CN104024332A

CN104024332A - Epoxy resin composition, semi-hardened epoxy resin composition, hardened epoxy resin composition, resin sheet, prepreg, laminate sheet, metal substrate, wiring board, method for producing semi-hardened epoxy resin composition, and method for producing

Info

Publication number: CN104024332A
Application number: CN201280053424.3A
Authority: CN
Inventors: 吉田优香; 竹泽由高; 宫崎靖夫; 高桥裕之
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2011-11-02
Filing date: 2012-10-31
Publication date: 2014-09-03
Also published as: TW201811561A; JP6102744B2; JP6171310B2; CN109293883A; JP2017101257A; JP6304419B2; TWI616334B; TW201720657A; TWI577720B; JP2013234313A; TW201333089A; JPWO2013065758A1; KR20140087015A; KR101958506B1; WO2013065758A1

Abstract

The present invention provides an epoxy resin composition including: an epoxy resin monomer represented by the following Formula (I); a hardening agent containing a novolak resin obtained from a divalent phenol compound; and an alumina filler containing-alumina. In the Formula (I), R1 to R4 each independently represent a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms.

Description

Resin combination and the resin sheet, prepreg, plywood, metal substrate, printing distributing board and the power semiconductor arrangement that use this resin combination

Technical field

The resin sheet, prepreg, plywood, metal substrate, printing distributing board and the power semiconductor arrangement that the present invention relates to resin combination and use this resin combination.

Background technology

Electronics, electric installation from motor, generator to printing distributing board, IC chip mostly comprises conductor for switching on and insulating material and forms.In recent years, be accompanied by the miniaturization of these equipment, thermal value increases, so how insulating material dispels the heat and become important problem.

As the insulating material using in these equipment, from viewpoints such as insulativity, thermotolerances, consider, be widely used the resin cured matter being formed by resin combination.But the thermal conductivity of resin cured matter is low conventionally, this becomes the larger principal element that hinders heat radiation, therefore wishes that exploitation has the resin cured matter of high thermal conductivity.

As the method that realizes the high thermal conduction of resin cured matter, there is the heat conductivity filler that filling consists of high thermal conductivity pottery in resin combination and make the method for matrix material.As high thermal conductivity pottery, known boron nitride, aluminum oxide, aluminium nitride, silicon-dioxide, silicon nitride, magnesium oxide, silicon carbide etc.By filling and take into account the heat conductivity filler of high thermal conductivity and electrical insulating property, thereby in matrix material, realize taking into account of high thermoconductivity and insulativity in resin combination.

With above-mentioned associated ground, in TOHKEMY 2009-13227 communique, reported following content: by also adding the mineral filler of a small amount of nano-particles size the above-mentioned heat conductivity filler except micron particle size, obtained the good electrically insulating material resin combination of electrical insulating property and heat conductivity.

And then, as the method that realizes the high thermal conduction of resin cured matter, studied the method for arranging in an orderly manner the high thermal conduction that realizes resin itself by make to have the monomer of mesomorphic group in molecule.As an example of such monomer, the epoxy monomer as shown in No. 4118691 communique of Japanese Patent has been proposed.

At this, as a mode that is equipped on the insulating material in electric installation, sometimes in order to improve dimensional stability, physical strength etc., use the fiber base materials such as woven cloths, non-woven, resin combination is immersed in this fiber base material, make prepreg.Pickling process as resin combination in fiber base material, has following method: the vertical coating method of mentioning after making fiber base material slip in resin combination and press the horizontal coating method that fiber base material floods on support membrane after coating resin composition.State in the use in the situation of such resin combination that comprises filler, consider the sedimentation of filler, many applicable horizontal coating methods that form deviation that are difficult for producing in fiber base material.

Summary of the invention

The problem that invention will solve

In the resin combination of above-mentioned heat conductivity filler of filling micron particle size, in order to realize the high thermoconductivity requiring in recent years, need to increase the loading level of filler.At height, fill in Packed resin combination, because the interaction of filling surface and resin is significantly risen viscosity, have thus the situation that is easily involved in air and comprises bubble.In addition,, due to filler chimeric frequency gets higher each other, therefore there is the significantly reduced situation of mobility.Consequently, with regard to height is filled Packed resin combination, by the bubble being produced by the bad hole causing of imbedding of the surface tissue of adhesives, when coating, be difficult to disappear, in the insulating material of being made by this resin combination, there is the tendency that insulation breakdown easily occurs due to these holes, bubble.

In addition, when resin combination being immersed in make prepreg in fiber base material, amount of filler in if tree oil/fat composition is many, and filler and fiber are chimeric and stop up, and resin does not fully ooze out from the surface of fiber base material or do not fill up the gap of fiber completely and residual hole sometimes.And then from the inadequate situation of oozing out of fiber base material surface, prepreg is to being caused interface peel by the bonding force of adhesives deficiency sometimes at resin.And then, sometimes by the hole in adhesives interface, fiber base material, also caused the reduction of insulativity.

At this, in order to improve the mobility of the resin combination of filling filler, conventionally there is such method: (1) reduces method, (2) of resin viscosity and reduces by the surface treatment of filler or the interpolation of dispersion agent the method that is bound in the amount of resin on filling surface.

But when only merely having reduced the viscosity of resin, although from the exudative improvement of the resin on fiber base material surface itself, the chimeric of filler and fiber improves.Therefore there is such problem: residual filler on fiber and only have resin to ooze out from the surface of fiber base material, and then when pressure is excessive, only have resin to ooze out and form the defects such as hole.There is in addition such problem: the excess stickiness of resin combination declines, the sedimentation of filler occurs on the thickness direction of the coated film of resin combination, thus the deep or light distribution that can produce filler on the thickness direction of coated film.

On the other hand, in the situation that only by the surface treatment of filler, the interpolation of dispersion agent has improved the mobility of resin combination, if increase the addition of surface-treated filler coating rate, dispersion agent for resin is fully oozed out from the surface of fiber base material, exist the Chemical bond of filler and resin to be hindered, as the thermal conductivity of matrix material, reduce such problem.

In addition, make in the situation that there is the high thermal conduction that the monomer of mesomorphic group arranges to realize resin combination in an orderly manner in molecule, owing to having that the monomer of mesomorphic group is easy to crystallization conventionally, be solid at normal temperatures, therefore sometimes compare operational difficulty with general resin-phase.And if then by the high filling of filler, above-mentioned difficulties increases, therefore moulding sometimes becomes more difficult.

As solution to the problems described above, can enumerate the method for the mineral filler of adding a small amount of nano-particles size, but under the condition shown in TOHKEMY 2009-13227 communique, result is: although insulation breakdown improves, to compare thermal conductivity lower with adder not.

Under such situation, problem of the present invention is, the resin combination that can take into account excellent heat conductivity and excellent mobility is provided.In addition problem is also, resin sheet, prepreg, plywood, metal substrate, printing distributing board and the power semiconductor arrangement with excellent heat conductivity and excellent insulativity that use this resin combination and form are provided.

For solving the method for problem

The inventor etc. conduct in-depth research in order to solve above-mentioned problem, and result has completed the present invention.That is, the present invention comprises following mode.

< 1 > resin combination, it comprises: the first filler, described the first filler in the size distribution of using laser diffractometry to measure, be more than or equal to 1nm and be less than in the scope of 500nm and there is peak, and comprise Alpha-alumina; The second filler, described the second filler in the size distribution of using laser diffractometry to measure, have peak in the scope of 1 μ m～100 μ m; And the thermosetting resin in molecule with mesomorphic group.

< 2 > resin combination, it comprises: the first filler, described the first filler is accumulated 50% corresponding median size (D50) and is more than or equal to 1nm and is less than 500nm from the small particle size side of weight build-up size-grade distribution, and comprises Alpha-alumina; The second filler, it is 1 μ m～100 μ m that described the second filler is accumulated 50% corresponding median size (D50) from the small particle size side of weight build-up size-grade distribution; And the thermosetting resin in molecule with mesomorphic group.

< 3 > are according to the resin combination described in above-mentioned < 1 > or < 2 >, and the containing ratio of above-mentioned the first filler is 0.1 volume %～10 volume % in cumulative volume.

< 4 > are according to the resin combination described in any one in above-mentioned < 1 >～< 3 >, and above-mentioned the second filler is nitride filler.

< 5 > are according to the resin combination described in above-mentioned < 4 >, and above-mentioned nitride filler comprises at least a kind in the group of selecting free boron nitride and aluminium nitride composition.

< 6 > are according to the resin combination described in any one in above-mentioned < 1 >～< 5 >, and the containing ratio of above-mentioned the second filler is 55 volume %～85 volume % in cumulative volume.

< 7 > are according to the resin combination described in any one in above-mentioned < 1 >～< 6 >, and above-mentioned thermosetting resin is epoxy resin.

< 8 > are according to the resin combination described in any one in above-mentioned < 1 >～< 7 >, and above-mentioned mesomorphic group has the structure that 3 above six-membered ring groups connect with straight chain shape.

< 9 > are according to the resin combination described in above-mentioned < 7 >, and above-mentioned epoxy resin represents by following general formula (III) or (IV).

[changing 1]

(in general formula (III), Ar ¹, Ar ²and Ar ³identical or different separately, represent any any one the represented divalent group in following general formula.R ¹, R ², R ³, R ⁴, R ⁵and R ⁶identical or different separately, the alkyl of expression hydrogen atom or carbon number 1～18.Q ¹and Q ²identical or different separately, represent the straight chain shape alkylidene group of carbon number 1～9, the methylene radical that forms this straight chain shape alkylidene group can be replaced by the alkylidene group of carbon number 1～18, in addition also can be inserted with between this methylene radical-O-or-N (R ⁷)-.At this, R ⁷the alkyl that represents hydrogen atom or carbon number 1～18.〕

[changing 2]

(at this, R represents the alkyl of hydrogen atom or carbon number 1～18 independently of one another, and a represents 1～8 integer, and b, e and g represent 1～6 integer, and c represents 1～7 integer, and d and h represent 1～4 integer, and f represents 1～5 integer.In addition,, in above-mentioned divalent group, when R is while being a plurality of, whole R can represent identical group, also can represent different groups.〕

[changing 3]

(in general formula (IV), R ¹～R ⁴the alkyl that represents independently of one another hydrogen atom or carbon number 1～3.〕

< 10 > are according to the resin combination described in any one in above-mentioned < 1 >～< 9 >, and it further comprises phenol novolac resin.

