TWI766134B - Thermosetting composition, cured product thereof, semiconductor packaging material, prepreg, circuit board, and build-up film - Google Patents

Abstract

The subject of the present invention is to provide a thermosetting composition, a thermosetting resin modifier, a cured product thereof, a semiconductor packaging material, a prepreg, a circuit board, and a build-up film, wherein the obtained cured product can be well-balanced To achieve good copper foil adhesion, elastic modulus, heat resistance and toughness. The present invention uses a thermosetting composition, which is a thermosetting composition comprising a thermosetting resin, a thermosetting agent and a modified resin, characterized in that the modified resin has a group selected from the group consisting of hydroxyl and carboxyl groups In at least one thermoplastic resin, the glass transition temperature of the modified resin is -100°C or more and 50°C or less, and the number average molecular weight of the modified resin is 600 or more and 50,000 or less.

Description

Thermosetting composition, cured product thereof, semiconductor packaging material, prepreg, circuit board, and build-up film

The present invention relates to a thermosetting composition, a thermosetting resin modifier, a cured product thereof, and a semiconductor packaging material, prepreg, circuit board, and build-up film using the same.

Thermosetting resins are used as packaging materials to protect semiconductor elements such as capacitors, diodes, transistors, and thyristors, and integrated circuits such as ICs and LSIs. With the miniaturization and thinning of electronic components, high density and high integration of printed wiring boards are required, and accordingly, semiconductor packaging materials are required to have low thermal expansion and the like.

As the semiconductor encapsulating material, a thermosetting resin composition containing an aromatic amine compound, an aliphatic amine compound, a siloxane compound, and a maleimide compound is proposed (for example, refer to Patent Document 1). Moreover, a resin composition containing a cyanate resin and a naphthyl ether type epoxy resin is proposed (for example, refer to Patent Document 2).

prior art literature Patent Literature

Patent Document 1 Japanese Patent Laid-Open No. 2017-178991

Patent Document 2 Japanese Patent Application Laid-Open No. 2016-006187

However, according to the review by the present inventors, conventional cured products formed of thermosetting resin compositions have good low thermal expansion properties, but cannot achieve good copper foil adhesion and elasticity in a sufficiently satisfactory balance modulus, heat resistance and toughness.

The subject of the present invention is to provide a thermosetting composition, a thermosetting resin modifier, a cured product thereof, a semiconductor packaging material, a prepreg, a circuit board, and a build-up film, and among the available cured products, A good balance is achieved to achieve good copper foil adhesion, elastic modulus, heat resistance and toughness.

The present invention uses a thermosetting composition, which is a thermosetting composition comprising a thermosetting resin, a thermosetting agent and a modified resin, wherein the modified resin is characterized in that the modified resin is selected from the group consisting of a hydroxyl group and a carboxyl group In at least one thermoplastic resin, the glass transition temperature of the modified resin is -100°C or more and 50°C or less, and the number average molecular weight of the modified resin is 600 or more and 50,000 or less.

According to the thermosetting composition of the present invention, the obtained cured product can exhibit excellent heat resistance, copper foil adhesion, and toughness.

FIG. 1 is an atomic force microscope image of the fractured surface of the cured product of Example 1. FIG.

FIG. 2 is an atomic force microscope image of the fractured surface of the cured product of Example 2. FIG.

FIG. 3 is an atomic force microscope image of the fractured surface of the cured product of Example 3. FIG.

FIG. 4 is an atomic force microscope image of the fractured surface of the cured product of Example 4. FIG.

FIG. 5 is an atomic force microscope image of the fractured surface of the cured product of Comparative Example 1. FIG.

FIG. 6 is an atomic force microscope image of the fractured surface of the cured product of Comparative Example 2. FIG.

Form for carrying out the invention

The thermosetting composition of the present invention contains a thermosetting resin (A), a thermosetting agent (B), and a modified resin (C). The said thermosetting composition may contain an inorganic filler (D), and may further contain a flame retardant (E), etc.

構造的樹脂、馬來醯亞胺樹脂、乙烯基苄基化合物、丙烯酸化合物、苯乙烯及馬來酸酐之共聚合物等，較佳為至少包含環氧樹脂。 As said thermosetting resin (A), epoxy resin, benzo-containing

The structured resin, maleimide resin, vinylbenzyl compound, acrylic compound, copolymer of styrene and maleic anhydride, etc., preferably contains at least epoxy resin.

As said epoxy resin, 1 type or 2 or more types can be used, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and tetramethyl biphenyl type epoxy resin are mentioned. , Diglycidoxy naphthalene compounds (1,6-diglycidoxynaphthalene, 2,7-diglycidoxynaphthalene, etc.), phenol novolac epoxy resin, cresol novolac Novolak epoxy resin, bisphenol A novolak epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, Phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation novolak type epoxy resin, naphthol-cresol co-condensation novolak type type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl novolac type epoxy resin, 1,1-bis(2,7-diglycidyloxy-1-naphthyl) ) alkane and other epoxy resins containing a naphthalene skeleton, phosphorus-modified epoxy resins in which phosphorus atoms are introduced into these various epoxy resins, and the like.

Among them, as the above-mentioned epoxy resins, cresol novolak type epoxy resins, phenol aralkyl type epoxy resins, and biphenyl novolac type epoxy resins are particularly preferred in view of obtaining cured products excellent in heat resistance. Resin; Naphthol novolac epoxy resin containing naphthalene skeleton, naphthol aralkyl epoxy resin, naphthol-phenol co-condensation novolak epoxy resin, naphthol-cresol co-condensation novolak epoxy resin Resin; crystalline biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, dibenzopyran type epoxy resin; aromatic ring modified novolak type epoxy resin containing alkoxy group (formaldehyde A compound formed by linking an aromatic ring containing a glycidyl group and an aromatic ring containing an alkoxy group) and the like.

In the thermosetting resin (A), the content of the epoxy resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and the upper limit is 100% by mass.

As said maleimide resin, 1 type or 2 or more types can be used, for example, the resin shown by any one of the following structural formulas is mentioned.

