for the substrate, a dicing saw with a dicing blade (DAD685 manufactured by DISCO, with a spindle speed of 40,000 rpm and a cutting speed of 20 mm / s) was used to obtain a 20 mm × 20 mm square test piece in such a way that the periphery of the silicon chip became 5 mm. The obtained test pieces (10 pieces each) were subjected to a thermal cycle test (repeated 1000 cycles of holding at -50°C for 10 minutes and 125°C for 10 minutes). The peeling state of the wafer from the resin film and the presence or absence of cracks after the thermal cycle test were confirmed. The case where there was no peeling or no cracking was marked as ○, the case where one or more peeling occurred was marked as ×, and the case where one or more cracks occurred was marked as ×. In addition, the presence or absence of peeling and cracks was confirmed by top-down observation using an optical microscope and cross-sectional SEM observation. The results are shown in Tables 3 and 4.

[0157] [Table 3]

[0158]

[0159] [Table 4]

[0160]

[0161] The above results show that the resin composition of the present invention, the resin film obtained from the resin composition, and the dry film comprising a support film and the resin film on the support film can form a resin cured product having high adhesion to substrates, electronic components, semiconductor elements, etc., especially substrates used in circuit boards, excellent toughness, excellent reliability as a protective film for electrical and electronic components, etc., low relative dielectric constant and dielectric loss tangent, and small warpage.

Claims

1. A resin composition comprising: (A) a polymer having a silylene skeleton, an isocyanuric acid skeleton containing an epoxy group, and a norbornane skeleton in its main chain; and (B) an epoxy curing accelerator, wherein the resin composition is capable of forming a cured resin having a relative dielectric constant of 2.5 or less at 10 GHz and a dielectric loss tangent of 0.005 or less at 10 GHz through thermal curing.

2. The resin composition according to claim 1, wherein The (A) polymer comprises a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), [Chemistry 1] Where a and b are positive numbers satisfying 0<a<1, 0<b<1 and a+b=1, X 1 is a divalent group represented by the following formula (X1), X 2 is a divalent group represented by the following formula (X2), [Chemistry 2] Where R 11 and R 12 are each independently a hydrogen atom or a methyl group, R 13 is an alkylene group having 1 to 8 carbon atoms, an ester bond or an ether bond may be inserted between its carbon-carbon bonds, x and y are each independently an integer of 0 to 7, and the dotted line is a bonding end. [Chemistry 3] Where R 21 and R 22 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, z is an integer of 0 to 10, and the dotted line represents a bonding end.

3. The resin composition according to claim 1, wherein The epoxy curing accelerator (B) is contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the polymer (A). The resin composition according to claim 1 , further comprising (C) a solvent. The resin composition according to claim 1 , wherein the curing temperature of the resin composition during thermal curing is 100 to 250° C. The resin composition according to claim 1 , which is a material for a protective film for electric and electronic components. 7 . A resin film obtained from the resin composition according to claim 1 .

8. A dry film comprising: A support film, and the resin film according to claim 7 on the support film. 9 . A cured resin product obtained by thermally curing the resin film according to claim 7 at 100 to 250° C.

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