< 11 > are according to the resin combination described in above-mentioned < 10 >, and above-mentioned phenol novolac resin comprises the compound with at least 1 represented structural unit in the group of selecting free following general formula (I-1) and (I-2) forming.

[changing 4]

General formula (I-1) and (I-2) in, R ¹represent independently of one another alkyl, aryl or aralkyl.R ²and R ³represent independently of one another hydrogen atom, alkyl, aryl or aralkyl.M represents 0～2 integer independently of one another, and n represents 1～7 integer independently of one another.

< 12 > are according to the resin combination described in above-mentioned < 10 > or < 11 >, in above-mentioned phenol novolac resin, the ratio that contains of the monomer consisting of the phenolic compound that forms described phenol novolac resin is 5 quality %～80 quality %.

< 13 > semicure resin combination, it is the semicure thing of the resin combination described in any one in above-mentioned < 1 >～< 12 >.

< 14 > curable resin composition, it is the cured article of the resin combination described in any one in above-mentioned < 1 >～< 12 >.

< 15 > resin sheet, it is the sheet-like formed body of the resin combination described in any one in above-mentioned < 1 >～< 12 >.

< 16 > are according to the resin sheet described in above-mentioned < 15 >, and its amount of flow under semi-cured state is 130%～210%.

< 17 > prepreg, it has fiber base material and is immersed in the resin combination described in any one in above-mentioned < 1 >～< 12 > in above-mentioned fiber base material.

< 18 > plywood, it has by adhesives and is configured in above-mentioned by the semicure resin combination layer on adhesives or curable resin composition layer, described semicure resin combination layer or curable resin composition layer are the resin combination described in any one in free above-mentioned < 1 >～< 12 > of choosing, resin sheet described in above-mentioned < 15 > or < 16 >, and semicure thing or the cured article of at least a kind in the group of the composition of the prepreg described in above-mentioned < 17 >.

< 19 > metal substrate, by tinsel, curable resin composition layer and metal sheet are laminated in this order, described curable resin composition layer is the resin combination described in any one being selected from above-mentioned < 1 >～< 12 >, resin sheet described in above-mentioned < 15 > or < 16 >, and the cured article of at least a kind of the prepreg described in above-mentioned < 17 >.

< 20 > printing distributing board, by metal sheet, curable resin composition layer and wiring layer are laminated in this order, described curable resin composition layer is the resin combination described in any one being selected from above-mentioned < 1 >～< 12 >, resin sheet described in above-mentioned < 15 > or < 16 >, and the cured article of at least a kind of the prepreg described in above-mentioned < 17 >.

< 21 > power semiconductor arrangement, it comprises: the semiconductor module that metal sheet, soldering-tin layer and semi-conductor chip are laminated in this order; Radiating component; And the cured article that is configured in the above-mentioned metal sheet of above-mentioned semiconductor module and < 15 > between above-mentioned radiating component or the resin sheet described in < 16 >.

Invention effect

According to the present invention, can provide the resin combination that can take into account excellent heat conductivity and excellent mobility.Resin sheet, prepreg, plywood, metal substrate and the printing distributing board with excellent heat conductivity and excellent insulativity that use this resin combination and form can be provided in addition.

Accompanying drawing explanation

Fig. 1 is the summary sectional view of an example that the formation of the curable resin composition that present embodiment relates to is briefly shown.

Fig. 2 is for the sketch chart of an example of the formation of the curable resin composition that present embodiment relates to is described.

Fig. 3 is for the sketch chart of an example of the formation of the curable resin composition that present embodiment relates to is described.

Fig. 4 is the sketch chart of an example that the formation of the curable resin composition different from present embodiment is shown.

Fig. 5 is the sketch chart of an example that the formation of the curable resin composition different from present embodiment is shown.

Fig. 6 is the summary sectional view of an example that the formation of the curable resin composition that comparative example 1 relates to is briefly shown.

Fig. 7 is the summary sectional view of an example that the formation of the curable resin composition that comparative example 2 and 4 relates to is briefly shown.

Fig. 8 is the summary sectional view of an example that the formation of the curable resin composition that comparative example 5 relates to is briefly shown.

Fig. 9 illustrates to use that laser diffractometry is measured, transverse axis to get the general figure that the particle diameter longitudinal axis is got the size distribution of frequency.It should be noted that, the peak in this specification sheets refers to the part shown in figure, is the maximum value distributing.

Figure 10 illustrates to use that laser diffractometry is measured, transverse axis to get the general figure that the particle diameter longitudinal axis is got the size distribution of weight build-up.It should be noted that, the median size in this specification sheets (D50) refers to the part shown in figure.

Figure 11 is the summary sectional view of an example that the formation of the power semiconductor arrangement that present embodiment relates to is shown.

Figure 12 is the summary sectional view of an example that the formation of the power semiconductor arrangement that present embodiment relates to is shown.

Embodiment

In this specification sheets, " operation " this term not only comprises independently operation, even in the situation that can not clearly distinguishing with other operations, if can realize the expection object of this operation, be also contained in this term.In addition, the numerical value that the front and back that the numerical range of using "～" to represent in this specification sheets represents to comprise "～" are recorded is respectively as minimum value and peaked scope.And then in this manual, about the amount of each composition in composition, in the situation that there is the multiple material that is equivalent to each composition in composition, unless otherwise specified, refer to the total amount of this many kinds of substance existing in composition.

< resin combination >

Resin combination of the present invention comprises: the first filler, described the first filler in the size distribution of using laser diffractometry to measure, be more than or equal to 1nm and be less than in the scope of 500nm and there is peak, and comprise Alpha-alumina; The second filler, described the second filler in the size distribution of using laser diffractometry to measure, have peak in the scope of 1 μ m～100 μ m; And the thermosetting resin in molecule with mesomorphic group.Above-mentioned resin combination for example can be by mixing the first filler, the second filler and the thermosetting resin in molecule with mesomorphic group to make, described the first filler is accumulated 50% corresponding median size (D50) and is more than or equal to 1nm and is less than 500nm from the small particle size side of weight build-up size-grade distribution, and comprise Alpha-alumina, it is 1 μ m～100 μ m that described the second filler is accumulated 50% corresponding median size (D50) from the small particle size side of weight build-up size-grade distribution.

Or resin combination of the present invention comprises: the first filler, described the first filler is accumulated 50% corresponding median size (D50) and is more than or equal to 1nm and is less than 500nm from the small particle size side of weight build-up size-grade distribution, and comprises Alpha-alumina; The second filler, it is 1 μ m～100 μ m that described the second filler is accumulated 50% corresponding median size (D50) from the small particle size side of weight build-up size-grade distribution; And the thermosetting resin in molecule with mesomorphic group.

Above-mentioned resin combination can further comprise other composition as required and form.By being this formation, can take into account excellent heat conductivity and excellent mobility.

By having the thermosetting resin of mesomorphic group and the first filler the use with specific median size that comprises Alpha-alumina in molecule, the thermal conductivity leap of curable resin composition improves.In No. 4118691 specification sheets of Japanese Patent, recorded the cured article of the thermosetting resin in molecule with mesomorphic group excellent aspect heat conductivity.But, in the situation that by this thermosetting resin and Alpha-alumina filler the use with specific median size, the heat conductivity of curable resin composition rises to according to the unforeseen degree of record of No. 4118691 communique of Japanese Patent.This for example can think that the higher order structure of the thermosetting resin with high order causes owing to forming on the Alpha-alumina filling surface as nanoparticle.

And then in the present invention, because the median size of the first filler is less than the median size of the second filler, so the thermal conductivity of curable resin composition improves greatly.Specifically, by being that the second filler of 1 μ m～100 μ m is more than or equal to 1nm with the median size (D50) that comprises Alpha-alumina and is less than the first filler combination of 500nm by median size (D50), the thermal conductivity of curable resin composition improves greatly.To this, the inventor etc. for example think as follows.But the present invention is not limited to the mechanism of inferring below.

Conventionally, in the curable resin composition being formed by filler and resin, on the interface between filler, there is resin.Due to resin and filler, to compare thermal conductivity low, is therefore difficult to transmit heat between filler.Therefore, no matter how high filling of filler made between filler closely sealedly, on filler interface, thermal conduction also can be lost greatly.On the other hand, in curable resin composition of the present invention, the thermosetting resin in molecule with mesomorphic group being present between filler transmits heat efficiently, and then by the first filler and the thermosetting resin in molecule with mesomorphic group are combined, heat conductivity between the first filler and between the first filler and the second filler improves more, therefore can think that the heat conduction loss on filler interface is few, the heat conductivity of result curable resin composition improves.

On one side with reference to accompanying drawing, this inferred to mechanism further describe on one side.

Fig. 1 is the sectional view that the curable resin composition that present embodiment relates to is briefly shown, the schematically illustrated heat conduction path of arrow in Fig. 1.As shown in Figure 1, the first filler 20 is because to compare median size less with the second filler 10, therefore can enter in curable resin composition by the second filler 10 formed gap each other.And then on the surface of the first filler 20, the cured article 30 consisting of the thermosetting resin with mesomorphic group forms the higher order structure as shown in the enlarged view of Fig. 1.Thus, the first filler 20 that is formed with from the teeth outwards the higher order structure of resin cured matter 30 forms the second filler 10 new heat conduction path connected to one another.Consequently, in curable resin composition, effectively heat conduction path increases, and can think and can access higher thermal conductivity.

In addition,, according to Fig. 2 and Fig. 3, more describe the reason that curable resin composition that present embodiment relates to can access high thermoconductivity in detail.

As Fig. 2 is schematically shown, on the surface of the first filler 20, the cured article 30 consisting of the thermosetting resin with mesomorphic group forms higher order structure.Therefore there is the higher order structure forming section (being labeled as 30a) that can effectively conduct heat in the surrounding at the first filler 20.There are the first filler 20 set of this higher order structure forming section 30a, can eliminate the region that loss occurs in thermal conduction.Therefore think and can between filler, very effectively conduct heat.