[In formula (1), R ¹ represents an organic group with a valence of a1, and R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , a1 represents an integer of 1 or more. ]

[In formula (2), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms. An alkyl group, a halogen atom, a hydroxyl group or an alkoxy group with 1 to 20 carbon atoms, L ¹ and L ² each independently represent a saturated hydrocarbon group with 1 to 5 carbon atoms, an aromatic hydrocarbon group with 6 to 10 carbon atoms, or a saturated hydrocarbon group A group with 6 to 15 carbon atoms composed of a hydrocarbon group and an aromatic hydrocarbon group. a3, a4, and a5 each independently represent an integer of 1 to 3, and n represents an integer of 0 to 10. ]

Among the nonvolatile components of the thermosetting composition, the content of the thermosetting resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and Preferably it is 99 mass % or less, More preferably, it is 98 mass % or less.

The thermosetting agent (B) reacts with the thermosetting resin (A) by heating, and as long as it is a compound that can harden the thermosetting composition, one type or two or more types can be used, and examples thereof include amine compounds. , amide compounds, active ester resins, acid anhydrides, phenolic resins, cyanate resins, etc. Among them, it is preferable that the thermosetting agent (B) contains at least one selected from the group consisting of active ester resins, phenolic resins and cyanate resins.

Examples of the amine compound include diaminediphenylmethane, diethylenetriamine, triethylenetetramine, diaminediphenylene, isophoronediamine, imidazole, BF ₃ -amine complexes, and guanidine derivatives Wait.

As said amide compound, the polyamide resin etc. which are synthesize|combined from dicyandiamine, the dimer of threooleic acid, and ethylene diamine are mentioned.

Although there are no particular limitations on the above-mentioned active ester resin, generally, phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactions in one molecule are preferably used. Compounds with high activity. The above-mentioned active ester resin is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and/or a naphthol compound is preferred The active ester resin is better. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyrometic acid, and the like, or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, and methylated bisphenol A. Phenol F, Methylated Bisphenol S, Phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, Dihydroxybenzophenone, Trihydroxybenzophenone, Tetrahydroxybenzophenone, Phloroglucinol, Phloroglucinol, Dicyclopentadiene-Phenol Addition resin, etc.

Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromic acid dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophenolic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexanoic anhydride Hydrogen phthalic anhydride, etc.

改性酚醛樹脂(以三聚氰胺、苯并胍胺等連結酚核之含有多元酚性羥基之化合物)、含有烷氧基之芳香環改性酚醛清漆樹脂(以甲醛連結酚核及含有烷氧基之芳香環之含有多元酚性羥基之化合物)等含有多元酚性羥基之樹脂；雙酚A、雙酚F等之雙酚化合物；聯苯、四甲基聯苯等之聯苯化合物；三苯基醇甲烷、四苯基醇乙烷；二環戊二烯-酚加成反應型樹脂，在含有此等各種之酚羥基之化合物中導入磷原子而成之磷改性酚化合物等。 Examples of the phenolic resin include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadienol addition type resins, phenol aralkyl resins (XYLOK resins), and naphthols. Aralkyl resins, Triphenylolmethane resins, Tetraphenyl alcohol ethane resins, Naphthol novolac resins, Naphthol-phenol co-condensation novolac resins, Naphthol-cresol co-condensation novolac resins , Biphenyl-modified phenolic resins (compounds containing polyphenolic hydroxyl groups linked to phenolic cores by bismethylene), phenolic resins containing naphthalene skeleton, biphenyl-modified naphthol resins (phenolic cores linked by bismethylenes) compound of polynaphthol), amino three

Modified phenolic resins (compounds containing polyphenolic hydroxyl groups linked to phenolic cores by melamine, benzoguanamine, etc.), aromatic ring-modified novolak resins containing alkoxy groups (phenolic cores linked to formaldehyde and compounds containing alkoxyl groups) Resins containing polyphenolic hydroxyl groups such as aromatic ring compounds containing polyphenolic hydroxyl groups); bisphenol compounds such as bisphenol A, bisphenol F, etc.; biphenyl compounds such as biphenyl and tetramethyl biphenyl; triphenyl Alcohol methane, tetraphenyl alcohol ethane; dicyclopentadiene-phenol addition reaction type resin, phosphorus-modified phenolic compounds obtained by introducing phosphorus atoms into compounds containing these various phenolic hydroxyl groups, etc.

As said cyanate resin, 1 type or 2 or more types can be used, for example, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin are mentioned. Cyanate resin, bisphenol sulfide type cyanate resin, phenylene ether type cyanate resin, naphthyl ether type cyanate resin, biphenyl type cyanate resin, tetramethyl biphenyl type cyanate resin , polyhydroxynaphthalene type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, Dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol novolac type cyanate resin, naphthol aralkyl type cyanate resin, naphthol- Phenol co-condensed novolak type cyanate resin, naphthol-cresol co-condensed novolak type cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate resin, biphenyl modified novolak type cyanic acid ester resin, anthracene cyanate resin, etc.

Among these cyanate resins, bisphenol A-type cyanate resin, bisphenol F-type cyanate resin, and bisphenol E-type cyanate ester are used in view of obtaining a cured product excellent in heat resistance. Resins, polyhydroxynaphthalene-type cyanate resins, naphthyl ether-type cyanate resins, and novolac-type cyanate resins are preferable, and in terms of obtaining cured products excellent in dielectric properties, dicyclopentadiene- Phenol addition reaction type cyanate resins are preferred.

The thermosetting composition of the present invention may further contain a hardening accelerator (B1). As said hardening accelerator (B1), 1 type or 2 or more types can be used, For example, phosphorus type compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acid, ammonium zirconium salts, etc. are mentioned. In particular, when used as a semiconductor encapsulating material, triphenylphosphine is preferable among phosphorus-based compounds, and 1,8- Biazbicyclo-[5.4.0]-undecene (DBU) is preferred.

The thermosetting composition of the present invention may further contain a maleimide compound (B2). However, the maleimide compound (B2) is different from the aforementioned maleimide resin. As the maleimide compound (B2), one type or two or more types can be used, and examples thereof include N-cyclohexylmaleimide, N-methylmaleimide, and N-n-butylmaleimide. N-aliphatic maleimide such as lyimide, N-hexylmaleimide, N-tertiary butylmaleimide, etc.; N-phenylmaleimide, N-( p-methylphenyl)maleimide, N-aromatic maleimide such as N-benzylmaleimide; 4,4'-diphenylmethane bismaleimide, 4 ,4'-diphenyl bismaleimide, meta-phenylene bismaleimide, bis(3-methyl-4-maleimidephenyl)methane, bis(3-ethyl -4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-methylene Bismaleimides such as lyimidophenyl)methane and bis(3,5-diethyl-4-maleimidophenyl)methane.

