JP6493745B2 - Thermosetting resin composition, prepreg, film with resin, laminate, printed wiring board and semiconductor package - Google Patents

Description

  The present invention relates to a thermosetting resin composition suitable for a semiconductor package or a printed wiring board, a prepreg using the thermosetting resin composition, a film with a resin, a laminated board, a printed wiring board, and a semiconductor package.

  With recent downsizing and higher performance of electronic equipment, printed wiring boards have advanced wiring density and higher integration, and accordingly, there has been an increasing demand for improved reliability of wiring laminates. In such applications, particularly semiconductor packages, it is required to have both excellent heat resistance and low thermal expansion.

As a laminated board for a printed wiring board, one obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric is used.
Epoxy resins have an excellent balance of insulation, heat resistance, and cost. However, in order to meet the demands for improved heat resistance due to the recent high-density mounting of printed wiring boards and multi-layered structures, the heat resistance is unavoidable. There is a limit to improvement. Since an epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring and increasing the filling of an inorganic filler such as silica (for example, see Patent Document 1). However, increasing the filling amount of the inorganic filler is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, and poor press molding.
Polybismaleimide resins widely used for high-density packaging and multi-layered laminates have drawbacks in adhesion and low thermal expansion.

Moreover, the thermosetting resin composition which has an epoxy resin, a phenol resin, and a modified imide resin as a main component is known (for example, refer patent document 2). Although this modified imide resin-containing composition is improved in moisture resistance and adhesiveness, it is obtained because it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in general-purpose solvents such as methyl ethyl ketone. There is a problem that the heat resistance of the modified imide resin is significantly inferior to that of the polybismaleimide resin.
Further, particularly in recent years, with semiconductor package substrates, warping due to the difference in thermal expansion coefficient between the chip and the substrate has become a major issue at the time of component mounting and package assembly along with the reduction in size and thickness.

  Further, in mobile communication devices typified by mobile phones, network infrastructure devices such as base station devices, servers and routers, or large computers, the speed of signals used and the increase in capacity are increasing year by year. Along with this, printed wiring boards mounted on these electronic devices are required to cope with higher frequencies, and a low dielectric constant and low dielectric loss tangent substrate material capable of reducing transmission loss is required. In recent years, practical applications and practical plans for new systems that handle high-frequency radio signals in the ITS field (related to automobiles and transportation systems) and indoor short-distance communication fields in addition to the electronic devices described above are available as applications that handle such high-frequency signals. In the future, it is expected that further low transmission loss substrate materials will be required for printed wiring boards to be mounted on these devices.

Japanese Patent Laid-Open No. 5-148343 JP-A-6-263843

  In view of the current situation, the present invention has heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and dielectric properties in a high frequency band (low dielectric constant and low dielectric loss tangent). And a prepreg, a film with resin, a laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting resin composition containing an amino-modified siloxane compound having thioacetal and azomethine and a specific maleimide compound has heat resistance, adhesion The present invention has been found to have excellent properties, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage, and high frequency dielectric properties (high frequency characteristics: low dielectric constant and low dielectric loss tangent). Reached.

That is, this invention provides the following thermosetting resin compositions, a prepreg, a film with resin, a laminated board, and a printed wiring board.
[1] One molecule obtained by reacting a thiol compound (i) having at least two primary thiol groups in one molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule Amino having a thioacetal and azomethine in the molecular structure obtained by reacting a thioacetal compound (a) having at least one aldehyde group and a siloxane compound (b) having at least two primary amino groups A thermosetting resin composition comprising a modified siloxane compound (I) and a maleimide compound (II) having at least two N-substituted maleimide groups in the molecular structure.
[2] The thermosetting resin composition according to the above [1], further comprising an amine compound (III) having an acidic substituent.
[3] The thermosetting resin composition according to the above [1] or [2], further comprising a thermoplastic elastomer (IV).
[4] The thermosetting resin composition according to any one of [1] to [3], further including a thermosetting resin (V).
[5] The thermosetting resin composition according to any one of [1] to [4], further comprising a curing accelerator (VI).
[6] The thermosetting resin composition according to any one of [1] to [5], further including an inorganic filler (VII).
[7] A prepreg obtained by impregnating or coating the thermosetting resin composition according to any one of the above [1] to [6] on a base material, and then forming a B-stage.
[8] A film with a resin obtained by applying the thermosetting resin composition according to any one of [1] to [6] to a support.
[9] A laminate obtained by laminating the prepreg according to [7].
[10] A laminate obtained by laminating the film with resin as described in [8] above.
[11] A multilayer printed wiring board produced using the laminated board according to [9] or [10].
[12] A semiconductor package obtained by mounting a semiconductor on the multilayer printed wiring board according to [11].

According to the present invention, a thermosetting resin composition excellent in heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics, and the thermosetting resin composition The used film with a prepreg resin, a laminate, a printed wiring board, and a semiconductor package can be provided.
A prepreg obtained by impregnating or applying the thermosetting resin composition of the present invention to a substrate, a film with a resin obtained by applying the thermosetting resin composition of the present invention to a support, and the prepreg or Laminates produced by laminating a film with resin, and multilayer printed wiring boards produced using the laminate, especially heat resistance, adhesion, glass transition temperature (Tg), low thermal expansion coefficient, elastic modulus It is excellent in low cure shrinkage and high frequency characteristics, and is useful as a highly integrated printed wiring board for electronic equipment and a semiconductor package using the same.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises a thiol compound (i) having at least two primary thiol groups in one molecule, and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule. In a molecular structure obtained by reacting a thioacetal compound (a) having at least one aldehyde group in one molecule and a siloxane compound (b) having at least two primary amino groups, obtained by reaction Is a thermosetting resin composition comprising an amino-modified siloxane compound (I) having thioacetal and azomethine and a maleimide compound (II) having at least two N-substituted maleimide groups in the molecular structure.
Hereinafter, each component will be described in order.

(Amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure)
The amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure has a thiol compound (i) having at least two primary thiol groups in one molecule, and has at least two aldehyde groups in one molecule. Reaction of thioacetal compound (a) having at least one aldehyde group in one molecule and siloxane compound (b) having at least two primary amino groups obtained by reacting aromatic aldehyde compound (ii) Can be obtained.
Here, thioacetal has a structure such as RCH (SR ′) ₂ , and azomethine means a Schiff base (—N═CH—).

Thiol compound (i) having at least two primary thiol groups in one molecule [hereinafter sometimes abbreviated as thiol compound (i). ] Is preferably a thiol compound having 3 or 4 thiol groups in one molecule, more preferably a thiol compound having 3 primary thiol groups in one molecule.
The thiol compound (i) is preferably represented by the following general formulas (ia), (ib), and (ic).

（一般式（ｉａ）、（ｉｂ）、（ｉｃ）中、Ａ_１は、芳香族又は炭素数１〜３０の脂肪族炭化水素又は複素環である。）

(In the general formulas (ia), (ib), and (ic), A ₁ is an aromatic or an aliphatic hydrocarbon having 1 to 30 carbon atoms or a heterocyclic ring.)