As Fig. 3 is schematically shown, first filler 20 with this higher order structure forming section 30a with landfill by the second filler 10 each other the mode in formed gap enter, thereby the reason based on described above can be conducted heat very effectively, can think and can access higher thermal conductivity.Same with Fig. 1, the schematically illustrated heat conduction path of arrow in Fig. 3.For example, can be according to the second filler 10, the higher order structure forming section (30a) being obtained by cured article 30, the first filler 20, the higher order structure forming section 30a being obtained by cured article 30, the such order of the second filler 10, without heat conduction loss conduct heat.

On the other hand, Fig. 4 with shown in Fig. 5 about an example of the formation of the curable resin composition different from present embodiment.

The schematically illustrated curable resin composition of Fig. 4 does not contain the situation of the first filler 20.In this case, owing to hindering thermal conduction in formed gap each other by the second filler 10, therefore think and cannot obtain high thermoconductivity.

The situation that the schematically illustrated curable resin composition of Fig. 5 comprises the filler (median size (D50) for example, consisting of the material beyond Alpha-alumina is more than or equal to 1nm and is less than the filler 40 of 500nm) that does not meet the first filler 20.In this situation, even if use the cured article 30 being formed by the thermosetting resin with mesomorphic group, can on the surface of filler 40, not form the higher order structure of cured article 30 yet.Therefore, filler 40 each other, the gap that forms between the second filler 20 and filler 40 hinders thermal conduction.Therefore think and cannot obtain high thermoconductivity.

In addition, Fig. 6 is the sectional view that the curable resin composition that comparative example 1 described later relates to is briefly shown, same with Fig. 1, the schematically illustrated heat conduction path of arrow in Fig. 6.As shown in Figure 6 by the second filler 10 with to have in the curable resin composition that cured article 30 that the thermosetting resin of mesomorphic group forms forms, with resin cured matter 30 landfills that formed higher order structure by the second filler 10 formed gap each other.Although it is higher that the resin cured matter 30 that has formed higher order structure and general resin cured matter are compared heat conductivity, the first filler 20 of higher order structure that has a resin cured matter 30 of mesomorphic group with being formed with from the teeth outwards in Fig. 6 is compared heat conductivity and is reduced.Therefore can think, with regard to curable resin composition as shown in Figure 6, compare heat conductivity with curable resin composition as shown in Figure 1 and reduce.

On the other hand, Fig. 7 is the sectional view that comparative example 2 described later and 4 curable resin compositions that relate to are briefly shown, same with Fig. 1, the schematically illustrated heat conduction path of arrow in Fig. 7.The filler 40 that is more than or equal to 1nm and is less than 500nm in the median size (D50) by beyond Alpha-alumina as shown in Figure 7 (for example, silica filler or gama-alumina filler), the second filler 10 and to have in the curable resin composition that cured article 30 that the thermosetting resin of mesomorphic group forms forms, with the median size (D50) beyond Alpha-alumina be more than or equal to 1nm and resin cured matter 30 landfills that are less than the filler 40 of 500nm and formed higher order structure by the second filler 10 formed gap each other.With regard to the median size (D50) beyond Alpha-alumina, be more than or equal to 1nm and be less than the filler 40 of 500nm and formed with regard to the resin cured matter 30 of higher order structure, the first filler 20 of higher order structure that has a resin cured matter 30 of mesomorphic group with being formed with from the teeth outwards in Fig. 1 is compared heat conductivity and is reduced.Therefore can think, with regard to curable resin composition as shown in Figure 7, compare heat conductivity with curable resin composition as shown in Figure 1 and reduce.

And then Fig. 8 is the sectional view that the curable resin composition that comparative example 5 described later relates to is briefly shown, same with Fig. 1, the schematically illustrated heat conduction path of arrow in Fig. 8.As shown in Figure 8 by the first filler 20, the second filler 10 with not have in the curable resin composition that cured article 50 that the thermosetting resin of mesomorphic group forms forms, with the first filler 20 and resin cured matter 50 landfills that do not form higher order structure by the second filler 10 formed gap each other.The first filler 20 is compared heat conductivity with the first filler 20 of higher order structure that does not form the resin cured matter 50 of higher order structure and being formed with from the teeth outwards in Fig. 1 and have the resin cured matter 30 of mesomorphic group and is reduced.Therefore can think, with regard to curable resin composition as shown in Figure 8, compare heat conductivity with curable resin composition as shown in Figure 1 and reduce.

At this, so-called higher order structure, refers to and comprises that its integrant is arranged and the structure that formed the higher order structure body of microcosmic ordered structure, for example, crystallization phases, mesomorphic phase meet.The existence of such higher order structure body is confirmed easily to judge by polarized light microscope observing.That is, in the observation under quadrature Niccol (cross Nicol) state, can be by seeing that the interference fringe causing because of depolarization distinguishes.

This higher order structure body exists with island conventionally in curable resin composition, and forms domain structure, and 1 Ge Gai island is corresponding to 1 higher order structure body.The integrant of this higher order structure body generally forms by covalent linkage itself.

In addition, the discoveries such as the inventor by using the thermosetting resin in molecule with mesomorphic group as thermosetting resin, form the higher order structure of the resin cured matter with high order on the first filling surface.And then also find, the thermosetting resin with mesomorphic group be take the first filler and is brought into play higher order as core, and the heat conductivity of resin cured matter itself also improves.In curable resin composition of the present invention, the first filler that is formed with from the teeth outwards the higher order structure of the resin cured matter with mesomorphic group enters the gap between the second filler, and heat conduction path is increased, and therefore can access higher thermal conductivity.

In addition, the existence of the higher order structure of the resin cured matter on the first filling surface can be found as follows.

(for example use polarizing microscope, the BX51 processed of Olympus Corp) to the cured article of the thermosetting resin with mesomorphic group that contains 5 volume %～10 volume % the first fillers (thickness: while 0.1 μ m～20 μ m) observing, centered by filler, observe fringe pattern, in the non-existent region of filler, do not observe fringe pattern.Hence one can see that, and the resin cured matter with mesomorphic group has formed higher order structure centered by filler.In addition, observation need to be carried out under the state that makes analyzer with respect to 60 ° of polarizer rotations, rather than carries out under quadrature Niccol state.If quadrature Niccol state, the region (being the region that resin does not form higher order structure) that does not observe fringe pattern becomes dark field, cannot partly distinguish with filler.But by making analyzer with respect to 60 ° of polarizer rotations, the region that does not observe fringe pattern does not become dark field, thereby can partly distinguish with filler.

What be explained is, be not limited to the first filler, so long as the high thermal conductivity ceramic packings such as boron nitride, aluminum oxide, aluminium nitride, silicon-dioxide just can be observed above-mentioned phenomenon, but the in the situation that of Alpha-alumina filler, even if median size (D50) is outside the scope of the first filler, the area of the fringe pattern forming centered by filler is also very large.

Above-mentioned resin combination combination comprises the first filler and second filler with specific median size (D50).Median size in the present invention (D50) refers to when the weight build-up size-grade distribution of describing from small particle size side, accumulates the particle diameter that reaches 50%.

At this, weight build-up size-grade distribution is measured with laser diffractometry.Use the particle size distribution of laser diffractometry can use laser diffraction and scattering particle size distribution device (for example, the LS13 processed of Beckman Coulter company) to carry out.For measuring with for the modulation of fillers dispersed liquid, in the situation that the dispersion liquid that filler is organic solvent, take aspect the sensitivity of installing as the mode of suitable light quantity is carried out with identical organic solvent diluting.In addition, in the situation that filler is powder, powder is dropped in the sodium-metaphosphate aqueous solution of 0.1 quality %, carry out ultrasonic wave dispersion, take and measuring as the concentration of suitable light quantity aspect the sensitivity of device.

The result of said determination is: for the first filler, in size distribution, being more than or equal to 1nm and being less than in the scope of 500nm, observe peak, for the second filler, in size distribution, observe peak in the scope of 1 μ m～100 μ m.

By making to contain the first filler that median size (D50) is more than or equal to 1nm and is less than 500nm in resin combination, in resin combination contained median size (D50) be 1 μ m～100 μ m lubricant effect each other of the second filler just much less, make resin combination also can access the lubricant effect between the second filler and fiber base material in impregnated in the prepreg of fiber base material gained.

The resin sheet forming for the resin combination that uses such mobility excellence and with for the tinsel of resin, formed bubble when landfill is made well when pasting, with by the hole at adhesives interface, so insulation breakdown improves.In addition, for the prepreg forming for this resin combination is immersed in fiber base material, in the gap of fiber base material, the second filler is not chimeric each other, can slide well, resin combination oozes out well from fiber base material, when pasting well landfill base material inner, with by the hole at adhesives interface, so insulation breakdown improves.And then, due to good mobility, while implementing hot pressing after coating, can make resin ooze out on the surface of fiber base material, it is good that cementability also becomes.

Because above-mentioned resin combination is excellent aspect heat conductivity and mobility, therefore has plywood, metal substrate and the printing distributing board of the curing insulation layer forming of this resin combination can be brought into play to higher heat conductivity and insulativity.

Below, the physical property for the material using in resin combination and resin combination describes.

(the first filler)

Above-mentioned resin combination comprises the first filler, described the first filler in the size distribution of using laser diffractometry to measure, be more than or equal to 1nm and be less than in the scope of 500nm and there is peak, and comprise Alpha-alumina.That is, above-mentioned resin combination comprises the first filler, and described the first filler is accumulated 50% corresponding median size (D50) and is more than or equal to 1nm and is less than 500nm from the small particle size side of weight build-up size-grade distribution, and comprises Alpha-alumina.

From improving the viewpoint of heat conductivity and mobility, consider, above-mentioned the first filler preferably has peak in the scope in the size distribution of using laser diffractometry to measure, at 1nm～450nm, more preferably in the scope of 50nm～450nm, there is peak, more preferably in the scope of 100nm～450nm, there is peak, further preferably in the scope of 100nm～300nm, there is peak, further preferably in the scope of 100nm～200nm, there is peak.

Or, from improving the viewpoint of heat conductivity and mobility, to consider, the median size of above-mentioned the first filler (D50) is preferably 1nm～450nm, 50nm～450nm more preferably, more preferably 100nm～450nm, more preferably 100nm～300nm, more preferably 100nm～200nm.