Among them, as the maleimide compound (B2), bismaleimides are preferred from the viewpoint of being a cured product with good heat resistance, and 4,4'-diphenylmethanebismaleimide is particularly preferred. imine, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (3,5-diethyl-4-maleimidophenyl)methane is preferred.

When the above-mentioned maleimide compound (B2) is used, the above-mentioned amine compound, the above-mentioned phenol compound, the above-mentioned acid anhydride-based compound, an imidazole compound, an organic metal salt, etc. may be contained as necessary.

The said modified resin (C) is a thermoplastic resin which has at least 1 sort(s) chosen from the group which consists of a hydroxyl group and a carboxyl group, and the thing which has a hydroxyl group is preferable.

The hydroxyl value of the modified resin (C) is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, further preferably 18 mgKOH/g or more, preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less , more preferably 120 mgKOH/g or less.

The quantity of at least one (preferably hydroxyl) selected from the group consisting of hydroxyl and carboxyl groups contained in the modified resin (C) is preferably 2 or more per molecule, preferably 6 or less , more preferably 4 or less, still more preferably 3 or less, particularly preferably 2.

The aforementioned modified resin (C) is preferably at least one selected from the group consisting of polyester resins and polyurethane resins, and more preferably polyester resins.

As said polyester resin, 1 type or 2 or more types can be used, for example, the polyester resin obtained by reacting a polyhydric alcohol and a polycarboxylic acid; the polyester resin obtained by ring-opening polymerization reaction of a cyclic ester compound; Polyester resin etc. obtained by copolymerization.

As the polyhydric alcohol for producing the polyester resin, one type or two or more types can be used, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and diethylene glycol. , aliphatic polyols such as neopentyl glycol and 1,3-butanediol; polyols with alicyclic structure such as cyclohexanedimethanol; polyols with aromatic structure such as bisphenol A and bisphenol F Polyols; polyols modified by alkylene oxide from the aforementioned polyols with aromatic structures, etc.

Among them, the polyol having an alicyclic structure, the polyol having an aromatic structure, and the polyol having an aromatic structure are preferably modified with alkylene oxide, and the polyol having an aromatic structure is preferably The structure polyol modified by alkylene oxide is more preferable.

The molecular weight of the aforementioned polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, and still more preferably 700 or less.

In the present specification, the number average molecular weight refers to a value calculated based on a hydroxyl value.

Examples of the alkylene oxide for modifying the polyol having an aromatic structure include ethylene oxide, propylene oxide, and other alkylene oxides having 2 or more and 4 or less carbon atoms (preferably, 2 or more and 3 or less). With respect to 1 mole of the polyol having an aromatic structure, the added mole of the alkylene oxide is preferably 2 moles or more, more preferably 4 moles or more, preferably 20 moles or less , more preferably 16 moles or less.

As said polycarboxylic acid, one type or two or more types can be used, for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedioic acid; terephthalic acid, isophthalic acid, Aromatic polycarboxylic acids such as phthalic acid, naphthalenedioic acid, etc.; their anhydrides or esters, etc.

Among them, those containing an aliphatic polycarboxylic acid are preferred. The content of the aliphatic polycarboxylic acid is preferably 5 mol % or more, more preferably 10 mol % or more, and preferably 100 mol % or less in the total of the above-described polycarboxylic acids.

As said polycarboxylic acid, it is also a preferable aspect that an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid are contained. Based on moles, the content of the aforementioned aromatic polycarboxylic acid and aliphatic polycarboxylic acid is preferably 1/99 or more, more preferably 30/70 or more, further preferably 50/50 or more, more preferably 99/ 1 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

Based on the quality, the content ratio of the polyol used in the manufacture of the polyester resin to the polycarboxylic acid (polyol/polycarboxylic acid) is preferably 20/80 or more, more preferably 30/70 or more, and further preferably 40/60 or more, preferably 99/1 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

As said cyclic ester compound, 1 type or 2 or more types can be used, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone , ε-ethyl caprolactone, ε-propyl caprolactone, 3-Penten-4-olide (3-Penten-4-olide), 12-dodecanolide (12-dodecanolide), γ- laurolactone.

The content rate of the oxyalkylene units having 4 or more carbon atoms contained in the polyester resin is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably It is 1 mass % or less.

The said polyester resin can be manufactured by making the said polyol and the said polycarboxylic acid react, for example. The reaction temperature is preferably 190°C or higher, more preferably 200°C or higher, more preferably 250°C or lower, and more preferably 240°C or lower. The reaction time is preferably 1 hour or more and 100 hours or less.

A catalyst may be coexisted during the above-mentioned reaction. As the above-mentioned catalyst, one type or two or more types can be used, for example, titanium-based catalysts such as tetraisopropyl titanate (tetraisopropyl titanate) and tetrabutyl titanate (tetrabutyl titanate); dibutyltin oxide ( Dibutyltin oxide) and other tin-based catalysts; p-toluenesulfonic acid and other organic sulfonic acid-based catalysts, etc.

The amount of the catalyst is preferably 0.0001 part by mass or more, more preferably 0.0005 part by mass or more, preferably 0.01 part by mass or less, more preferably 0.01 part by mass or less, relative to 100 parts by mass of the polyol and the polycarboxylic acid in total. 0.005 parts by mass or less.

The aforementioned polyurethane resin is a reaction product of a polyol and a polyisocyanate, and has a hydroxyl group at the terminal.

As a polyol for the manufacture of the said polyurethane resin, a polyether polyol, a polyester polyol, a polycarbonate polyol, etc. are mentioned.

As said polyether polyol, the thing obtained by addition-polymerizing (ring-opening polymerization) an alkylene oxide by using one or two or more types of compounds having two or more active hydrogen atoms as an initiator can be mentioned.

As said starter, ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, for example, are mentioned. , straight-chain diols such as 1,6-hexanediol; branched-chain diols such as neopentyl glycol, 1,2-propanediol, 1,3-butanediol; glycerol, trimethylol Trivalent alcohols such as ethane, trimethylolpropane, gallic phenol, etc; Acids; phosphoric acid; polyamines such as ethylenediamine and ethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetrithiol, etc.