  As thiol compounds (ia to ic), 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, 1,3,5-benzenetrithiol, trithiocyanuric acid, trimethylolpropane tris (3 -Mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. Can be mentioned. You may use these individually by 1 type or in mixture of 2 or more types.

  Among these, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, which has high reactivity at the time of reaction and can achieve higher heat resistance, is preferable. From the viewpoint of low thermal expansion and dielectric properties, trimethylolpropane tris (3-mercaptopropionate) is preferred.

Aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule [hereinafter sometimes simply referred to as aromatic aldehyde compound (ii). ] Is preferably an aromatic aldehyde compound having 2 or 3 aldehyde groups in one molecule, more preferably an aromatic aldehyde compound having 2 aldehyde groups in one molecule.
The aromatic aldehyde compound (ii) has an aromatic hydrocarbon group, and as long as it has an aliphatic hydrocarbon group. For example, the aromatic aldehyde compound (ii) also has a structure of aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group in the molecule.
The aromatic aldehyde compound (ii) is preferably represented by the following general formula (ii).

（一般式（ｉｉ）中、Ａ^１１は、下記一般式（１１）又は（１２）で表される基である。）

(In the general formula (ii), A ¹¹ is a group represented by the following general formula (11) or (12).)

（一般式（１１）中、Ｒ^１１は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐ１は０〜４の整数である。）

(In General Formula (11), each R ¹¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P1 is an integer of 0 to 4.)

（一般式（１２）中、Ｒ^１２及びＲ^１３は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^１２は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合、又は下記一般式（１３）で表される基である。ｑ１及びｒ１は各々独立に０〜４の整数である。）

(In General Formula (12), R ¹² and R ¹³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹² is an alkylene group having 1 to 5 carbon atoms and 2 carbon atoms. Or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond, or a group represented by the following general formula (13): q1 and r1 each independently represents 0 to 4; (It is an integer.)

（一般式（１３）中、Ｒ^１４及びＲ^１５は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^１３は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ１及びｔ１は各々独立に０〜４の整数である。）

(In General Formula (13), R ¹⁴ and R ¹⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹³ is an alkylene group having 1 to 5 carbon atoms and 2 carbon atoms. An alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond of ˜5, and s1 and t1 are each independently an integer of 0-4.)

Examples of the aliphatic hydrocarbon group represented by R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.
Among these, R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. If p1 is an integer of 2 or more, among the plurality of R ¹¹ may be different even in the same.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹² and R ¹³ are the same as those in the case of R ¹¹ . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, and still more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ¹² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. It is done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics. More preferred is a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ¹² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
A ¹² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
q1 and r1 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. If q1 or r1 is an integer of 2 or more, plural R ¹² s or R ¹³ together may each be the same or different.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹⁴ and R ¹⁵ include the same as those in the case of R ¹² and R ¹³ , and preferable ones are also the same.
Alkylene group having 1 to 5 carbon atoms which A ¹³ represents, alkylidene group having 2 to 5 carbon ^atoms, alkylene group of 1 to 5 carbon atoms ^{which A 12} represents, the same as the alkylidene group having 2 to 5 carbon atoms include The preferred ones are the same.
A ¹³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferably as described above.
s1 and t1 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. If s1 or t1 is an integer of 2 or more, plural R ¹⁴ s or R ¹⁵ together may each be the same or different.
The general formula (13) is preferably represented by the following general formula (13 ′).

（一般式（１３’）中のＡ^１３、Ｒ^１４、Ｒ^１５、ｓ１及びｔ１は、一般式（１３）中のものと同じである。）

(A ¹³ , R ¹⁴ , R ¹⁵ , s1 and t1 in the general formula (13 ′) are the same as those in the general formula (13).)

A ¹¹ is a group represented by the general formula (11) from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. It is preferable that it is a group represented by the following general formula (11 ′).

（一般式（１１’）中、Ｒ^１１及びｐ１は、一般式（１１）中のものと同じである。）

(In General Formula (11 ′), R ¹¹ and p1 are the same as those in General Formula (11).)

  Examples of the aromatic aldehyde compound (ii) include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2′-bipyridine-4,4′-dicarboxaldehyde and the like. Among these, for example, terephthalaldehyde, which can be further reduced in thermal expansion, has high reactivity during reaction, is excellent in solvent solubility, and is easily available commercially, is preferable.

Siloxane compound (b) having at least two primary amino groups [hereinafter sometimes referred to simply as siloxane compound (b). ] Preferably has one or more primary amino groups at both molecular ends, more preferably one primary amino group at each molecular end, and one primary amino group only at both molecular ends. More preferably, it has a group.
The siloxane compound (b) has a linear siloxane skeleton, and preferably has a dimethyl silicone skeleton in the molecule.
The amino group equivalent of the siloxane compound (b) is preferably 200 to 7000, more preferably 300 to 6000, still more preferably 400 to 4000, and particularly preferably 600 to 3000.

A commercially available product can be used as the siloxane compound (b), and “KF-8010” (amino group equivalent 430), “X-22-161A” (amino group equivalent 800), “X-22-161B” ( Amino group equivalent 1500), “KF-8012” (amino group equivalent 2200), “KF-8008” (amino group equivalent 5700), “X-22-9409” (amino group equivalent 700), “X-22-1660B -3 "(amino group equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.)," BY-16-853U "(amino group equivalent 460)," BY-16-853 "(amino group equivalent 650)," BY -16-853B "(amino group equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.), etc., and these may be used alone or in admixture of two or more. There.
Among these, for example, from the viewpoint of reactivity during synthesis and low thermal expansion, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16-853B X-22-161A and X-22-161B are preferable, and X-22-161B is more preferable.

(Method for producing amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure)
First, a thiol compound (i) having at least two primary thiol groups in one molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule are subjected to a dehydration condensation reaction in an organic solvent. [Hereinafter referred to as dehydration condensation reaction 1.] To obtain a thioacetal compound (a) having at least one aldehyde group in one molecule. Next, the compound and the siloxane compound (b) having at least two primary amino groups are subjected to a dehydration condensation reaction [hereinafter referred to as dehydration condensation reaction 2] in an organic solvent. ], An amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure can be obtained.
According to this reaction method, the molecular weight of the thioacetal in the molecule of the amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure can be easily controlled, and the adhesive strength of the resin composition containing this can be improved. It is particularly effective to increase the elastic modulus.

Organic solvents that can be used for each dehydration condensation reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; ester systems such as γ-butyrolactone A solvent etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, from the viewpoint of solubility, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, and γ-butyrolactone are preferable, and remain as a residual solvent when producing a prepreg and a resin-coated film. Propylene glycol monomethyl ether and toluene which are difficult are more preferable.
Further, since the reaction is a dehydration condensation reaction, water is generated as a by-product. For the purpose of removing water as a by-product, it is preferable to react while removing water as a by-product by azeotropy with an aromatic solvent, for example.

  In each dehydration condensation reaction, a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; methylimidazole and phenylimidazole. Examples thereof include imidazole compounds such as: phosphorus-based catalysts such as triphenylphosphine. These can be used individually by 1 type or in mixture of 2 or more types. From the viewpoint of allowing the dehydration condensation reaction to proceed efficiently, an acidic catalyst is preferable, and p-toluenesulfonic acid is more preferable.