If the median size of the first filler (D50) is more than or equal to 500nm, the first filler cannot fully enter the gap between the second filler, and result is that in resin combination, all loading levels of filler can tail off, the tendency that exists heat conductivity to reduce.In addition,, when the median size (D50) of the first filler is less than 1nm, existence cannot fully obtain the situation of the oilness of the second filler each other or between the second filler and fiber base material.

The median size of the first filler ask method as previously mentioned.

Above-mentioned the first filler comprises Alpha-alumina.By comprising Alpha-alumina, existence can access the tendency of sufficient heat conductivity.In addition, by comprising Alpha-alumina, can access the resin combination of high-melting-point, high mechanical strength and electrical insulating property excellence, the fillibility of the first filler improves.

From the viewpoint of heat conductivity and fillibility, consider, the shape of above-mentioned Alpha-alumina is preferably circle.The shape of above-mentioned Alpha-alumina can be measured by scanning electronic microscope (SEM).

Above-mentioned the first filler can further comprise the aluminum oxide beyond Alpha-alumina.In the situation that further comprise the aluminum oxide beyond Alpha-alumina, the aluminium oxide particles beyond Alpha-alumina is preferably circle.The shape of above-mentioned filler can similarly be measured with the shape of above-mentioned Alpha-alumina.As the aluminum oxide beyond Alpha-alumina, can enumerate gama-alumina, θ-aluminum oxide, δ-aluminum oxide etc.

Above-mentioned the first filler also can further comprise the pottery beyond aluminum oxide as required.For example, can comprise boron nitride, aluminium nitride, silicon-dioxide, magnesium oxide, silicon nitride, silicon carbide etc.

From the viewpoint of heat conductivity and mobility, consider, in above-mentioned the first filler, the containing ratio of Alpha-alumina is preferably more than or equals 80 volume % of the cumulative volume of the first filler, is more preferably more than or equal to 90 volume %, more preferably 100 volume %.When using Alpha-alumina, it is large that the higher order structure in molecule with the thermosetting resin of mesomorphic group forms power, and existence can access the tendency of sufficient heat conductivity.

In addition, the existence of the Alpha-alumina in the first filler can be confirmed by X-ray diffraction spectrum.Specifically, for example can, according to the record of No. 3759208 specification sheets of Japanese Patent, using the distinctive peak of Alpha-alumina as index, confirm the existence of Alpha-alumina.

In above-mentioned resin combination, the containing ratio of the first contained filler is not particularly limited.The first filler preferably contains with 0.1 volume %～10 volume % in the cumulative volume of all solids composition of resin combination.If contain the first filler with 0.1 volume %～10 volume % in cumulative volume in resin combination, can access following effect: more improve the oilness between the second filler and between the second filler and fiber base material, and more improve the thermal conductivity of resin combination.

From improving the viewpoint of heat conductivity and mobility, consider, the containing ratio of the first filler is preferably 0.2 volume %～10 volume %, more preferably 0.2 volume %～8 volume %.

At this, all solids composition of so-called resin combination, refers to the remaining component of removing volatile component and obtaining from resin combination.

In addition, in this specification sheets, the containing ratio of the first filler (volume %) is made as the value of obtaining according to following formula.

The containing ratio of the first filler (volume %)=(Aw/Ad)/((Aw/Ad)+(Bw/Bd)+(Cw/Cd)+(Dw/Dd)+(Ew/Ed)) * 100

At this, each variable is as follows.

Aw: the quality ratio of components (quality %) of the first filler

Bw: the quality ratio of components (quality %) of the second filler

Cw: the quality ratio of components (quality %) of thermosetting resin

Dw: the quality ratio of components (quality %) of solidifying agent

Ew: the quality ratio of components (quality %) of other any compositions (except organic solvent)

Ad: the proportion of the first filler

Bd: the proportion of the second filler

Cd: the proportion of thermosetting resin

Dd: the proportion of solidifying agent

Ed: the proportion of other any compositions (except organic solvent)

Above-mentioned the first filler can be used separately a kind or two or more mix is used.For example, can be used together median size (D50) and be included in Alpha-aluminas of more than two kinds in the scope that is more than or equal to 1nm and is less than 500nm, that D50 is different, but be not limited to this combination.

In the situation that describe that transverse axis is got particle diameter, the longitudinal axis is got the size distribution curve of frequency, above-mentioned the first filler can have simple spike, also can have a plurality of peaks.By using size distribution curve to have first filler at a plurality of peaks, the fillibility between the second filler improves more, as the heat conductivity raising of curable resin composition.The first filler that size distribution curve has a plurality of peaks for example can will have first filler combination of more than two kinds of different median sizes (D50) and form.

Combination for above-mentioned the first filler, for example, when enumerating the situation that 2 kinds of aluminum oxide with different median sizes (D50) are combined, it is the filler (a) of median size (D50) for being more than or equal to 250nm and being less than 500nm, with median size (D50) for be less than or equal to filler (a) 1/2 and be more than or equal to 1nm and be less than the mixed fillers of the filler (b) of 250nm, preferably with the whole volumes with respect to above-mentioned the first filler, filler (a) is 90 volume %～99 volume %, and filler (b) be 1 volume %～10 volume % (wherein, filler (a) and cumulative volume % (b) are 100 volume %) ratio fill.

(the second filler)

Above-mentioned resin combination comprise at least a kind in the size distribution of using laser diffractometry to measure, in the scope of 1 μ m～100 μ m, there is second filler at peak.That is, above-mentioned resin combination comprises the second filler that at least a kind of median size of being obtained by weight build-up size-grade distribution (D50) is 1 μ m～100 μ m.

As long as above-mentioned the second filler has the heat conductivity higher than the resin cured matter of curable resin, and median size (D50) is 1 μ m～100 μ m, just be not particularly limited, can from conventionally in order to improve heat conductivity as choice for use suitably the material of filler.In addition, above-mentioned the second filler is preferably electrical insulating property.

The heat conductivity of above-mentioned the second filler is as long as be more not particularly limited higher position than resin cured matter.For example, preferably thermal conductivity is more than or equal to 1W/mK, is more preferably more than or equal to 10W/mK.

As above-mentioned the second filler, specifically can enumerate boron nitride, aluminium nitride, aluminum oxide, silicon-dioxide, magnesium oxide etc.From more improving the viewpoint of heat conductivity, consider, be preferably nitride filler, be wherein preferably at least a kind in boron nitride and aluminium nitride.

Above-mentioned the second filler can be used separately a kind or two or more mix is used.For example, can be by boron nitride and aluminium nitride use, but be not limited to this combination.

Above-mentioned the second filler containing ratio is not particularly limited, but preferably with 55 volume %～85 volume % in the cumulative volume of all solids composition of resin combination, contains.In if tree oil/fat composition, the containing ratio of the second filler is more than or equal to 55 volume %, and thermal conductivity is more excellent.In addition,, if be less than or equal to 85 volume %, formability and cementability improve.Containing ratio about the second filler in the present invention, from improving the viewpoint of thermal conductivity, consider, more preferably 60 volume %～85 volume % in the cumulative volume of all solids composition of resin combination, consider from the viewpoint of mobility, more preferably 65 volume %～85 volume %.

In addition, in this specification sheets, the containing ratio of the second filler (volume %) is made as the value of obtaining according to following formula.

The content of the second filler (volume %)=(Bw/Bd)/((Aw/Ad)+(Bw/Bd)+(Cw/Cd)+(Dw/Dd)+(Ew/Ed)) * 100

At this, each variable is as follows.

Aw: the quality ratio of components (quality %) of the first filler

Bw: the quality ratio of components (quality %) of the second filler

Cw: the quality ratio of components (quality %) of thermosetting resin

Dw: the quality ratio of components (quality %) of solidifying agent

Ad: the proportion of the first filler

Bd: the proportion of the second filler

Cd: the proportion of thermosetting resin

Dd: the proportion of solidifying agent

Ed: the proportion of other any compositions (except organic solvent)

In the situation that describe that transverse axis is got particle diameter, the longitudinal axis is got the size distribution curve of frequency, above-mentioned the second filler can have simple spike, also can have a plurality of peaks.By using size distribution curve to have second filler at a plurality of peaks, the fillibility of the second filler improves, as the heat conductivity raising of curable resin composition.

In the situation that describing size distribution curve, when above-mentioned the second filler has simple spike, preferably in the scope of 1 μ m～80 μ m, there is peak, more preferably in the scope of 1 μ m～50 μ m, there is peak, further preferably in the scope of 1 μ m～30 μ m, there is peak, further preferably in the scope of 1 μ m～20 μ m, there is peak.That is, from the viewpoint of heat conductivity, consider, the median size of the second filler (D50) is preferably 1 μ m～80 μ m, more preferably 1 μ m～50 μ m, more preferably 1 μ m～30 μ m, more preferably 1 μ m～20 μ m.In addition the second filler that, size distribution curve has a plurality of peaks for example can will have second filler combination of more than two kinds of different median sizes (D50) and form.

Combination for above-mentioned the second filler, for example, when enumerating the situation that 2 kinds of filler groups with different median sizes (D50) are closed, it is the filler (A) that median size (D50) is more than or equal to 10 μ m and is less than or equal to 100 μ m, with median size (D50) for be less than or equal to filler (A) 1/2 and be more than or equal to 1 μ m and be less than the mixed fillers of the filler (B) of 10 μ m, preferably with the whole volumes with respect to above-mentioned the second filler, filler (A) is 60 volume %～90 volume %, and filler (B) be 10 volume %～40 volume % (wherein, filler (A) and cumulative volume % (B) are 100 volume %) ratio fill.

In addition, enumerating when thering is the situation of 3 kinds of filler combination of different median sizes, it is the filler (A ') that median size (D50) is more than or equal to 10 μ m and is less than or equal to 100 μ m, median size (D50) for be less than or equal to filler (A ') 1/2 and be more than or equal to 5 μ m and be less than the filler (B ') of 10 μ m, with median size (D50) for be less than or equal to filler (B ') 1/2 and be more than or equal to 1 μ m and be less than the mixed fillers of the filler (C ') of 5 μ m, preferably with the whole volumes with respect to above-mentioned the second filler, filler (A ') is 30 volume %～89 volume %, filler (B ') is 10 volume %～40 volume %, and filler (C ') be 1 volume %～30 volume % (wherein, filler (A '), the cumulative volume % of (B ') and (C ') is 100 volume %) ratio fill.