As said alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, etc. are mentioned, for example.

As the polyether polyol, polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran in the above initiator is preferable.

Examples of the polyester polyol include polyester polyols obtained by esterification of low molecular weight polyols (for example, polyols having a molecular weight of 50 to 300) and polycarboxylic acids; cyclic ε-caprolactone and the like. Polyester polyols obtained by ring-opening polymerization of ester compounds; copolymerized polyester polyols of these.

As the low molecular weight polyol, a polyol having a molecular weight of 50 or more and 300 or less can be used, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Diol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol and other aliphatic polyols having 2 to 6 carbon atoms ; 1,4-cyclohexanediol, cyclohexanedimethanol and other polyols containing alicyclic structure; bisphenol A, bisphenol F and other bisphenol compounds and their alkylene oxide adducts, etc. Aromatic structure polyols, etc.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedioic acid; and aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedioic acid. polycarboxylic acids; and acid anhydrides or ester-forming derivatives of the aforementioned aliphatic polycarboxylic acids and aromatic polycarboxylic acids, and the like.

As said polycarbonate polyol, the reactant of carbonate and a polyol, the reactant of phosgene, bisphenol A, etc. are mentioned, for example.

As said carbonate, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, etc. are mentioned, for example.

Examples of the polyol which can react with the aforementioned carbonate include the polyols exemplified as the above-mentioned low-molecular-weight polyols; polyether polyols (polyethylene glycol, polypropylene glycol, etc.), polyester polyols (polyadipic acid) High molecular weight polyol (number average molecular weight of 500 or more and 5,000 or less) such as dihexanol ester, etc.

The number-average molecular weight of the polyol used for the production of the polyurethane resin is preferably 500 or more, more preferably 700 or more, preferably 3,000 or less, and more preferably 2,000 or less.

As said polyisocyanate, 1 type or 2 or more types can be used, For example, 4, 4'- diphenylmethane diisocyanate, 2, 4'- diphenylmethane diisocyanate, carbodiimide (carbodiimide) modification|denaturation are mentioned, for example Aromatic polyisocyanates of diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, stubble diisocyanate, tetramethyl stubble diisocyanate, etc.; VI Aliphatic polyisocyanates such as methylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated stubble diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc. containing alicyclic structure polyisocyanates, etc.

The equivalent ratio of the hydroxyl groups of the polyol used for the manufacture of the urethane resin to the isocyanate groups of the polyisocyanates [isocyanate group/hydroxyl group], on a molar basis, is preferably 0.1 or more, more preferably It is 0.2 or more, preferably 0.9 or less, more preferably 0.7 or less.

The polyurethane resin can be produced by reacting the polyol used for producing the above-mentioned polyurethane resin with a polyisocyanate. When the terminal of the obtained polyurethane resin is an isocyanate group, a chain extender having a hydroxyl group may be further reacted.

As the chain extender having the aforementioned hydroxyl group, one type or two or more types can be used, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butanediol. , 1,4-butanediol, hexamethylene glycol, sucrose, methyl glycol, glycerol, sorbitol and other glycol compounds; bisphenol A, 4,4'-dihydroxybiphenyl, 4,4 Phenolic compounds such as '-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylene, hydrogenated bisphenol A, hydroquinone, etc.; water, etc.

The solubility parameter of the modified resin (C) is preferably 9.0 (cal/cm ³ ) ^0.5 or more, more preferably 9.7 (cal/cm ³ ) ^0.5 or more, preferably 10.5 (cal/cm ³ ) ^0.5 or less, more Preferably, it is 10.3 (cal/cm ³ ) ^0.5 or less.

The difference between the solubility parameters of the mixture of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) (the mixture - modified resin (C)) is preferably -2 (cal/cm ^{3 )} . ) ^0.5 or more, more preferably -1.5 (cal/cm ³ ) ^0.5 or more, further preferably -1 (cal/cm ³ ) ^0.5 or more, more preferably 0 (cal/cm ³ ) ^0.5 or more, particularly preferably 0.2 (cal/cm ³ ) ^0.5 or more, preferably 2 (cal/cm ³ ) ^0.5 or less, more preferably 1.5 (cal/cm ³ ) ^0.5 or less, still more preferably 0.8 (cal/cm ³ ) ^0.5 or less. With the difference between the solubility parameters of the mixture and the modified resin (C) within an appropriate range, they are compatible before thermal hardening, and at the same time, with thermal hardening (ie, the thermosetting resin (A) and the thermal hardener (B) Reaction) The compatibility of the aforementioned mixture (also including the reaction process) and the modified resin (C) is reduced, and after thermal curing, the reactants of the thermosetting resin (A) and the thermosetting agent (B) are modified. Phase separation of the resin (C) is considered to be possible.

The solubility parameter of the aforementioned mixture can be calculated based on the method of Fedors (Polymer Engineering and Science, 1974, vol. 14, No. 2), and the solubility parameter of each compound contained in the curable resin (A) and the thermosetting agent (B) can be calculated , and calculated as a weighted average based on the ratio of the mass standards of each compound. In addition, the solubility parameter of the aforementioned modified resin (C) can be calculated based on the method of Fedors, the solubility parameter of the unit derived from each compound used as the raw material of the modified resin (C), and based on the mass standard of the unit derived from each compound The ratio is obtained as a weighted average.

The glass transition temperature of the modified resin (C) is -100°C or higher, preferably -80°C or higher, more preferably -70°C or higher, and 50°C or lower, preferably 40°C or lower, more preferably 30°C ℃ or lower.

The number average molecular weight of the modified resin (C) is 500 or more, preferably 1,000 or more, more preferably 1,500 or more, and 50,000 or less, preferably 30,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less .

The number average molecular weight of the aforementioned modified resin (C) can be calculated based on the aforementioned functional valence.

The aforementioned modified resin (C) (epoxy resin modifier) is at least one resin selected from the group consisting of polyester resins and polyurethane resins, and has a hydroxyl group, and the glass transition temperature is -100°C or more and 50°C or less, and the number average molecular weight is preferably 600 or more and 50,000 or less.