(Dehydration condensation reaction 1)
First, a thioacetal compound (a) having at least one aldehyde group in one molecule [hereinafter simply referred to as a thioacetal compound (a)] by dehydrating condensation reaction of the thiol compound (i) and the aromatic aldehyde compound (ii) in an organic solvent. Sometimes referred to as thioacetal compound (a). ] Is obtained.
Here, the amount of thiol compound (i) and aromatic aldehyde compound (ii) used is, for example, the number of aldehyde groups of aromatic aldehyde compound (ii) [the amount of aromatic aldehyde compound (ii) used / aromatic aldehyde compound ( The aldehyde group equivalent of ii) is 1.1 to 5 times the number of primary thiol groups of thiol compound (i) [the amount of thiol compound (i) used / primary thiol group equivalent of thiol compound (i)]. It is preferably used, more preferably 1.5 to 5 times, and even more preferably 2 to 4 times. When the ratio is 1.1 times or more, the reaction proceeds sufficiently, and the product has a formyl group. When the ratio is 5 times or less, characteristics such as high adhesion to metal are exhibited. The number of thioacetals necessary for this can be ensured.

  Moreover, it is preferable that the usage-amount of the organic solvent in the dehydration condensation reaction 1 shall be 25-2000 mass parts with respect to 100 mass parts of total of thiol compound (i) and aromatic aldehyde compound (ii), for example, 40 It is more preferable to set it as -1000 mass parts, and it is still more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, the solubility does not become insufficient, and when it is 2000 parts by mass or less, the reaction does not take a long time.

A thioacetal compound (a) is obtained by charging the above-mentioned raw materials, organic solvent and, if necessary, a reaction catalyst into a reactor, followed by stirring for 0.1 to 10 hours while heating or keeping warm as necessary to cause a dehydration condensation reaction.
The reaction temperature is preferably 70 to 150 ° C., for example, and the reaction is preferably performed while removing water as a by-product, and 100 to 130 ° C. is more preferable. By setting the temperature to 70 ° C. or higher, the reaction rate does not slow down, and by setting the temperature to 150 ° C. or lower, no high boiling point solvent is required for the reaction solvent, and when the prepreg or resin-coated film is produced, It is hard to remain and heat resistance does not decrease.

(Dehydration condensation reaction 2)
Next, a thioacetal compound (a) obtained by the dehydration condensation reaction 1 and a siloxane compound (b) having at least two amino groups are subjected to a dehydration condensation reaction in an organic solvent, whereby a thioacetal compound is introduced into the molecular structure. An amino-modified siloxane compound (I) having acetal and azomethine can be obtained.
Here, the use amount of the thioacetal compound (a) and the siloxane compound (b) is, for example, the number of primary amino groups of the siloxane compound (b) [the use amount of the siloxane compound (b) / the primary amino group of the siloxane compound (b). Equivalent]] is used in a range of 1 to 10 times the number of aldehyde groups of the thioacetal compound (a) [the amount of thioacetal compound (a) used / the aldehyde group equivalent of thioacetal compound (a)]. Is preferred. By setting the ratio to 1 or more, the solubility in a solvent does not decrease. By setting the ratio to 10 or less, the thermosetting resin containing the amino-modified siloxane compound (I) having thioacetal and azomethine is used. Adhesiveness does not decrease.

  Moreover, it is preferable that the usage-amount of the organic solvent in the dehydration condensation reaction 2 shall be 25-2000 mass parts with respect to 100 mass parts of total of a thioacetal compound (a) and a siloxane compound (b), for example, 40- It is more preferable to set it as 1000 mass parts, and it is still more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, the solubility does not become insufficient, and when it is 2000 parts by mass or less, the reaction does not take a long time.

An amino-modified siloxane compound having a thioacetal and an azomethine is prepared by charging the above raw materials, an organic solvent and, if necessary, a reaction catalyst into a reactor and stirring and dehydrating and condensing for 0.1 to 10 hours while heating or keeping warm as necessary. I) is obtained.
The reaction temperature is preferably 70 to 150 ° C., for example, and the reaction is preferably performed while removing water as a by-product, and 100 to 130 ° C. is more preferable. By setting the temperature to 70 ° C. or higher, the reaction rate does not slow down, and by setting the temperature to 150 ° C. or lower, no high boiling point solvent is required for the reaction solvent, and when the prepreg or resin-coated film is produced, It is hard to remain and heat resistance does not decrease.

The amino-modified siloxane compound (I) having thioacetal and azomethine obtained through the dehydration condensation reactions 1 and 2 can be confirmed by performing IR measurement. The IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the peak and azomethine groups around 1440cm ^-1 attributable to _-CH 2 -S- (-N = CH-) appears, also, primary amino group by peak around at 3,440 cm ^-1 and 3370cm ^-1 due to confirm the presence in, favorably reaction proceeds, it is possible to confirm that the desired compound is obtained.

Further, the weight average molecular weight (Mw) of the amino-modified siloxane compound (I) having an aromatic azomethine is not particularly limited, but is preferably 8,000 to 400,000, and more preferably 15,000 to 250,000. More preferably 30,000 to 70,000. If the weight average molecular weight (Mw) is 8,000 or more, low curing shrinkage and low thermal expansion are less likely to be reduced, and if it is 400,000 or less, compatibility and elastic modulus are less likely to be lowered. In the present specification, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene. For example, the following conditions are used. Can do.
Examples of the measuring apparatus include the apparatus described in the examples, an autosampler (AS-8020, manufactured by Tosoh Corporation), a column oven (860-C0, manufactured by JASCO Corporation), an RI detector (830-RI, JASCO Corporation). Co., Ltd.), UV / VIS detector (870-UV, JASCO Corporation), HPLC pump (880-PU, JASCO Corporation) can be used.
In addition, as the column used, for example, TSKgel SuperHZ2000 and 2300 manufactured by Tosoh Corporation can be used, and the measurement conditions include, for example, a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent as tetrahydrofuran. Is possible.

(Maleimide compound (II) having at least two N-substituted maleimide groups in the molecular structure)
The thermosetting resin composition of the present invention further has a maleimide compound (II) having at least two N-substituted maleimide groups in the molecular structure [hereinafter sometimes simply referred to as a maleimide compound (II). ] Is contained.
The maleimide compound (II) is preferably a maleimide compound represented by the following general formula (II).

（一般式（II）中、Ａ^３１は、下記一般式（３１）、（３２）、（３４）又は（３５）で表される基である。）

(In the general formula ^{(II), A 31} is represented by the following general formula (31), (32), a group represented by (34) or (35).)

（一般式（３１）中、Ｒ^３１は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐ２は０〜４の整数である。）

(In the general formula (31), each R ³¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P2 is an integer of 0 to 4.)