For the median size (D50) of above-mentioned filler (A) and (A '), in the situation that resin combination is applicable to resin sheet described later or plywood, preferably according to the thickness of the resin sheet as target or the curable resin composition layer in plywood, suitably select, in addition, in the situation that resin combination is applicable to prepreg described later, preferably according to the fineness of the mesh of the thickness of the prepreg as target and fiber base material, suitably select.

The in the situation that of not special other restrictions, from the viewpoint of thermal conductivity, to consider, the median size of above-mentioned filler (A) and (A ') is more preferred more greatly.On the other hand, from the viewpoint of thermal resistance, consider, above-mentioned thickness is attenuate as far as possible in the scope that can guarantee required insulativity preferably.Therefore, the median size of above-mentioned filler (A) and (A ') is preferably 10 μ m～100 μ m, from the viewpoint of filler fillibility, thermal resistance, thermal conductivity, consider, 10 μ m～80 μ m more preferably, 10 μ m～50 μ m more preferably, more preferably 1 μ m～30 μ m, more preferably 1 μ m～20 μ m.

Above-mentioned filler (A) and (A ') are preferably boron nitride or aluminium nitride, but above-mentioned filler (B) and (B '), filler (C ') need not be boron nitride or aluminium nitride.For example, can be also aluminum oxide.

As mentioned above, form the second filler in the situation that the filler group with different median sizes (D50) is closed, in the second filler is all, median size (D50) is 1 μ m～100 μ m.

In addition, above-mentioned resin combination also can further comprise as required median size (D50) be more than or equal to 1nm and be less than 500nm and the scope of 1 μ m～100 μ m outside and there is the 3rd filler of heat conductivity.Even and by median size (D50) in the situation that be more than or equal to 1nm and be less than 500nm and extraneous the 3rd filler of 1 μ m～100 μ m, median size (D50) is that the second filler of 1 μ m～100 μ m also preferably contains with 55 volume %～85 volume % in the cumulative volume of resin combination.

The median size of above-mentioned the 3rd filler (D50) is preferably more than or equals 500nm and be less than 1 μ m, is more preferably more than or equal to 500nm and is less than or equal to 800nm.In addition,, in the situation that above-mentioned resin combination comprises the 3rd filler, the containing ratio of the 3rd filler is not particularly limited.For example, in the cumulative volume of resin combination, be preferably 1 volume %～40 volume %, 1 volume %～20 volume % more preferably.

In addition, the optimal way of the heat conductivity of the 3rd filler and above-mentioned the second filler are same.

In above-mentioned resin combination, the median size (D50) of the second contained filler is not particularly limited with respect to the ratio (the second filler/the first filler) of the median size (D50) of the first filler.From the viewpoint of heat conductivity and mobility, consider, be preferably 10～500, more preferably 30～300.In addition, in the situation that the size distribution curve of the second filler has a plurality of peaks, the corresponding particle diameter in peak that preferably becomes maximum particle diameter is 10～500 with respect to the ratio of the median size (D50) of the first filler, more preferably 30～300, more preferably 100～300.

In above-mentioned resin combination, the containing ratio of the second contained filler (volume %) is not particularly limited with respect to the ratio (the second filler/the first filler) of the containing ratio (volume %) of the first filler.From the viewpoint of heat conductivity and mobility, consider, be preferably 5～500, more preferably 5～350.

(thermosetting resin)

Above-mentioned resin combination comprises at least a kind of thermosetting resin in molecule with mesomorphic group.

At this, so-called mesomorphic group, refers to by the performance of molecular interaction the functional group that easily shows crystallinity, liquid crystal liquid crystal property.Specifically can enumerate xenyl, phenylamino benzoic acid ester group, azobenzene, stilbene radicals and derivative thereof etc. as representative.

As the thermosetting resin in the present invention, so long as there is the compound of at least 1 mesomorphic group and at least 2 Thermocurable functional groups in molecule, be just not particularly limited.Specifically can enumerate the modified resin of epoxy resin, polyimide resin, polyamide-imide resin, cyanate resin, resol, melamine resin, vibrin, cyanate ester resin and these resins etc.These resins can be used alone or two or more kinds may be used.

From stable on heating viewpoint, consider, above-mentioned thermosetting resin is preferably at least a kind of the resin that is selected from epoxy resin, resol and cyanate resin, considers, more preferably epoxy resin from the viewpoint of cementability.Above-mentioned epoxy resin can be used alone or two or more kinds may be used.

The particular content in molecule with the epoxy resin (following, also referred to as " containing mesomorphic epoxy resin ") of mesomorphic group for example can be with reference to the record of No. 4118691 communique of Japanese Patent.

In addition, the anisotropic structure that resin is recorded in whether having No. 4118691 communique of Japanese Patent in the semicure thing of resin combination and cured article, can for example, by carrying out the X-ray diffraction (, Rigaku company X ray resolver processed) of semicure resin combination and curable resin composition, judge.Using CuK _α1 line, while measuring with the scope of tube voltage 40kV, tube current 20mA, 2 θ=2 °～30 °, if resin has semicure resin combination and the curable resin composition of the anisotropic structure of recording in No. 4118691 specification sheets of Japanese Patent, in the scope of 2 θ=2 °～10 °, there is diffraction peak.In addition, because the diffraction peak of the heat conductivity filler consisting of high thermal conductivity pottery appears in ° above scope of 2 θ=20, therefore can distinguish clearly with the peak of resin.

Below, the concrete example that contains mesomorphic epoxy resin is shown, but thermosetting resin in the present invention is not limited to this.

As containing mesomorphic epoxy resin, for example can enumerate the represented epoxy resin of following general formula (II) (being recorded in No. 4118691 communiques of Japanese Patent), the represented epoxy resin of following general formula (III) (is recorded in No. 4619770 communique of Japanese Patent, TOHKEMY 2008-13759 communique), the epoxy resin (being recorded in TOHKEMY 2011-74366 communique) that following general formula (IV) is represented, the epoxy resin (being recorded in TOHKEMY 2010-241797 communique) that following logical formula V is represented, the epoxy resin (being recorded in TOHKEMY 2011-98952 communique) that following chemical formula (VI) is represented etc.

[changing 5]

In general formula (II), n is 4,6 or 8.

[changing 6]

In general formula (III), Ar ¹, Ar ²and Ar ³identical or different separately, represent any any one the represented divalent group in following general formula.R ¹, R ², R ³, R ⁴, R ⁵and R ⁶identical or different separately, the alkyl of expression hydrogen atom or carbon number 1～18.Q ¹and Q ²identical or different separately, represent the straight chain shape alkylidene group of carbon number 1～9, the methylene radical that forms this straight chain shape alkylidene group can be replaced by the alkylidene group of carbon number 1～18, in addition also can be inserted with between this methylene radical-O-or-N (R ⁷)-.At this, R ⁷the alkyl that represents hydrogen atom or carbon number 1～18.

[changing 7]

At this, R represents the alkyl of hydrogen atom or carbon number 1～18 independently of one another, and a represents 1～8 integer, and b, e and g represent 1～6 integer, and c represents 1～7 integer, and d and h represent 1～4 integer, and f represents 1～5 integer.In addition,, in above-mentioned divalent group, when R is while being a plurality of, whole R can represent identical group, also can represent different groups.

[changing 8]

In general formula (IV), R ¹～R ⁴the alkyl that represents independently of one another hydrogen atom or carbon number 1～3.

[changing 9]

In logical formula V, R ¹represent independently of one another the alkyl of hydrogen atom, carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ²represent independently of one another the alkyl of hydrogen atom, carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ³represent independently of one another the alkyl of hydrogen atom, carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ⁴represent independently of one another the alkyl of hydrogen atom, carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ⁵represent hydrogen atom, the alkyl of carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ⁶represent hydrogen atom, the alkyl of carbon number 1～3 or the alkoxyl group of carbon number 1～3, R ⁷the alkoxyl group that represents hydrogen atom, methyl or carbon number 1～3, R ⁸the alkoxyl group that represents hydrogen atom, methyl or carbon number 1～3.

[changing 10]

In addition, YL6121H (Mitsubishi chemical Co., Ltd's system) etc. can be enumerated in commercially available prod.

Above-mentionedly contain the epoxy resin that mesomorphic epoxy resin is preferably the structure that the six-membered ring group that has in mesomorphic group more than 3 connects with straight chain shape.Such resin easily forms higher order structure, can access more high thermoconductivity.The six-membered ring group number connecting with straight chain shape contained in mesomorphic group, preferably greater than or equal to 3, is considered more preferably 3 or 4 from the viewpoint of formability.

The contained six-membered ring group connecting with straight chain shape can be from take the six-membered ring group of the aromatic nucleus that acene classes such as benzene, pyridine, toluene or naphthalene etc. are representative in mesomorphic group, can be also the six-membered ring group from aliphatics rings such as hexanaphthene, tetrahydrobenzene, piperidines.Wherein, preferably at least 1 be the six-membered ring group from aromatic nucleus, more preferably in mesomorphic group among contained six-membered ring group of take the connection of straight chain shape 1 as aliphatics ring, remaining ring be all aromatic nucleus.

Above-mentioned containing among mesomorphic epoxy resin, the epoxy resin of the structure connecting with straight chain shape about the six-ring having in mesomorphic group more than 3, above-mentioned general formula (II)～(VI) meet.Wherein, from the viewpoint of heat conductivity, consider, be preferably general formula (III) or the represented epoxy resin of general formula (VI).And then, following general formula (VII), (VIII), (IX) and (X) represented epoxy resin due to except heat conductivity also excellent aspect mobility, cementability, therefore can be ideally suited for above-mentioned resin combination.

[changing 11]

(1-recording in No. 4619770 communique of Japanese Patent (3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl)-1-tetrahydrobenzene)

[changing 12]

(1-recording in No. 4619770 communique of Japanese Patent (3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl) benzene)

[changing 13]

(4-{4-recording in TOHKEMY 2011-74366 communique (2,3-glycidoxy) phenyl } cyclohexyl 4-(2,3-glycidoxy) benzoic ether)

[changing 14]

(4-{4-recording in TOHKEMY 2011-74366 communique (2,3-glycidoxy) phenyl } cyclohexyl 4-(2,3-glycidoxy)-3-methyl) benzoic ether)

In addition, above-mentioned thermosetting resin can be monomer, can be also to utilize solidifying agent etc. to make monomer carry out the state of the prepolymer that partial reaction forms.The most general easy crystallizations of resin in molecule with mesomorphic group, the solubleness in solvent is also low, but by making it carry out partial reaction, polymerization can suppress crystallization, and therefore formability improves sometimes.