Although the aforementioned thermosetting composition is in a compatible state before the thermosetting reaction, it is preferable that the thermosetting resin (A) and the modified resin (C) are phase-separated after the thermosetting reaction. In the phase-separated state after the above-mentioned thermosetting reaction, the reactants of the thermosetting resin (A) and the thermosetting agent (B) form a sea portion, and the modified resin (C) forms an island portion, thereby forming a sea-island phase separation. Constructor is better. The reactant of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) may also form a co-continuous structure. By being in a compatible state before the thermosetting reaction, the modified resin (C) can be uniformly dispersed in the mixture of thermosetting resin (A) and thermosetting agent (B). After the curing reaction, the reactants of the thermosetting resin (A) and the thermosetting agent (B) are separated from the modified resin (C), and the chemical and mechanical properties of the modified resin (C) can be maintained, so that the In the obtained hardened product, the domain of the modified resin (C) can be uniformly dispersed in the reactant of the thermosetting resin (A) and the thermosetting agent (B), and it is considered that it can provide both more excellent heat resistance. A hardened product with good properties, copper foil adhesion, and toughness.

The presence or absence of the phase separation system in the cured product can be confirmed by the presence or absence of cloudiness of the cured product, and the presence of sea and island portions when the fractured surface of the cured product is observed with an atomic force microscope (AFM).

The content of the modified resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, relative to 100 parts by mass of the thermosetting resin (A). It is 60 mass parts or less, More preferably, it is 45 mass parts or less. In addition, it may be 35 parts by mass or less, further 15 parts by mass or less, particularly 10 parts by mass or less.

The thermosetting composition of the present invention may further contain an inorganic filler (D). Since the inorganic filler (D) is included, the thermal expansion rate of the insulating layer can be further reduced. As the inorganic filler, one type or two or more types can be used, and examples thereof include silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, Aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc.; silica is preferred; fused silica is more preferred. In addition, the shape of the aforementioned silica may be either a crushed shape or a spherical shape, and the spherical shape is preferred from the viewpoint of increasing the blending amount and suppressing the melt viscosity of the thermosetting composition.

In particular, when the thermosetting composition of the present invention is used for semiconductor packaging materials (preferably power transistors and high thermal conductivity semiconductor packaging materials for power integrated circuits), silica (for example, fused silica, crystalline silica, Preferably crystalline silica), aluminum oxide, silicon nitride are preferred.

The content of the inorganic filler in the thermosetting composition is preferably 0.2 mass % or more, more preferably 30 mass % or more, further preferably 50 mass % or more, still more preferably 70 mass % or more, particularly preferably It is 80 mass % or more, Preferably it is 95 mass % or less, More preferably, it is 90 mass % or less. When the content of the inorganic filler is increased, it is easy to improve the flame retardancy, moist heat resistance, solder crack resistance and reduce the thermal expansion rate.

The thermosetting composition of the present invention may further contain a flame retardant (E). It is preferable that the said flame retardant (E) is a non-halogen type which does not contain a halogen atom substantially. As said flame retardant (E), one type or two or more types can be used, and examples thereof include phosphorus-based flame retardants, nitrogen-based flame retardants, polysiloxane-based flame retardants, inorganic-based flame retardants, and organic metal salts. Department of flame retardants, etc.

As the phosphorus-based flame retardant, one type or two or more types can be used, and examples thereof include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic phosphates such as phosphamide. Nitrogen-containing phosphorus compounds; in addition to general-purpose organic phosphorus-based compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, etc. There are 9,10-dihydro-9-oxo-10-phosphaphenanthrene = 10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide), 10-(2,5-dihydroxybenzene) base) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide (10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene 10-oxide), 10-(2,7- Dihydroxynaphthyl)-10H-9-oxo-10-phosphaphenanthrene=10-oxide (10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene 10-oxide) and other cyclic organic Phosphorus compounds and organic phosphorus compounds such as derivatives obtained by reacting with compounds such as epoxy resins and phenolic resins.

When the aforementioned phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconia, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant.

The aforementioned red phosphorus is preferably subjected to surface treatment, and as a surface treatment method, for example (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or the like can be mentioned. (ii) A method of coating treatment with a mixture of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc., and thermosetting resins such as phenolic resins; (iii) A method of double coating treatment with a thermosetting resin such as a phenolic resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, and titanium hydroxide.

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

化合物等，其中三

化合物、三聚氰酸化合物、異三聚氰酸化合物較佳。使用前述氮系阻燃劑時，亦可併用金屬氫氧化物、鉬化合物等。 As said nitrogen-based flame retardant, for example, three

Compounds, Cyanuric Compounds, Isocyanuric Compounds, Phosphatidyl

compounds, etc., three of which

Compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred. When the aforementioned nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

化合物，可列舉例如三聚氰胺、乙胍

、苯并胍胺、三聚二氰乙腈、蜜白胺、琥珀醯胍胺、伸乙基二-三聚氰胺、多磷酸三聚氰胺、三胍胺等之外，還有例如(i)硫酸甲脒基三聚氰胺、硫酸蜜勒胺、硫酸蜜白胺等之硫酸胺基三

化合物、(ii)酚、甲酚、二甲苯酚、丁基苯酚、壬基酚等之酚類與三聚氰胺、苯并胍胺、乙胍

、甲醯胍胺等之三聚氰胺類及甲醛之共縮合物、(iii)前述(ii)之共縮合物與酚甲醛縮合物等之酚醛樹脂類之混合物、(iv)將前述(ii)、(iii)進一步以桐油、異構化亞麻仁油等改性而成之物等。 as the aforementioned three

Compounds such as melamine, acetguanidine

, benzoguanamine, melamine acetonitrile, melam, succinylguanamine, ethylene di-melamine, melamine polyphosphate, triguanamine, etc., there are for example (i) formamidinium sulfate melamine , melam sulfate, melam sulfate, etc.

Compounds, (ii) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc. and melamine, benzoguanamine, acetguanidine

, co-condensates of melamines such as formguanamine and formaldehyde, (iii) mixtures of the co-condensates of (ii) above and phenolic resins such as phenol-formaldehyde condensates, (iv) the above-mentioned (ii), ( iii) Further modified with tung oil, isomerized linseed oil, etc.

As a specific example of the said cyanuric acid compound, cyanuric acid, melamine cyanurate, etc. are mentioned, for example.