（一般式（３２）中、Ｒ^３２及びＲ^３３は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^３２は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合、又は下記一般式（３３）で表される基である。ｑ２及びｒ２は各々独立に０〜４の整数である。）

(In General Formula (32), R ³² and R ³³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³² is an alkylene group having 1 to 5 carbon atoms and 2 carbon atoms. Or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond, or a group represented by the following general formula (33): q2 and r2 are each independently 0 to 4; (It is an integer.)

（一般式（３３）中、Ｒ^３４及びＲ^３５は各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ａ^３３は炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ２及びｔ２は各々独立に０〜４の整数である。）

(In General Formula (33), R ³⁴ and R ³⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³³ is an alkylene group having 1 to 5 carbon atoms and 2 carbon atoms. An alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond of ˜5, and s2 and t2 are each independently an integer of 0-4.)

（一般式（３４）中、ｎ２は０〜１０の整数である。）

(In general formula (34), n2 is an integer of 0-10.)

（一般式（３５）中、Ｒ^３６及びＲ^３７は各々独立に、水素原子又は炭素数１〜５の脂肪族炭化水素基である。ｕ２は１〜８の整数である。）

(In General Formula (35), R ³⁶ and R ³⁷ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U2 is an integer of 1 to 8.)

Examples of the aliphatic hydrocarbon group represented by R ³¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.
Among these, R ³¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p2 is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When p2 is an integer of 2 or more, the plurality of R ³¹ may be the same or different.

Aliphatic hydrocarbon group of 1 to 5 carbon atoms which R ³² and ^{R 33} represent, as the halogen atom ^include the same ones as for ^{R 31.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, and still more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ³² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. It is done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics. More preferred is a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ³² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
Among the above options, A ³² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q2 and r2 are each independently an integer of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. If q2 or r2 is an integer of 2 or more, among the plurality of R ³² s or R ³³ may each be the same or different.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³⁴ and R ³⁵ include the same as those in the case of R ³² and R ³³ , and preferable ones are also the same.
Alkylene group having 1 to 5 carbon atoms which A ³³ represents, alkylidene group having 2 to 5 carbon ^atoms, alkylene group of 1 to 5 carbon atoms ^{which A 32} represents, the same as the alkylidene group having 2 to 5 carbon atoms include The preferred ones are the same.
A ³³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferably as described above.
s2 and t2 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s2 or t2 is an integer of 2 or more, the plurality of R ³⁴ or R ³⁵ may be the same or different from each other.
The general formula (33) is preferably represented by the following general formula (33 ′).

（一般式（３３’）中のＡ^３３、Ｒ^３４、Ｒ^３５、ｓ２及びｔ２は、一般式（３３）中のものと同じである。）

(A ³³ , R ³⁴ , R ³⁵ , s2 and t2 in the general formula (33 ′) are the same as those in the general formula (33).)

A ³¹ is a group represented by the general formula (32) from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. It is preferable that it is a group represented by the following general formula (32 ′).

（一般式（３２’）中のＡ^３２、Ｒ^３２、Ｒ^３３、ｑ２及びｒ２は、一般式（３２）中のものと同じである。）

(A ³² , R ³² , R ³³ , q2 and r2 in the general formula (32 ′) are the same as those in the general formula (32).)

In the general formula (34), n2 is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability.
In the general formula (35), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ³⁶ and R ³⁷ include the same as those in the case of the aliphatic hydrocarbon group of R ³¹ , and preferable ones are also the same. It is.
u2 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

As A ³¹ in the group represented by the general formula (II), from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics, A group represented by any one of the formulas is preferred.

  As the maleimide compound (II), bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5 '-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, etc. Can be mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4, which has a high reaction rate and can have higher heat resistance. 4'-diphenylmethane bismaleimide and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred. From the viewpoint of solubility in a solvent, 3,3'-dimethyl-5,5'-diethyl- 4,4′-Diphenylmethane bismaleimide and bis (4-maleimidophenyl) methane are more preferable, and bis (4-maleimidophenyl) methane is more preferable from the viewpoint of being inexpensive.
The content of the maleimide compound (II) in the thermosetting resin composition of the present invention is based on 100 parts by mass of the total solid content of the thermosetting resin composition (excluding inorganic fillers). Preferably it is 30-80 mass parts, More preferably, it is 35-65 mass parts. If it is this range, since an elasticity modulus and low thermal expansibility improve, it is preferable.

(Other ingredients)
(Amine compound having acidic substituent (III))
The thermosetting resin composition of the present invention may further contain an amine compound (III) having an acidic substituent. The number of acidic substituents possessed by the amine compound (III) is preferably 1 or 2, and more preferably 1.
Here, examples of the acidic substituent include a hydroxyl group, a carboxyl group, and a sulfonic acid group. The amine compound (III) having an acidic substituent preferably has at least one selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group.
Examples of the amine compound (III) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, and o-aminobenzene. Examples include sulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline from the viewpoint of solubility and synthesis yield. M-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance, and p-aminophenol is more preferable from the viewpoint of low thermal expansion.

  When the thermosetting resin composition of the present invention contains an amine compound (III) having an acidic substituent, the content thereof is a solid content in the thermosetting resin composition (however, an inorganic filler is added). Is preferably 0.5 to 20 parts by mass, and more preferably 0.7 to 15 parts by mass with respect to 100 parts by mass of the total. By setting it as this range, heat resistance and low thermal expansion property are improved.

The amino-modified siloxane compound (I) having a thioacetal and azomethine in the molecular structure, the maleimide compound (II), and the amine compound (III) having an acidic substituent are contained in the thermosetting resin composition as they are. It may be used after reacting at least a part of each component, for example, by heating or keeping warm, if necessary, and other components may be added to the thermosetting resin composition as necessary. After containing together, at least a part of each component may be reacted, for example, by heating or keeping warm. Here, the reaction of the amino-modified siloxane compound (I) having a thioacetal and azomethine in the molecular structure and the maleimide compound (II) is referred to as a modified imide resin (J) having a thioacetal in the molecular structure. In addition, an amino-modified siloxane compound (I) having a thioacetal and azomethine in the molecular structure, a maleimide compound (II), and an amine compound (III) having an acidic substituent are reacted with an acidic substituent. It may be called the modified imide resin (K) which has a thioacetal.
In this case, the content of the maleimide compound (II) in the thermosetting resin composition is such that the equivalent of the maleimide group of the maleimide compound (II) is in the molecular structure from the viewpoint of prevention of gelation and heat resistance. The amount is preferably more than the equivalent of the primary amino group of the amino-modified siloxane compound (I) having thioacetal and azomethine and the amine compound (III) having an acidic substituent. The content of the amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure is about 7 to 35 times the content of the amine compound (III) having an acidic substituent. From the viewpoint of
When heating, the temperature is preferably 70 to 200 ° C., and the reaction time is preferably 0.5 to 10 hours.

The organic solvent that can be used in the above reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents; ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Containing solvent; Sulfur atom-containing solvent such as dimethyl sulfoxide. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable. Low toxicity and high volatility make it difficult to remain as a residual solvent in the production of a prepreg or resin-coated film. From the viewpoint, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable.
The amount of the organic solvent used is an amino-modified siloxane compound (I) having a thioacetal and azomethine in the molecular structure, a maleimide compound (II), and an amine compound having an acidic substituent (III) from the viewpoint of solubility and reaction time. It is preferable to set it as 25-1000 mass parts per 100 mass parts of total amount of, and it is more preferable to set it as 40-700 mass parts.