From the viewpoint of formability, cementability and heat conductivity, consider, above-mentioned thermosetting resin preferably contains with 10 volume %～40 volume % in the cumulative volume of all solids composition of resin combination, more preferably with 15 volume %～35 volume %, contain, further preferably with 15 volume %～30 volume %, contain.

In addition, in the situation that above-mentioned resin combination comprises solidifying agent described later, curing catalyst, the containing ratio that comprises these solidifying agent, curing catalyst at the containing ratio of this said thermosetting resin.

The containing ratio of contained thermosetting resin in above-mentioned resin combination (volume %) is not particularly limited with respect to the ratio (thermosetting resin/the first filler) of the containing ratio (volume %) of the first filler.From the viewpoint of heat conductivity and mobility, consider, be preferably 1～200, more preferably 2.5～150.

Among above-mentioned epoxy resin, there is the tendency that forms the higher order structure with higher order centered by Alpha-alumina contained in the first filler in the represented epoxy monomer of general formula (III) or general formula (IV).Consequently, the tendency that exists the heat conductivity leap after solidifying to improve.Its reason can think, by there is Alpha-alumina, the above-mentioned epoxy resin that has formed higher order structure becomes effective heat conduction path, thereby can access high thermal conductivity.

In addition, in the situation that the D50 of contained Alpha-alumina is more than or equal to 1nm and is less than 500nm in resin combination, the higher order structure of above-mentioned epoxy monomer forms effect and is tending towards becoming significantly, and it is remarkable that the raising of heat conductivity is also tending towards becoming.

General formula (III) or the represented epoxy monomer of general formula (IV) change into mesomorphic phase temperature, be that melt temperature is up to 150 ℃.Therefore,, when wanting to make above-mentioned epoxy monomer melting, although also relevant with used solidifying agent, curing catalysts, on the whole curing reaction can carry out with melting simultaneously.Consequently, can before forming higher order structure, above-mentioned epoxy monomer become cured article.Yet, be more than or equal to 1nm and be less than in the system of Alpha-alumina of 500nm comprising D50, there is tendency as follows: even if at high temperature heating also can access the cured article that above-mentioned epoxy monomer has formed higher order structure.

Its reason can think, forms effect remarkable by the higher order structure that uses above-mentioned D50 to be more than or equal to 1nm and to be less than the above-mentioned epoxy monomer that the Alpha-alumina of 500nm produces.Can think because before being more than or equal to 1nm by D50 and being less than and carrying out the curing reaction of above-mentioned epoxy monomer centered by the Alpha-alumina of 500nm, can form rapidly higher order structure.

And then general formula (III) or the represented epoxy monomer of general formula (IV), can only show nematic structure during for resin monomer.Therefore, in molecular structure, there is more difficult formation higher order structure in the epoxy monomer of mesomorphic group.But by making the matrix material forming with the filler combination that comprises Alpha-alumina, general formula (III) or the represented epoxy monomer of general formula (IV) demonstrate compares the smectic structure with higher order with nematic structure.Consequently, demonstrate according to the high thermal conductivity of the unforeseen degree of cured article being formed by resin monomer.

Be explained, nematic structure and smectic structure are respectively a kind of of liquid crystal structure.Nematic structure is molecular long axis towards the same direction and only has the liquid crystal structure of orientation order.And smectic structure is the liquid crystal structure that also has the position-order of one dimension and have layer structure except orientation order.About order, smectic structure is higher than nematic structure.Therefore, the heat conductivity of resin cured matter is also higher when showing the situation of smectic structure.

While using above-mentioned method to utilize polarizing microscope to observe for the cured article of the composition of the different Alpha-alumina of the D50 that makes to contain 5 volume %～10 volume % in the represented epoxy monomer of general formula (III) or general formula (IV), in the situation that the Alpha-alumina that D50 is more than or equal to 1nm and is less than 500nm shows that the area in the region of fringe pattern becomes maximum.Can judge thus, when using D50 to be more than or equal to 1nm and being less than the Alpha-alumina of 500nm, the higher order structure of the represented epoxy monomer of general formula (III) or general formula (IV) forms effect highly significant.

In general formula (III), Ar ¹, Ar ²and Ar ³identical or different separately, be preferably the represented divalent group of following general formula (1), (3) or (8), more preferably Ar ¹, Ar ³for (8) and Ar ²for (3).R ¹, R ², R ³, R ⁴, R ⁵and R ⁶identical or different separately, be preferably hydrogen atom or methyl, more preferably hydrogen atom.Q ¹and Q ²identical or different separately, be preferably the straight chain shape alkylidene group of carbon number 1～4, more preferably methylene radical.

[changing 15]

In general formula (IV), preferred R ¹～R ⁴be the alkyl of hydrogen atom or carbon number 1～2, more preferably hydrogen atom or methyl, more preferably hydrogen atom independently of one another.

And then, preferred R ¹～R ⁴in 2～4 be hydrogen atom, preferably 3 or 4 is hydrogen atom, preferably 4 is all hydrogen atom.At R ¹～R ⁴in any be in the situation of alkyl of carbon number 1～3, preferred R ¹and R ⁴in at least one party be the alkyl of carbon number 1～3.

(solidifying agent)

Above-mentioned resin combination preferably comprises at least a kind of solidifying agent.As solidifying agent, as long as thermosetting resin thermofixation just can be not particularly limited.Solidifying agent while being epoxy resin as above-mentioned thermosetting resin is that solidifying agent, amine are that solidifying agent, phenol are the catalyst type solidifying agent such as solidifying agent and mercaptan are the polyaddition type solidifying agent such as solidifying agent, imidazoles etc. such as enumerating acid anhydrides.

Wherein, from stable on heating viewpoint, consider, preferably using and being selected from amine is that solidifying agent and phenol are at least a kind in solidifying agent, and then considers from the viewpoint of storage stability, and more preferably using phenol is at least a kind in solidifying agent.

As amine, be solidifying agent, can use without particular limitation normally used amine is solidifying agent, can be also that commercially available amine is solidifying agent.Wherein, from the viewpoint of solidified nature, consider, be preferably the multifunctional solidifying agent with 2 above functional groups, and then consider more preferably there is the multifunctional solidifying agent of rigid backbone from the viewpoint of heat conductivity.

As bifunctional amine, it is solidifying agent, for example can enumerate 4,4 '-diaminodiphenyl-methane, 4，4′-diaminodipohenyl ether, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diamino-3,3 '-dimethoxy-biphenyl, 4,4 '-diamino-phenyl benzoic ether, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, Isosorbide-5-Nitrae-diaminonaphthalene, 1,8-diaminonaphthalene etc.

Wherein, from the viewpoint of thermal conductivity, consider, be preferably at least a kind that is selected from 4,4 '-diaminodiphenyl-methane and 1,5-diaminonaphthalene, more preferably 1,5-diaminonaphthalene.

As phenol, be solidifying agent, can use without particular limitation normally used phenol is solidifying agent, can use commercially available low molecule phenolic compound, the resol that their phenolic varnish are formed.

As low molecule phenolic compound, such as using the mono-functional phenols compounds such as phenol, ortho-cresol, meta-cresol, p-cresol, the bifunctional phenol compounds such as pyrocatechol, Resorcinol, Resorcinol, and then 1，2，3-trihydroxybenzene, 1,2, the tri-functional phenols compounds such as 4-trihydroxybenzene, phloroglucinol etc.In addition also can use by methene chain etc. using these phenol novolac resins that low molecule phenolic compound connect and phenolic varnish form as solidifying agent.

As phenol, it is solidifying agent, from the viewpoint of thermal conductivity, consider, the phenol novolac resin that is preferably the bifunctional phenol compounds such as pyrocatechol, Resorcinol and Resorcinol or by methene chain, they is formed by connecting, and then from stable on heating viewpoint, consider the phenol novolac resin more preferably by methene chain, these low molecular bifunctional phenol compounds being formed by connecting.

As phenol novolac resin, specifically can enumerate the resin that cresols novolac resin, pyrocatechol novolac resin, Resorcinol novolac resin, Resorcinol novolac resin etc. form a kind of phenolic compound phenolic varnish, the resin that pyrocatechol Resorcinol novolac resin, Resorcinol Resorcinol novolac resin etc. form the above phenolic compound phenolic varnish of 2 kinds or its.

Wherein, above-mentioned phenol novolac resin is preferably the phenol novolac resin that comprises the compound with at least 1 represented structural unit in the group that is selected from following general formula (I-1) and (I-2) forms.

[changing 16]

Above-mentioned general formula (I-1) and (I-2) in, R ¹represent independently of one another alkyl, aryl or aralkyl.R ¹represented alkyl, aryl and aralkyl, can further have substituting group if possible.As this substituting group, can enumerate alkyl, aryl, halogen atom, hydroxyl etc.

M represents 0～2 integer independently of one another, when m is 2, and 2 R ¹can be the same or different.In the present invention, m is preferably 0 or 1 independently of one another, more preferably 0.

In addition, n represents 1～7 integer independently of one another.

Above-mentioned general formula (I-1) and (I-2) in, R ²and R ³represent independently of one another hydrogen atom, alkyl, aryl or aralkyl.R ²and R ³represented alkyl, aryl and aralkyl, can further have substituting group if possible.As this substituting group, can enumerate alkyl, aryl, halogen atom, hydroxyl etc.

As the R in the present invention ²and R ³, from the viewpoint of storage stability and heat conductivity, consider, be preferably hydrogen atom, alkyl or aryl, be preferably the alkyl of hydrogen atom, carbon number 1～4 or the aryl of carbon number 6～12, more preferably hydrogen atom.

And then from stable on heating viewpoint consideration, also preferred R ²and R ³in at least one party be aryl, the aryl of carbon number 6～12 more preferably.

In addition, above-mentioned aryl can comprise heteroatoms on aromatic group, the heteroaryl that the total number that is preferably heteroatoms and carbon is 6～12.