The blending amount of the nitrogen-based flame retardant is appropriately selected according to the type of nitrogen-based flame retardant, components other than the thermosetting composition, and the degree of flame retardancy required. Resin, hardener, non-halogen flame retardant, other fillers, additives, etc. are all blended in 100 parts by mass of the thermosetting composition, preferably in the range of 0.05 to 10 parts by mass, especially with Blending in the range of 0.1 to 5 parts by mass is preferred.

The polysiloxane-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include polysiloxane oil, polysiloxane rubber, and polysiloxane resin.

As the inorganic flame retardant, one or two or more kinds can be used, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide. compounds; zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, Metal oxides of copper oxide, tungsten oxide, etc.; metal carbonate compounds of zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, etc.; aluminum, iron, Metal powders of titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.; boron compounds of zinc borate, zinc metaborate, barium metaborate, boric acid, borax, etc.; Seaplea (Bokusui Brown Co. .), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ series, ZnO-P ₂ O ₅ -MgO series, P ₂ O ₅ -B ₂ O ₃ -PbO-MgO series, P-Sn -OF series, PbO-V ₂ O ₅ -TeO ₂ series, Al ₂ O ₃ -H ₂ O series, low melting point glass such as lead borosilicate series, etc.

Examples of the organometallic salt-based flame retardant include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, metal atoms and aromatic compounds Compounds of family compounds or heterocyclic compounds through ionic bonding or coordination bonding, etc.

The thermosetting composition of the present invention may further contain an organic solvent (F). Since this thermosetting composition contains an organic solvent (F), a viscosity can be reduced, and it becomes suitable especially for the manufacturer of a printed circuit board.

As the organic solvent (F), one type or two or more types can be used, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ethers such as propylene glycol monomethyl ether. Solvents; acetate solvents such as ethyl acetate, butyl acetate, serosol acetate, propylene glycol monomethyl ether acetate, ethyl diethylene glycol acetate, carbitol acetate, etc.; Carbitol solvents such as rosu, methyl serosol, butyl carbitol, etc.; aromatic hydrocarbon solvents such as toluene, xylene, etc.; dimethylformamide, dimethylacetamide, N-methyl Amide solvents such as pyrrolidone and the like.

In particular, when the thermosetting composition of the present invention is used for a printed wiring board, as the organic solvent (F), a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents such as propylene glycol monomethyl ether; acetate solvents such as propylene glycol monomethyl ether acetate, ethyl diethylene glycol acetate, etc.; A carboxamide solvent such as carboxamide is preferable.

In addition, when the thermosetting composition of the present invention is used for a build-up film, as the aforementioned organic solvent (F), ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc.; ethyl acetate, butyl acetate, acetone, etc. Acetate solvents such as lothreol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; carbitol solvents such as serosol, butyl carbitol, etc.; toluene, xylene, etc. Aromatic hydrocarbon solvents; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferred.

When the organic solvent (F) is contained, its content in the thermosetting composition is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, More preferably, it is 70 mass % or less.

The thermosetting composition of the present invention may further contain conductive particles. Since it contains electroconductive particle, it can be used as an electroconductive paste, and it becomes suitable for anisotropic electroconductive material.

The thermosetting composition of the present invention may further contain a rubber, a filler, and the like. Because it contains rubber, fillers, etc., it is suitable for build-up films.

The thermosetting composition of the present invention may further contain various additives such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier.

The thermosetting composition of the present invention can be obtained by mixing the above-mentioned components, and then thermosetting it into a cured product. As the shape of the cured product, a laminate, a molded product, an adhesive layer, a coating film, a thin film, and the like can be mentioned.

Examples of applications of the thermosetting composition of the present invention include semiconductor packaging materials, printed wiring board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, and adhesive films for build-up. Among the above-mentioned applications, it can be used as a so-called electronic component-embedded substrate for embedding passive components such as capacitors and active components such as IC chips in printed wiring boards, insulating materials for electronic circuit boards, and adhesive films for build-up. insulating material used. Among these, from the viewpoint of so-called high heat resistance, low thermal expansion, and solvent solubility, it is preferable to use it for printed wiring board materials and build-up adhesive films.

As a method for preparing a semiconductor encapsulating material from the thermosetting composition of the present invention, the thermosetting resin (A), the thermosetting agent (B), and The modified resin (C) and each component used as needed are obtained until they become uniform.

When the thermosetting composition of the present invention is used for a semiconductor encapsulation material, semiconductor encapsulation molding can be performed. Specifically, the composition can be molded by injection molding, or the composition can be molded using a transfer injection molding machine, an injection molding machine, or the like, and further. By heating at 50-200 degreeC for 2-10 hours, the semiconductor device which is a molded object can be obtained.

In addition, a method of producing a printed circuit board using the thermosetting composition of the present invention includes impregnating a reinforcing base material with the curable composition, covering with copper foil, and performing thermocompression bonding. As said reinforcement base material, paper, glass cloth, glass nonwoven fabric, aromatic polyamide paper, aromatic polyamide cloth, glass mat, glass roving, etc. are mentioned. More specifically, first, by heating the above-mentioned thermosetting composition (preferably at 50 to 170° C. depending on the type of the organic solvent (F)), a prepreg which is a cured product can be obtained. In the said prepreg, the content rate of resin is preferably 20 mass % or more and 60 mass % or less. Then, the above-mentioned prepreg is laminated, covered with copper foil, and heated and crimped at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa to obtain the intended printed circuit board.

When using the thermosetting composition of the present invention as a conductive paste, for example, a method of dispersing conductive particles (fine conductive particles) in the thermosetting composition to prepare a composition for anisotropic conductive films, A method of forming a paste resin composition for circuit connection and anisotropic conductive adhesive in a liquid state at room temperature.

As a method for obtaining the interlayer insulating material for build-up substrates from the thermosetting composition of the present invention, for example, the thermosetting composition is applied on a circuit-forming wiring board by spray coating method, curtain coating method, etc., and then cured. . Then, if necessary, predetermined through holes are drilled, and then the surface is washed with hot water by a roughening agent to form irregularities, and then metal such as copper is plated. As the plating method, electroless plating and electrolytic plating are preferred, and examples of the roughening agent include an oxidizing agent, an alkali, an organic solvent, and the like. Such an operation is repeated in sequence as desired, and a build-up substrate can be obtained by alternately building up layers to form a resin insulating layer and a conductor layer of a predetermined circuit pattern. However, the drilling of the through-hole portion is performed after the formation of the outermost resin insulating layer. In addition, the resin-attached copper foil, which is formed by semi-hardening the thermosetting composition on the copper foil, is heated and crimped at 170 to 300° C. to the wiring board for forming the circuit to form a rough surface, and the step of plating treatment is omitted. , and build-up substrates can also be produced.