(Thermoplastic elastomer (IV))
The thermosetting resin composition of the present invention may further contain a thermoplastic elastomer (IV).
As thermoplastic elastomer (IV), styrene thermoplastic elastomer, olefin thermoplastic elastomer, urethane thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, acrylic thermoplastic elastomer, silicone thermoplastic elastomer And derivatives thereof. These are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, in terms of heat resistance and insulation reliability, styrene thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, and silicone thermoplastic elastomers are preferable, and styrene thermoplastic elastomers are more preferable.
The styrene-based thermoplastic elastomer is not particularly limited as long as it is a thermoplastic elastomer having a structural unit derived from styrene (see below).

Examples of the structural unit other than the structural unit derived from styrene in the styrene-based thermoplastic elastomer include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, and a structural unit derived from maleic anhydride. Styrenic thermoplastic elastomers may be used alone or in combination of two or more.
The structural unit derived from butadiene and the structural unit derived from isoprene are preferably hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
The styrene-based thermoplastic elastomer includes a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) from the viewpoints of heat resistance, adhesion to a conductor, glass transition temperature, thermal expansion coefficient, elastic modulus, and high frequency characteristics. , SBBS), and a hydrogenated product of styrene-isoprene-styrene block copolymer (SEPS), preferably a hydrogenated product of styrene-butadiene-styrene block copolymer (SEBS, SBBS) is more preferred.
The hydrogenated styrene-butadiene-styrene block copolymer includes SEBS in which the hydrogenation rate of carbon-carbon double bonds is usually 90% or more (preferably 95% or more), and 1 in the butadiene block. , SBBS in which the carbon-carbon double bonds at the 2-bonding sites are partially hydrogenated (the hydrogenation rate with respect to the total carbon-carbon double bonds is approximately 60 to 85%). Among these, SEBS is more preferable.

Moreover, as a thermoplastic elastomer (IV), what has a reactive functional group in a molecular terminal or a molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminal or molecular chain, compatibility with the resin is improved, and internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. As a result, it is possible to significantly reduce the warpage of the substrate.
Moreover, the reactive functional group possessed in the molecular terminal or molecular chain is preferably an epoxy group, a hydroxyl group, a carboxyl group, an amino group, or an amide group from the viewpoint of adhesion to the metal foil, and has heat resistance and insulation reliability. From the viewpoint, an epoxy group, a hydroxyl group, and an amino group are more preferable.

  When the thermosetting resin composition contains a thermoplastic elastomer (IV), the content of the resin is good in compatibility with the resin and can effectively express the low curing shrinkage and low thermal expansion of the cured product. From a viewpoint, 0.1-50 mass parts is preferable with respect to the sum total of 100 mass parts of solid content (however, except an inorganic filler) of a thermosetting resin composition, 2-30 mass parts is more preferable, 5-30 mass parts is more preferable.

(Thermosetting resin (V))
The thermosetting resin composition of the present invention may further contain a thermosetting resin. Examples of the thermosetting resin (V) include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, Silicone resin, triazine resin, melamine resin and the like can be mentioned. These may be used alone or in combination of two or more. Among these, an epoxy resin and a cyanate resin are preferable from the viewpoints of moldability and electrical insulation.

As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable. Here, the epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin is preferable.
Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton, and in each of the above types of epoxy resins, bisphenols such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are also included. Type epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, etc .; phenol Aralkyl epoxy resin; Stilbene epoxy resin; Dicyclopentadiene epoxy resin; Naphthalene bone such as naphthol novolac epoxy resin and naphthol aralkyl epoxy resin Type epoxy resin; triazine skeleton containing epoxy resin; fluorene skeleton containing epoxy resin; triphenolmethane type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy resin; dihydroanthracene type epoxy resin; Epoxy resins; classified into phosphorus-containing epoxy resins in which a phosphorus compound is introduced. These may be used alone or in combination of two or more.
Among these, from the viewpoint of heat resistance and flame retardancy, a biphenyl aralkyl type epoxy resin and a naphthalene skeleton-containing type epoxy resin are preferable.

Examples of the cyanate resin include novolak-type cyanate resins, bisphenol A-type cyanate resins, bisphenol E-type cyanate resins, and bisphenol-type cyanate resins such as tetramethylbisphenol F-type cyanate resins, and prepolymers in which these are partially triazine. be able to. Among these, a novolac-type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These may be used alone or in combination of two or more.
When a thermosetting resin composition contains a thermosetting resin (V), the content is 100 mass of the sum total of solid content (however, except an inorganic filler) in a thermosetting resin composition. 1-50 mass parts is preferable with respect to part, 1-30 mass parts is more preferable, and 1-20 mass parts is further more preferable.

(Curing accelerator (VI))
The thermosetting resin composition of the present invention may contain a curing accelerator (VI).
When the thermosetting resin contains an epoxy resin, examples of the curing accelerator include 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene- Cyclic amidine compounds such as diazabicycloalkenes such as 7 (DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; Phenol novolak salts of amidine compounds or derivatives thereof; maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone; 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy Compounds having intramolecular polarization formed by adding a compound having a π bond such as quinone compounds such as 1,4-benzoquinone and phenyl-1,4-benzoquinone and diazophenylmethane; tetraphenylborate salt of DBU, DBN Cyclic amidinium compounds such as tetraphenylborate salt, tetraphenylborate salt of 2-ethyl-4-methylimidazole, tetraphenylborate salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethyl Tertiary amine compounds such as aminoethanol and tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylacetate Ammonium salts such as ammonium, benzoic acid tetra-n-hexylammonium, tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris ( Alkyl / alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxy) Tertiary) phosphine such as phenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; Phosphine compounds such as complexes of phosphine and organic boron; the tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone Quinone compounds such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenyl A compound having intramolecular polarization formed by adding a compound having a π bond, such as methane; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethyl Phenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4′-hydroxybiphenyl, etc. A compound having intramolecular polarization obtained by reacting with a halogenated phenol compound of the above, followed by a dehydrohalogenation step; tetraphenylphosphonium, tetra p-tolylborate and the like having no phenyl group bonded to a boron atom Substituted phosphonium and tetrasubstituted borates; salts of tetraphenylphosphonium and phenolic compounds And so on.
Imidazole derivatives (isocyanate mask imidazole) obtained by reacting imidazoles and derivatives thereof with polyisocyanate compounds, and imidazole derivatives obtained by reacting imidazole groups with epoxy resins are preferred.
The amount of the curing accelerator used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.1 to 1 part by mass per 100 parts by mass of the epoxy resin. It is particularly preferable to do this. Excellent heat resistance and copper foil adhesion can be obtained by setting the use amount of the curing accelerator to 0.1 parts by mass or more, and heat resistance, aging stability and press formability by setting it to 10 parts by mass or less. Does not drop.