The solidifying agent the present invention relates to can comprise independent a kind and have general formula (I-1) or (I-2) compound of represented structural unit, also can comprise two or more.Be preferably the situation of the compound that at least comprises (I-1) the represented structural unit from Resorcinol that there is general formula.

The compound with the represented structural unit of above-mentioned general formula (I-1) also can further comprise at least a kind from the part-structure of the phenolic compound beyond Resorcinol.As the phenolic compound beyond the Resorcinol in above-mentioned general formula (I-1), such as enumerating phenol, cresols, pyrocatechol, Resorcinol, 1，2，3-trihydroxybenzene, THB, phloroglucinol etc.In the present invention, can comprise independent a kind of part-structure from them, also can combine and comprise two or more.

In addition,, in thering is the compound of the represented structural unit from pyrocatechol of above-mentioned general formula (I-2), can comprise too at least a kind from the part-structure of the phenolic compound beyond pyrocatechol.

At this, the so-called part-structure from phenolic compound, refers to from the phenyl ring of phenolic compound and partly removes 1 or 2 hydrogen atoms and 1 valency that forms or the group of divalent.In addition the position that, hydrogen atom is removed is not particularly limited.

In the present invention, part-structure as the phenolic compound from beyond Resorcinol, from the viewpoint of heat conductivity, cementability and storage stability, consider, be preferably from being selected from phenol, cresols, pyrocatechol, Resorcinol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene and 1,3, the part-structure of at least a kind in 5-trihydroxybenzene, more preferably from the part-structure of at least a kind being selected from pyrocatechol and Resorcinol.

In addition, have in the compound of the represented structural unit of general formula (I-1), for the ratio that contains of the part-structure from Resorcinol, be not particularly limited.From the viewpoint of Young's modulus, consider, preferably from the part-structure of Resorcinol with respect to have the represented structural unit of general formula (I-1) compound all-mass contain ratio for being more than or equal to 55 quality %.And then consider from the viewpoint of second-order transition temperature (Tg) and linear expansivity, more preferably be more than or equal to 60 quality %, more preferably be more than or equal to 80 quality %, from the viewpoint of heat conductivity, consider, be more preferably more than or equal to 90 quality %.

And then above-mentioned phenol novolac resin more preferably comprises and has the freely phenol novolac resin of the compound of at least 1 represented part-structure in the group of following general formula (II-1)～(II-4) form of choosing.

[changing 17]

[changing 18]

[changing 19]

[changing 20]

In above-mentioned general formula (II-1)～(II-2), m and n are positive number independently of one another, represent the repeat number of repeating unit separately.Ar represent following general formula (II-a) and (II-b) in any represented group.

[changing 21]

Above-mentioned general formula (II-a) and (II-b) in, R ¹¹and R ¹⁴represent independently of one another hydrogen atom or hydroxyl.R ¹²and R ¹³the alkyl that represents independently of one another hydrogen atom or carbon number 1～8.

The solidifying agent with at least 1 represented part-structure in above-mentioned general formula (II-1)～(II-4) can be by generating the aftermentioned manufacture method of bifunctional phenol compound's phenolic varnish with by-product form.

The main chain backbone that the represented part-structure of above-mentioned general formula (II-1)～(II-4) can be used as solidifying agent comprises, and a part that also can be used as in addition side chain comprises.And then the repeating unit separately that forms any the represented part-structure in above-mentioned general formula (II-1)～(II-4) can randomly comprise, and also can have rule and comprise, and can also comprise with block-wise.

In addition,, in above-mentioned general formula (II-1)～(II-4), the position of substitution of hydroxyl as long as be just not particularly limited on aromatic nucleus.

For each above-mentioned general formula (II-1)～(II-4), having a plurality of Ar can be whole identical atomic groups, also can comprise atomic group of more than two kinds.In addition, Ar represent above-mentioned general formula (II-a) and (II-b) in any represented group.

Above-mentioned general formula (II-a) and (II-b) in R ¹¹and R ¹⁴be hydrogen atom or hydroxyl independently of one another, but consider from the viewpoint of heat conductivity, be preferably hydroxyl.In addition R, ¹¹and R ¹⁴the position of substitution be not particularly limited.

In addition, above-mentioned general formula (II-a) and (II-b) in R ¹²and R ¹³the alkyl that represents independently of one another hydrogen atom or carbon number 1～8.As above-mentioned R ¹²and R ¹³in the alkyl of carbon number 1～8, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl and octyl group.In addition, above-mentioned general formula (II-a) and (II-b) in R ¹²and R ¹³the position of substitution be not particularly limited.

From realizing the viewpoint of effect of the present invention, particularly excellent heat conductivity, consider, above-mentioned general formula (II-a) and (II-b) in Ar be preferably group (the middle R of above-mentioned general formula (II-a) being selected from from dihydroxy-benzene ¹¹for hydroxyl, R ¹²and R ¹³group for hydrogen atom) and from the group of dihydroxy naphthlene (R in above-mentioned general formula (II-b) ¹⁴group for hydroxyl) at least a kind.

At this, so-called " from the group of dihydroxy-benzene ", refers to from the aromatic nucleus of dihydroxy-benzene and partly removes 2 hydrogen atoms and the divalent group that forms, the position that hydrogen atom is removed is not particularly limited.In addition about " from group of dihydroxy naphthlene " etc., be also same implication.

In addition, from the productivity of above-mentioned composition epoxy resin, the viewpoint of mobility consider, Ar is more preferably from the group of dihydroxy-benzene, more preferably be selected from by from 1, in the group of 2-dihydroxy-benzene (pyrocatechol) and the group that forms from the group of 1,3-dihydroxy-benzene (Resorcinol) at least a kind.And then consider from improving more especially the viewpoint of heat conductivity, as Ar, preferably at least comprise the group from Resorcinol.

In addition, from improving especially the viewpoint of heat conductivity, consider, the represented structural unit of repeat number n preferably comprises the group from Resorcinol.

About comprising the containing ratio from the structural unit of the group of Resorcinol, preferably in the total mass of the compound of at least 1 represented part-structure in thering is general formula (II-1)～(II-4) for being more than or equal to 55 quality %, be preferably more than or equal 60 quality %, more preferably be more than or equal to 80 quality %, be more preferably more than or equal to 90 quality %.

For m and the n in above-mentioned general formula (II-1)～(II-4), from the viewpoint of mobility, consider, be preferably m/n=20/1～1/5, more preferably 20/1～5/1, more preferably 20/1～10/1.In addition, from the viewpoint of mobility, consider, (m+n) be preferably and be less than or equal to 20, be more preferably less than or equal to 15, be more preferably less than or equal to 10.

In addition, lower value (m+n) is not particularly limited.

With regard to thering is the phenol novolac resin of at least 1 represented part-structure in general formula (II-1)～(II-4), particularly in the situation that Ar be in substituted or non-substituted dihydroxy-benzene and substituted or non-substituted dihydroxy naphthlene at least any, compare with merely phenolic varnish form by them resin etc., it is easily synthetic, and existence can access the tendency of the solidifying agent that softening temperature is low.The advantages such as manufacture, the operation that therefore, has a resin combination that comprises this resin also becomes easily.

In addition, for the phenol novolac resin with any the represented part-structure in above-mentioned general formula (II-1)～(II-4), can depart from ionization mass analysis (FD-MS) by electric field, easily determine that above-mentioned part-structure is as its sheet segment components.

In the present invention, the molecular weight with the phenol novolac resin of any the represented part-structure in above-mentioned general formula (II-1)～(II-4) is not particularly limited.From the viewpoint of mobility, consider, as number-average molecular weight (Mn), be preferably and be less than or equal to 2000, be more preferably less than or equal to 1500, be more preferably more than or equal to 350 and be less than or equal to 1500.In addition, as weight-average molecular weight (Mw), be preferably and be less than or equal to 2000, be more preferably less than or equal to 1500, be more preferably more than or equal to 400 and be less than or equal to 1500.

These Mn and Mw measure by the usual method with GPC.

In the present invention, the hydroxyl equivalent with the phenol novolac resin of any the represented part-structure in above-mentioned general formula (II-1)～(II-4) is not particularly limited.From the viewpoint of the cross-linking density relevant with thermotolerance, consider, hydroxyl equivalent is preferably counted and is more than or equal to 50 and be less than or equal to 150 with mean value, more preferably be more than or equal to 50 and be less than or equal to 120, be more preferably more than or equal to 55 and be less than or equal to 120.

In the present invention, above-mentioned phenol novolac resin also can comprise as the monomer that forms the phenolic compound of above-mentioned phenol novolac resin.As the ratio (following, also referred to as " monomer contains ratio ") that contains of monomer that forms the phenolic compound of phenol novolac resin, be not particularly limited.From the viewpoint of heat conductivity, thermotolerance and formability, consider, be preferably 5 quality %～80 quality %, more preferably 15 quality %～60 quality %, more preferably 20 quality %～50 quality %.

By making monomer contain ratio, be less than or equal to 80 quality %, when curing reaction, the crosslinked monomer without contribution tailed off, it is many that crosslinked high molecular thing becomes, and therefore forms more highdensity higher order structure, and heat conductivity improves.In addition, by making it be more than or equal to 5 quality %, when moulding, be easy to flow, therefore more improve with the adaptation of filler, can realize more excellent heat conductivity and thermotolerance.

In the situation that above-mentioned resin combination comprises solidifying agent, the content of the solidifying agent in resin combination is not particularly limited.For example, at solidifying agent, be amine be solidifying agent in the situation that, preferred amines is that the Ahew (amine equivalent) of solidifying agent and the ratio (amine equivalent/epoxy equivalent (weight)) of the epoxy equivalent (weight) that contains mesomorphic epoxy resin are 0.5～2, more preferably 0.8～1.2.In addition, at solidifying agent, be that phenol is be solidifying agent in the situation that, preferably the Ahew (phenolic hydroxyl group equivalent) of phenolic hydroxyl group and the ratio (phenolic hydroxyl group equivalent/epoxy equivalent (weight)) of the epoxy equivalent (weight) that contains mesomorphic epoxy resin are 0.5～2, more preferably 0.8～1.2.

(curing catalyst)

The in the situation that of using phenol to be solidifying agent, also can as required and use curing catalyst in above-mentioned resin combination.By also, with curing catalyst, can further be cured fully.Kind, the use level of curing catalyst are not particularly limited, and can consider from viewpoints such as speed of response, temperature of reaction, keeping property, select suitable curing catalyst.As the concrete example of curing catalyst, can enumerate imidazole compound, organophosphorus based compound, tertiary amine and quaternary ammonium salt etc.They can be used alone or two or more kinds may be used.