The method for producing a build-up film from the thermosetting composition of the present invention includes, for example, coating the thermosetting composition of the present invention on a support film to form a resin composition layer to form a build-up film for a multilayer printed wiring board. method.

When the thermosetting composition of the present invention is used for a build-up film, it is important that the film is softened at the temperature of the build-up (usually 70°C to 140°C) in the vacuum build-up method, and the film is laminated with the circuit board. At the same time, the filled resin existing in the via hole or the through hole of the circuit substrate exhibits fluidity (resin fluidity), and it is preferable to blend the above-mentioned components to exhibit this characteristic.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable that the resin can be filled within this range. In addition, when laminating on both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

The method for producing the above-mentioned adhesive film, specifically, can be produced by the following method: after preparing the thermosetting composition of the present invention in the form of a varnish, coating the composition in the form of a varnish on the surface of the support film (Y), and further The layer (X) of the thermosetting composition is formed by drying the organic solvent by heating, blowing hot air, or the like.

The thickness of the layer (X) to be formed is usually more than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

In addition, the middle layer (X) of the present invention may be protected by a protective film described later. By protecting with a protective film, adhesion or damage to the surface of the resin composition layer such as dust can be prevented.

The aforementioned support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate, and the like. Polyester, polycarbonate, polyimide; further, metal foils such as release paper, copper foil, aluminum foil, etc. are mentioned. In addition, the support film and the protective film may be subjected to mold release treatment in addition to matting treatment and corona treatment.

Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. In addition, the thickness of the protective film is preferably set to 1 to 40 μm.

After the above-mentioned support film (Y) is laminated on a circuit board, or after forming an insulating layer by heat curing, it is peeled off. If the support film (Y) is peeled off after heating and curing the adhesive film, adhesion of dust and the like can be prevented in the curing step. When peeling off after hardening, a mold release process is usually given to the support film in advance.

Next, in the method of manufacturing a multilayer printed wiring board using the adhesive film obtained as described above, for example, when the protective film protective layer (X) is used, it is peeled off, and the layer (X) directly contacts the circuit board, Lamination is performed on one side or both sides of the circuit board by, for example, a vacuum lamination method. The method of lamination can be batch or continuous with rolls. In addition, before lamination is performed, the thin film and the circuit board may be heated and bonded in advance if necessary.

For the conditions of lamination, the crimping temperature (lamination temperature) is preferably set to 70 to 140°C, and the crimping pressure is preferably set to 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ^{2 )} . ), the lamination is preferably carried out under a reduced pressure below 20mmHg (26.7hPa).

As a method for obtaining the cured product of the present invention, it is possible to follow the curing method of a general thermosetting composition. For example, the heating temperature conditions can be appropriately selected according to the type and application of the curing agent used in combination. The composition is heated in the temperature range of about 20~300℃.

[Example]

Hereinafter, an Example is given and this invention is demonstrated more concretely.

[Synthesis Example 1] Synthesis of polyester resin A

779.1 parts by mass of bisphenol A-type glycol ether (trademark; manufactured by DIC Corporation, "Hyprox MDB-561") and 132.9 parts by mass of isophthalic acid (hereinafter referred to as "iPA") were fed into the reaction apparatus. With 40.4 parts by mass of sebacic acid (hereinafter referred to as "SebA".), temperature rise and stirring were started.

Then, after raising the internal temperature to 230° C., 0.10 parts by mass of TiPT was fed, and the reaction was carried out at 230° C. for 24 hours to synthesize a polyester resin.

The hydroxyl value of the obtained polyester resin was 36.9, the number average molecular weight was 3,040, and the glass transition temperature was -14°C.

[Synthesis example 2] Synthesis of polyester resin B

395.6 parts by mass of ethylene glycol and 838.8 parts by mass of adipic acid were fed into the reaction apparatus, and heating and stirring were started.

Subsequently, after raising the internal temperature to 220° C., 0.03 parts by mass of TiPT was fed, and a condensation reaction was performed at 220° C. for 24 hours to synthesize a polyester resin.

The hydroxyl value of the obtained polyester resin was 56.2, the number average molecular weight was 2,000, and the glass transition temperature was not shown.

[Synthesis Example 3] Synthesis of Urethane Resin A

1000.0 parts by mass of polytetramethylene glycol (trademark; manufactured by Mitsubishi Chemical Co., Ltd., "PTMG-1000") was added to the reaction apparatus, and 128.8 parts by mass of toluene diisocyanate (trademark; Mitsui Chemicals SKC Polyurethane) was fed. "COSMONATE T-80", manufactured by Urethane Co., Ltd.). Then, after raising the external temperature to 80° C., the reaction was continued for 10 hours, and the urethane resin A was synthesized.

The hydroxyl value of the obtained urethane resin was 28.0, the number average molecular weight was 4,010, and the glass transition temperature was -22°C.

[Example 1]

80 parts of o-cresol novolak type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON N-680") and 20 parts of bisphenol A type epoxy resin were blended in a mixing container. (trademark; manufactured by DIC Corporation, "EPICLON 850-S"), 50 parts of a novolak-type phenolic resin (trademark; manufactured by DIC Corporation, "PHENOLITE TD-2131") as a hardener, and 30 parts of The both-terminal OH group polyester obtained in Synthesis Example 1 was stirred at an internal temperature of 130° C. until it was dissolved. 1 part of triphenylphosphine as a hardening accelerator was added, and after stirring for 20 seconds, the epoxy resin composition (X1) which is the thermosetting composition of this invention was obtained by vacuum degassing.

[Example 2, 3]

The procedure was carried out in the same manner as in Example 1, except that 45 parts by mass (Example 2) and 60 parts by mass (Example 3) of the both-terminal OH group polyester (polyester resin A) obtained in Synthesis Example 1 were used, respectively. , to obtain epoxy resin compositions (X2) and (X3) which are thermosetting compositions of the present invention.