  When the thermosetting resin contains a cyanate resin, metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used as the curing accelerator. Specifically, 2-ethylhexanoate and naphthene are used. It is used as organometallic salt compounds such as acid salts and organometallic complexes such as acetylacetone complexes. It is preferable to set it as 1-300 ppm with respect to cyanate resin 1 (g), It is more preferable to set it as 2-200 ppm, It is further more preferable to set it as 2-150 ppm. When the blending amount of the curing accelerator is less than 1 ppm, the reactivity and curability tend to be insufficient, and when it exceeds 300 ppm, the reaction is difficult to control, or the curing becomes too fast and the moldability tends to deteriorate. is there.

(Inorganic filler (VII))
The thermosetting resin composition of the present invention may further contain an inorganic filler (VII). Inorganic fillers (VII) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, aluminum borate, silicon carbide, short glass fiber, fine glass powder, hollow glass, etc. It is done. Preferred examples of the glass include E glass, T glass, and D glass. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
Among these, silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is more preferable from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance, and flame retardancy. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the production method. Among these, fused silica is preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

  When fused silica is used as the inorganic filler, the average particle size is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.1 to 2 μm, particularly preferably. 0.2-1 μm. By making the average particle diameter of the fused silica 0.1 μm or more, the fluidity at the time of high filling can be kept good, and by making it 10 μm or less, the mixing probability of coarse particles is reduced and coarse particles It is possible to suppress the occurrence of defects due to. Here, the average particle size is a particle size at a point corresponding to a volume of just 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  The blending amount of the inorganic filler is preferably 0 to 300 parts by mass, more preferably 50 to 100 parts by mass of the total solid content in the thermosetting resin composition (excluding the inorganic filler). It is 270 mass parts, More preferably, it is 100-250 mass parts, Most preferably, it is 150-230 mass parts. By making the compounding quantity of an inorganic filler into this range, the moldability and low thermal expansion property of a prepreg and a film with a resin can be kept favorable.

  The thermosetting resin composition of the present invention has a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, to the extent that the thermosetting property is not impaired as the resin composition. You may contain a fluorescent whitening agent, an adhesive improvement agent, etc. You may use these individually by 1 type or in mixture of 2 or more types.

(Thermoplastic resin)
Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.

(Organic filler)
Examples of organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin Etc. and a core-shell resin filler having a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like Is mentioned.

(Flame retardants)
Examples of the flame retardant include phosphorus flame retardant, metal hydrate, halogen flame retardant and the like. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates are preferred, and halogen-based flame retardants are usually limited to use in electronic components that are not discarded or burned.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides; phosphorus Acid; phosphine oxide and the like.
Examples of organic phosphorus flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogen-containing phosphorous compounds, and cyclic organophosphorus compounds. It is done.
Examples of the metal hydrate include aluminum hydroxide hydrate and magnesium hydroxide hydrate.
Examples of the halogen flame retardant include a chlorine flame retardant and a bromine flame retardant.

(UV absorber, etc.)
As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenone-based, benzyl ketal-based, and thioxanthone-based photopolymerization initiators. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesion improver include urea compounds such as urea silane; coupling agents such as silane, titanate, and aluminate.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with an silane-based or titanate-based coupling agent or a surface-treating agent such as a silicone oligomer, or an integral blend treatment.

(Organic solvent)
From the viewpoint of facilitating handling by diluting the thermosetting resin composition of the present invention and from the viewpoint of facilitating the production of a prepreg or a film with a resin described later, the thermosetting resin composition is made into a varnish state by containing an organic solvent. It is also preferable to use a varnish. In the present specification, the varnish may be referred to as a resin varnish.
The organic solvent is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents; aromatic solvents such as toluene, xylene and mesitylene; nitrogen-containing solvents including amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atoms including sulfoxide solvents such as dimethyl sulfoxide Examples of the solvent include: ester solvents including lactone solvents such as γ-butyrolactone.
One organic solvent may be used alone, or two or more organic solvents may be used in combination.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, ketone solvents are more preferable, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are more preferable, and methyl ethyl ketone is particularly preferable.
The solid (nonvolatile content) concentration of the varnish finally obtained is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass of the entire varnish. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to obtain a prepreg and a resin-coated film in which an appropriate amount of the thermosetting resin composition is adhered while maintaining good coating properties.

[Prepreg]
The prepreg of the present invention is coated with the above-described thermosetting resin composition of the present invention by a method of impregnating the substrate or by impregnating or spraying the substrate, followed by extrusion, slitting or the like (collectively, “ It may be referred to as “impregnation or coating”). Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention can be obtained by impregnating or coating the thermosetting resin composition of the present invention on a substrate and semi-curing (B-stage), for example, by heating. As this base material, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and polytetrafluoroethylene; and mixtures thereof. In other applications, for example, carbon fibers can be used for fiber reinforced substrates.

  These base materials have a shape such as a woven fabric, a nonwoven fabric, a low-ink, a chopped strand mat, or a surfacing mat. The material and shape are selected depending on the intended use and performance of the molded product, and if necessary, two or more kinds of materials and shapes can be combined. The thickness of the base material can be, for example, about 0.02 to 0.5 mm, and the surface treated with a silane coupling agent or the like or mechanically subjected to fiber opening treatment has heat resistance and It is suitable in terms of moisture resistance and processability.

  The prepreg of the present invention is, for example, impregnated or coated on a substrate so that the amount of the thermosetting resin composition attached to the substrate is 20 to 90% by mass in terms of the resin content of the prepreg after drying. After that, it can usually be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The film with resin of the present invention is obtained by coating the thermosetting resin composition on a support. Specifically, the resin-coated film of the present invention is a film in which a semi-cured film of a thermosetting resin composition is formed on the support surface. The said thermosetting resin composition is apply | coated to a support body film, an organic solvent is volatilized by drying, and a resin composition layer can be formed by carrying out semi-hardening (B stage-izing). However, this semi-cured state is a state in which when the thermosetting resin composition is cured, the adhesive strength between the insulating resin layer and the circuit pattern substrate forming the same is ensured, and the embedding property of the circuit pattern substrate ( It is preferable that fluidity is ensured. As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and it is appropriately used depending on the thickness of the insulating resin layer. As a drying method, heating or hot air blowing can be used.

  The drying condition after applying the thermosetting resin composition to the support is, for example, that the content of the organic solvent in the thermosetting resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Let dry. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, the insulating resin composition layer becomes It is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the insulating resin composition layer formed in the resin-attached film is usually not less than the thickness of the conductor layer that the circuit board has. The thickness of the conductor layer is preferably, for example, 5 to 70 μm, more preferably 5 to 50 μm, and still more preferably 5 to 30 μm for reducing the thickness and thickness of the multilayer printed wiring board.

  The support in the film with resin is a film made of polyolefin such as polyethylene, polypropylene or polyvinyl chloride, polyester such as polyethylene terephthalate or polyethylene naphthalate, polycarbonate or polyimide; release paper; metal foil such as copper foil or aluminum foil Is mentioned. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment.