[Example 4]

Except that 30 parts by mass of the both-terminal OH group polyurethane (urethane resin A) obtained in Synthesis Example 3 was used in place of 30 parts by mass of the both-terminal OH groups obtained in Synthesis Example 1 Except polyester (polyester resin A), it carried out similarly to Example 1, and obtained the epoxy resin composition (X4) which is the thermosetting composition of this invention.

[Comparative Example 1]

80 parts of o-cresol novolak type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON N-680") and 20 parts of bisphenol A type epoxy resin were blended in a mixing container. (trademark; manufactured by DIC Co., Ltd., "EPICLON 850-S"), novolak-type phenol resin (trademark; manufactured by DIC Co., Ltd., "PHENOLITE TD-2131") as a hardener, 50 parts, at an internal temperature of 130 Stir at ℃ until dissolved. After adding 1 part of triphenylphosphine as a hardening accelerator and stirring for 20 seconds, the epoxy resin composition (Y1) of the present invention was obtained by vacuum degassing.

[Comparative Example 2]

Except that 30 parts by mass of the both-terminal OH-group polyester (polyester resin B) obtained in Synthesis Example 2 was used in place of 30 parts by mass of the both-terminal OH-group polyester (polyester resin A) obtained in Synthesis Example 1 ), it carried out similarly to Example 1, and obtained the epoxy resin composition (Y2).

The following evaluations were performed about the obtained epoxy resin compositions (X1)-(X4), (Y1), and (Y2). Table 1 shows the solubility parameters and results of the modified resin (C) used in each epoxy resin composition.

[Evaluation method of copper foil adhesion]

The epoxy resin compositions obtained in the examples and comparative examples were cast at 130° C. into a casting plate formed by sandwiching a 2 mm thick rubber spacer with a glass plate covered with copper foil on one side, at 175 °C. Thermal hardening at ℃ for 5 hours. The obtained cured product was cut into a size of 10 mm in width and 60 mm in length, and the 90° peel strength was measured using a peel tester.

Measuring equipment: Shimadzu Autoplotter (manufactured by Shimadzu Corporation)

Type: AG-1

Test speed: 50mm/m

[Evaluation method of glass transition temperature (Tg) and storage modulus (E')]

The epoxy resin compositions obtained in Examples and Comparative Examples were cast at 130° C. into a casting plate formed by sandwiching a 2 mm-thick rubber spacer with a glass plate, followed by thermosetting at 175° C. for 5 hours. The obtained cured product was cut into a size of 5 mm in width x 55 mm in length, and the storage modulus (E') and the wear modulus (E") were measured under the following conditions.

When E'/E" is set as tan δ, the temperature at which tan δ becomes the maximum is measured and set as the glass transition temperature (Tg, unit; °C).

In addition, the storage modulus (E') at 25°C was measured.

Measuring machine: Dynamic viscoelasticity measuring machine (manufactured by SII NanoTechnology Inc.)

Type: DMA6100

Measuring temperature range: 0℃~300℃

Heating rate: 5°C/min

Frequency: 1Hz

Measurement Mode: Bend

[Evaluation method of fracture toughness]

The epoxy resin compositions obtained in Examples and Comparative Examples were cast at 130°C on a casting plate formed by sandwiching a 4 mm thick rubber spacer with a glass plate, and thermally hardened at 175°C for 5 hours.

The obtained hardened product was cut into a test piece having a width of 13 mm, a length of 80 mm and a thickness of 4 mm, and was processed in accordance with ASTM D5045-93 (ISO 13586), and the fracture toughness (unit; MPa·m ^0.5 ) was measured.

The notch of the test piece before the test was prepared by placing a razor blade on the test piece and impacting the razor blade with a hammer.

In addition, when using the resin composition of the present invention as a semiconductor packaging material, there are many cases where it is required to improve the microscopic fracture toughness, and there are cases where the macroscopic fracture toughness as evaluated by this evaluation method is not required. In some cases, the content of the modified resin (C) is smaller, and the toughness improvement effect may be exhibited.

Measuring equipment: Shimadzu Autoplotter (manufactured by Shimadzu Corporation)

Type: AG-X plus

Test speed: 10mm/min

Distance between marking lines: 50mm

The epoxy resin compositions (X1) to (X4) of Examples 1 to 4 are thermosetting compositions of the present invention, and the obtained cured products exhibit excellent heat resistance, copper foil adhesion and toughness . On the other hand, in Comparative Example 1, which did not contain the modified resin (C), the copper foil adhesion and toughness were poor. Comparative Example 2 is an example using a resin having no glass transition temperature, and the copper foil adhesion, heat resistance, and toughness are all inferior.

Claims (9)

A thermosetting composition, which is a thermosetting composition comprising a thermosetting resin, a thermosetting agent and a modified resin, characterized in that: the modified resin is selected from the group consisting of a hydroxyl group and a carboxyl group. At least one thermoplastic resin, the glass transition temperature of the modified resin is -100°C or more and 50°C or less, and the number average molecular weight of the modified resin is 500 or more and 4,010 or less, relative to 100 parts by mass of the thermosetting resin, The content of the modified resin is 0.1 part by mass or more and 60 parts by mass or less. The thermosetting composition according to claim 1, wherein the modified resin is at least one selected from the group consisting of polyester resins and polyurethane resins. The thermosetting composition according to claim 1 or 2, wherein the hydroxyl value of the modified resin is 2 mgKOH/g or more and 350 mgKOH/g or less. The thermosetting composition according to claim 1 or 2, wherein the solubility parameter of the modified resin is 9.0 (cal/cm ³ ) ^0.5 or more and 10.5 (cal/cm ³ ) ^0.5 or less. A hardened product of the thermosetting composition according to any one of claims 1 to 4. A semiconductor packaging material composed of the thermosetting composition according to any one of claims 1 to 4. A prepreg, which is a semi-hardened product having the thermosetting composition according to any one of Claims 1 to 4 and an impregnated base material of a reinforcing base material. A circuit board comprising a plate-shaped excipient of the thermosetting composition according to any one of claims 1 to 4 and a copper foil. A build-up film comprising the cured product of the thermosetting composition according to any one of claims 1 to 4 and a base film.

Images