For example, the thickness of the support is preferably 10 to 150 μm, more preferably 25 to 50 μm. A protective film according to the support can be further laminated on the surface of the thermosetting resin composition layer on which the support is not in close contact. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from being mixed.
The film with resin can also be wound and stored in a roll shape.

  As a form of the method for producing a multilayer printed wiring board by forming a laminated board using the resin-coated film of the present invention, for example, a resin-coated film is laminated on one or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Further, in a laminated board obtained by alternately laminating conductor layers and insulating layers, and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned ( Circuits) are also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

  In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to circuit board. In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the resin-coated film on the circuit board, the insulating resin layer can be formed on the circuit board by cooling it to around room temperature and then peeling it off when the support is peeled off and thermosetting. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 to 220 ° C for 20 to 180 minutes, more preferably 160 to 200 ° C for 30. Selected in the range of ~ 120 minutes.

  If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide laser or YAG laser is the most common method.

  Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin composition layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Roughening treatment is performed with an oxidizing agent such as to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, a known subtractive method, semi-additive method, or the like can be used.

[Laminated board]
The laminate of the present invention can be formed by laminate molding using the prepreg or the resin-coated film of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper or aluminum on one or both sides thereof.
As the molding conditions for producing the laminated plate, for example, the method of the laminated plate for electric insulation material and the multilayer plate can be applied, and a temperature of 100 to 250 is used using a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine or the like. It can shape | mold in the range of 0.1 degreeC and the heating time for 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a laminated board.

[Multilayer printed wiring board]
The multilayer printed wiring board according to the present invention is manufactured by forming a circuit on the surface of the laminated board. For example, a circuit board can be obtained by wiring a conductor layer of a laminated board according to the present invention by a normal etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing, and formation of an interlayer wiring by plating or conductive paste.

[Semiconductor package]
The semiconductor package according to the present invention is manufactured by mounting a semiconductor chip, a memory, or the like at a predetermined position of the multilayer printed wiring board.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
The copper clad laminate obtained in the following examples was measured and evaluated for performance by the following method.

(1) Curing Shrinkage Ratio of Resin Plate The resin plate obtained in each example was cut out to prepare a 5 mm square resin plate, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). After mounting the resin plate in the Z direction on the device, load 5g, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 min hold) to 260 ° C (2 min hold) to 20 ° C (5 min hold) Measured with The cure shrinkage rate of the resin plate was evaluated from the initial dimension of the resin plate and the dimensional change at 20 ° C. before starting the temperature increase and 20 ° C. after the temperature increase.

(2) High frequency characteristics (dielectric constant and dielectric loss tangent)
After removing the copper-clad laminate obtained in each example by etching, the copper-clad laminate was cut into a size of 60 mm in length and 2 mm in width, and Dk and Df at 10 GHz at an atmospheric temperature of 25 ° C. Calculated from unloaded Q value. The measurement was performed using a vector network analyzer E8364B manufactured by Agilent Technologies, CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Electronics Co., Ltd., respectively.

(3) Evaluation of solder heat resistance with copper A 25 mm square evaluation board was produced from the copper clad laminate obtained in each example, and the evaluation board was floated in a solder bath at a temperature of 288 ° C. for 120 minutes, and the appearance was visually observed. By observing, the solder heat resistance with copper was evaluated according to the following evaluation criteria.
A: No swelling C: With swelling

(4) Copper foil adhesion (copper foil peel strength)
The copper-clad laminate obtained in each example is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and the adhesion of the copper foil (90 ° peel strength) using a tensile tester Was measured.
The wiring board preferably has a peel strength of 0.7 KN / m or more.

(5) Glass transition temperature (Tg)
A copper-clad laminate obtained in each example was immersed in a copper etching solution to prepare a 5 mm square evaluation substrate from which the copper foil was removed, and a thermal machine was used by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). Analysis was carried out. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(6) Coefficient of thermal expansion A copper-clad laminate obtained in each example was immersed in a copper etchant to produce a 5 mm square evaluation substrate from which the copper foil was removed, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. The thermomechanical analysis was performed by the compression method. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of thermal expansion coefficient (linear expansion coefficient).

(7) Flexural Modulus A copper-clad laminate obtained in each example was immersed in a copper etching solution to produce a 50 mm long and 25 mm wide evaluation board from which copper foil was removed, and 5 ton tensilon manufactured by Orientec Co., Ltd. Was measured at a crosshead speed of 1 mm / min and a span distance of 20 mm.
In addition, as a wiring board, the bending elastic modulus of 28 GPa or more is preferable.

  In each example, the compounds (I-1) to (I-2), (J-1) and (K-1) produced in the following production examples were used.

Production Example 1: Production of amino-modified siloxane compound (I-1) having thioacetal and azomethine in the molecular structure Heating and cooling capacity of 2 L with thermometer, stirrer and moisture meter with reflux condenser In a reaction vessel, trimethylolpropane tris (3-mercaptopropionate) (i-1) “TMMP” (manufactured by SC Organic Chemical Co., Ltd.) as a thiol compound (i) having at least two primary thiol groups in one molecule. 13.4 g 17.6 g of terephthalaldehyde (ii) “TPAL” (manufactured by Toray Fine Chemical Co., Ltd.) as an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule, propylene glycol monomethyl ether 46 0.5 g and react at 115 ° C for 4 hours, then heated to 130 ° C and concentrated at atmospheric pressure And water, thioacetal compound (a) is a thioacetal compound-containing solution having at least one aldehyde group in the molecule: (solid content concentration 60 wt%).
Next, siloxane compound (b) “X-22-161B” (manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent 1500) as a siloxane compound (b) having at least two primary amino groups is added to the reaction solution. 5 g and 513.3 g of propylene glycol monomethyl ether were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by atmospheric concentration, and an amino-modified siloxane compound having thioacetal and azomethine in the molecular structure ( I-1) A containing solution (Mw: 40000, solid content concentration: 90% by mass) was obtained.
Note that, by IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, the peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups Confirmed that it exists.

Production Example 2: Production of amino-modified siloxane compound (I-2) having thioacetal and azomethine in the molecular structure Heating and cooling capacity of 2 L with thermometer, stirrer and moisture meter with reflux condenser In a reaction vessel, pentaerythritol tetrakis (3-mercaptopropionate) (i-2) “PEMP” (SC Organic Chemical Co., Ltd.) 15.4 g, terephthalaldehyde (ii) “TPAL” (Toray Fine Chemical Co., Ltd.) ) 21.6 g and 56.5 g of propylene glycol monomethyl ether were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by normal pressure concentration, and a thioacetal compound-containing solution (solid content concentration: 60 mass) %).
Next, 413.8 g of siloxane compound (b) “X-22-161B” (manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent 1500) and 645.7 g of propylene glycol monomethyl ether are added to the reaction solution at 115 ° C. After reacting for 4 hours, the temperature was raised to 130 ° C. and dehydrated by atmospheric concentration, and a solution containing amino-modified siloxane compound (I-2) having thioacetal and azomethine (Mw: 50000, solid content concentration: 90% by mass) Got.
Note that, by IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, the peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups Confirmed that it exists.

Production Example 3 Production of Modified Imide Resin (J-1) Having Thioacetal in Molecular Structure In a reaction vessel with a volume of 2 L that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. , 77.8 g of an amino-modified siloxane compound (I-1) -containing solution (solid content concentration: 90% by mass) having thioacetal and azomethine, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (c -2) 246.9 g and propylene glycol monomethyl ether 425.3 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and modified imide resin having thioacetal (J-1) A containing solution (Mw: 7000, solid content concentration: 60% by mass) was obtained.
The modified imide resin (J-1) corresponds to a product obtained by previously reacting an amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure with a maleimide compound (II).

Production Example 4: Production of modified imide resin (K-1) having acidic substituent and thioacetal in the molecular structure Heating and cooling capacity 2 L with thermometer, stirrer, moisture meter with reflux condenser 94.7 g of a solution containing an amino-modified siloxane compound (I-1) having thioacetal and azomethine (solid content concentration: 90% by mass), 2,2-bis [4- (4-maleimidophenoxy) phenyl ] After adding 225.6 g of propane (c-2), 2.3 g of p-aminophenol, and 427.4 g of propylene glycol monomethyl ether, the mixture was reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure. A modified imide resin (K-1) -containing solution (Mw: 5000, solid content concentration: 60% by mass) having an acidic substituent and an aromatic azomethine was obtained.
The modified imide resin (K-1) includes an amino-modified siloxane compound (I) having thioacetal and azomethine in the molecular structure, and a maleimide compound having at least two N-substituted maleimide groups in the molecular structure ( This corresponds to a reaction between II) and an amine compound (III) having an acidic substituent.

Here, in the said manufacture example, the weight average molecular weight (Mw) was converted from the calibration curve using a standard polystyrene by the gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name]) and approximated by a cubic equation. The GPC conditions are shown below.
Apparatus: (Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]),
(Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]),
(Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
Column; TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation, trade name)
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 20mg / 5mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

Examples 1-19, Comparative Examples 1-6
Each component is mixed at a blending ratio shown in Tables 1 to 4 (parts by mass: in the case of a solution, it is a solid content conversion value), and the solid content (nonvolatile content) concentration is 65% by mass using methyl ethyl ketone as a solvent. A varnish was prepared. Next, this varnish was impregnated and coated on an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
The varnish is applied to a 16 μm polyethylene terephthalate film using a film applicator (PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying is 35 μm, and heated at 160 ° C. for 10 minutes. Drying was performed to obtain a semi-cured resin powder.
This resin powder is put into a polytetrafluoroethylene resin mold (length: 4 cm, width: 3 cm), and the glossy surface of 12 μm electrolytic copper foil is placed up and down at a pressure of 2.0 MPa and a temperature of 240 ° C. After pressing for 60 minutes, the electrolytic copper foil was removed to obtain a resin plate having a thickness of 1 mm.
The result of having tested or evaluated using the obtained copper clad laminated board and the resin board was shown to Tables 1-4.

Hereinafter, each component in Tables 1 to 4 will be described.
Maleimide compound (II)
(II-1) Bis (4-maleimidophenyl) methane [manufactured by Kay Kasei Co., Ltd .; trade name: BMI]
(II-2) 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (manufactured by Daiwa Kasei Kogyo Co., Ltd .; trade name: BMI-4000)

Amine compound having acidic substituent (III)
p-aminophenol (manufactured by Kanto Chemical Co., Inc.)

Thermoplastic elastomer (IV)
(IV-1) Tuftec (registered trademark) H1043: Hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation)
(IV-2) Epofriend (registered trademark) CT-310: Epoxy-modified styrene-butadiene copolymer resin [manufactured by Daicel Corporation]
(IV-3) Tuftec (registered trademark) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation)

Thermosetting resin (V)
(V-1) Naphthalene skeleton-containing epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-7000L, more specifically, α-naphthol / cresol novolac type epoxy resin]
(V-2) Biphenyl aralkyl type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-3000H]

Curing accelerator (VI)
(VI-1): Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-8809L, addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole]
(VI-2): Triphenylphosphine triphenylborane [made by Hokuko Chemical Co., Ltd., trade name: TPP-S]

Inorganic filler: fused silica (manufactured by Admatechs Co., Ltd .: trade name: SC2050-KNK, average particle size: 0.5 μm, surface treatment: vinylsilane coupling agent (1% by mass / solid content), dispersion medium: methyl isobutyl ketone , Solid concentration 70 mass%, density 2.2 g / cm ³ )
Aromatic amine compound: 4,4′-diamino-3,3′-diethyldiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD AA]
Aromatic aldehyde compound: terephthalaldehyde (Toray Fine Chemical Co., Ltd., TPAL)
Siloxane compound: X-22-161B [manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent 1500]

As is clear from Tables 1 to 4, the thermosetting resin compositions of the examples have a low cure shrinkage and excellent low cure shrinkage, and further have heat resistance, thermal expansion, copper foil adhesion, and elastic modulus. Excellent in high frequency characteristics.
On the other hand, in the thermosetting resin composition of the comparative example, the curing shrinkage rate of the resin plate is large, and also in the characteristics of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, the elastic modulus and the high frequency characteristics are compared with the examples. And it is inferior to any of the characteristics.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, a resin-coated film obtained by coating on a support, and a laminate produced by laminating the prepreg In particular, it has high heat resistance, low curing shrinkage, high adhesion, high glass transition temperature, low thermal expansion, high elastic modulus, and excellent high frequency characteristics, and for highly integrated semiconductor packages and electronic devices. It is useful as a multilayer printed wiring board.

Claims (12)

  A thiol compound (i) having at least two primary thiol groups in one molecule and obtained by reacting an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule at least in one molecule An amino-modified siloxane compound having thioacetal and azomethine in the molecular structure obtained by reacting a thioacetal compound (a) having one aldehyde group with a siloxane compound (b) having at least two primary amino groups (I) A thermosetting resin composition comprising a maleimide compound (II) having at least two N-substituted maleimide groups in the molecular structure.   The thermosetting resin composition according to claim 1, further comprising an amine compound (III) having an acidic substituent.   Furthermore, the thermosetting resin composition of Claim 1 or Claim 2 formed by containing a thermoplastic elastomer (IV).   Furthermore, the thermosetting resin composition as described in any one of Claims 1-3 formed by containing a thermosetting resin (V).   Furthermore, the thermosetting resin composition as described in any one of Claims 1-4 containing a hardening accelerator (VI).   Furthermore, the thermosetting resin composition as described in any one of Claims 1-5 formed by containing an inorganic filler (VII).   A prepreg obtained by impregnating or coating the thermosetting resin composition according to any one of claims 1 to 6 on a base material and then forming a B-stage.   The film with a resin obtained by coating the thermosetting resin composition as described in any one of Claims 1-6 on a support body.   A laminate obtained by laminating the prepreg according to claim 7.   A laminate obtained by laminating and forming the resin-coated film according to claim 8.   The multilayer printed wiring board manufactured using the laminated board of Claim 9 or 10.   The semiconductor package which mounts a semiconductor on the multilayer printed wiring board of Claim 11.