Wherein, from stable on heating viewpoint, consider, be preferably at least a kind in the group of the complex compound composition that selects free organic phosphine compound and organic phosphine compound and organoboron compound.

As organic phosphine compound, specifically can enumerate triphenylphosphine, phenylbenzene (p-methylphenyl) phosphine, three (alkyl phenyl) phosphine, three (alkoxyl phenyl) phosphine, three (alkyl alkoxy phenyl) phosphine, three (dialkyl phenyl organic) phosphines, three (trialkyl phenyl) phosphine, three (tetraalkyl phenyl) phosphine, three (dialkoxy phenyl) phosphine, three (tri-alkoxy phenyl) phosphines, three (tetraalkoxy benzene base) phosphine, trialkyl phosphine, dialkyl aryl phosphine, alkyl diaryl phosphine etc.

In addition, as the complex compound of organic phosphine compound and organoboron compound, specifically can enumerate tetraphenyl boric acid tetraphenylphosphoniphenolate (tetraphenylphosphonium tetraphenylborate), four ptolylboronic acid tetraphenylphosphoniphenolates (tetraphenylphosphonium tetra-p-tolylborate), tetraphenyl boric acid 4-butyl-phosphonium, normal-butyl triphenyl boric acid tetraphenylphosphoniphenolate, tetraphenyl boron acid butyl triphenyl phosphonium, tetraphenyl boric acid methyl three fourth base Phosphonium etc.

Curing catalyst can be used alone or two or more kinds may be used.As the method for making efficiently semicure resin combination described later and curable resin composition, can enumerate epoxy monomer and the reaction of phenol novolac resin are started to 2 kinds of methods that curing catalysts mixing is used that temperature is different with speed of response.

Also with curing catalyst of more than two kinds in the situation that, blending ratio can for example, decide according to the desired characteristic of above-mentioned semicure resin combination (flexibility that, needs which kind of degree) without particular limitation.

In the situation that above-mentioned resin combination comprises curing catalyst, in resin combination, the containing ratio of curing catalyst is not particularly limited.From the viewpoint of formability, consider, be preferably the 0.5 quality %～1.5 quality % in molecule with the thermosetting resin of mesomorphic group and the total quality of solidifying agent, more preferably 0.5 quality %～1 quality %, more preferably 0.75 quality %～1 quality %.

(silane coupling agent)

Above-mentioned resin combination preferably further comprises at least a kind of silane coupling agent.As the effect of adding silane coupling agent, performance is on the surface of the first filler, the second filler and surround the effect (being equivalent to tackiness agent) that forms covalent linkage between its thermosetting resin around, thereby have and transmit efficiently hot effect, and then by preventing the immersion of moisture, thereby also contribute to improve insulating reliability.

Kind as above-mentioned silane coupling agent, is not particularly limited, and can use commercially available silane coupling agent.If considered and the intermiscibility of thermosetting resin (being preferably epoxy resin), the solidifying agent that comprises as required and the heat conduction loss on the interface between minimizing resin and filler, the silane coupling agent in the present invention, preferably using endways with epoxy group(ing), amino, sulfydryl, urea groups or hydroxyl.

Concrete example as silane coupling agent, can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, APTES, 3-(2-amino-ethyl) TSL 8330, 3-(2-amino-ethyl) TSL 8330, 3-TSL 8330, 3-phenyl amino propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl triethoxyl silane, 3-urea groups propyl-triethoxysilicane etc.In addition, can also further enumerate and take the silane coupling agent oligopolymer (Hitachi changes into Coated Sand Co., Ltd. system) that SC-6000KS2 is representative.

These silane coupling agents can be used alone or two or more kinds may be used.

(organic solvent)

Above-mentioned resin combination can further comprise at least a kind of organic solvent.By comprising organic solvent, can make it be applicable to various moulding processs.As organic solvent, can use normally used organic solvent.Specifically can enumerate alcohol series solvent, ether series solvent, ketone series solvent, acid amides series solvent, aromatic hydrocarbons series solvent, ester series solvent, nitrile series solvent etc.For example, can use methyl iso-butyl ketone (MIBK), N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), METHYLPYRROLIDONE, gamma-butyrolactone, tetramethylene sulfone, pimelinketone, methylethylketone etc.They can use separately a kind, also can be also to use by mixed solvent form of more than two kinds.

(other composition)

Resin combination in the present invention can also comprise as required other composition except mentioned component.Such as enumerating elastomerics, dispersion agent etc.As elastomerics, can enumerate acrylic resin, more particularly, can enumerate homopolymer or multipolymer derived from (methyl) vinylformic acid or (methyl) acrylate.As dispersion agent, can enumerate the Ajisper processed of aginomoto Finetech Co., Ltd. series, nanmu and originally change into that HIPLAAD processed of Co., Ltd. is serial, Co., Ltd. spends king's Homogenol series processed etc.Two or more kinds may be used for these dispersion agents.

< semicure resin combination >

Semicure resin combination of the present invention, from above-mentioned resin combination, carries out semicure processing to above-mentioned resin combination and forms.With regard to above-mentioned semicure resin combination, for example, while being shaped to sheet, the resin sheet forming with resin combination by not carrying out semicure processing is compared, and operability improves.

At this, above-mentioned semicure resin combination has following feature: the viscosity of above-mentioned semicure resin combination is 10 at normal temperature (25～30 ℃) ⁴pas～10 ⁵pas, and be reduced to 10 at 100 ℃ ²pas～10 ³pas.In addition, the curable resin composition after described later solidifying can be because of heating melting.In addition, above-mentioned viscosity for example, is measured by Measurement of Dynamic Viscoelasticity (DMA) (, the ARES-2KSTD processed of TA Instruments company).In addition, condition determination is 3 ℃/min of frequency 1Hz, loading 40g, heat-up rates, by shearing test, is undertaken.

As above-mentioned semicure, process, can enumerate at 100 ℃～200 ℃ temperature the above-mentioned resin combination heating method of 1 minute～30 minutes.

< curable resin composition >

Curable resin composition of the present invention, from above-mentioned resin combination, is cured processing to above-mentioned resin combination and forms.Above-mentioned curable resin composition is excellent aspect heat conductivity and insulativity, this can think because, for example contained curable resin in molecule with mesomorphic group and specific filler combination and formed higher order structure in resin combination.

Curable resin composition can be manufactured by the resin combination of its uncured state or above-mentioned semicure resin combination being cured process.The method of above-mentioned solidification treatment can suitably be selected according to the object of the formation of resin combination, curable resin composition etc., but is preferably heating, pressure treatment.

For example, can by by the resin combination of its uncured state or above-mentioned semicure resin combination 100 ℃～250 ℃ heating 1 hour～10 hours, preferably within 1 hour～8 hours, obtain curable resin composition 130 ℃～230 ℃ heating.

< resin sheet >

Resin sheet of the present invention is shaped to sheet by above-mentioned resin combination and forms.Above-mentioned resin sheet for example can be by above-mentioned resin combination is coated in mold release film, and remove the solvent comprising as required and manufacture.Above-mentioned resin sheet is owing to being formed by above-mentioned resin combination, so heat conductivity, mobility and pliability are excellent.

The thickness of above-mentioned resin sheet is not particularly limited, and can suitably select according to object.For example, as the thickness of resin sheet, can be made as 50 μ m～500 μ m, from thermal conductivity, electrical insulating property and flexual viewpoint, consider, be preferably 80 μ m～300 μ m.

Above-mentioned resin sheet is such as manufacturing as follows: in the mold release film such as PET film, the varnish shape resin combination that coating is modulated to adding the organic solvents such as methylethylketone, pimelinketone in above-mentioned resin combination is (following, also referred to as " resinous varnish ") and form after coating layer, from coating layer, remove at least a portion of above-mentioned organic solvent and be dried.

The coating of resinous varnish can utilize known method to implement.Specifically can enumerate the methods such as comma coating, mould painting, die lip coating, intaglio plate coating.As the thickness for regulation, form the coating process of resin combination layer, applicable make applied thing by the comma coating method between gap, by nozzle coating, regulated the mould Tu Fa etc. of the resinous varnish of flow.For example, in the situation that the thickness of the coating layer (resin combination layer) before dry is 50 μ m～500 μ m, preferably use comma coating method.

As long as drying means can be removed at least a portion of organic solvent contained in resinous varnish and just be not particularly limited, can from normally used drying means, suitably select according to organic solvent contained in resinous varnish.Conventionally can enumerate 80 ℃～150 ℃ of left and right and carry out the method for heat treated.

The resin combination layer of above-mentioned resin sheet is owing to not almost being cured reaction, although therefore there is pliability, not enough as the flexibility of sheet material, sheet material independence deficiency under having removed as the state of the above-mentioned PET film of supporter, operational difficulty.

Above-mentioned resin sheet is preferably and carries out to forming the resin combination of this resin sheet the semicure resin combination that semicure processing forms.That is the B rank sheet material that, above-mentioned resin sheet is preferably further heat treated until reach semi-cured state (B scalariform state) and forms.Above-mentioned resin sheet is by processing the semicure resin combination form and form by above-mentioned resin combination being carried out to semicure, thereby thermal conductivity and electrical insulating property are excellent, excellent as pliability and the work-ing life of B rank sheet material.

At this, B rank sheet material has following feature: its viscosity is 10 at normal temperature (25～30 ℃) ⁴pas～10 ⁵pas, and be reduced to 10 at 100 ℃ ²pas～10 ³pas.In addition, the curable resin composition after described later solidifying can be because of heating melting.In addition, above-mentioned viscosity is measured by DMA (3 ℃/min of frequency 1Hz, loading 40g, heat-up rates).

About above-mentioned resin sheet being carried out to the condition of heat treated, as long as can make resin combination layer reach B scalariform state, be just not particularly limited, can suitably select according to the formation of resin combination.When heat treated, the object in the space (hole) the resin combination layer producing while being coated with from eliminating, is preferably selected from the heating treatment method in thermovacuum compacting, hot-roll lamination etc.Thus, can manufacture efficiently smooth B rank sheet material.

Specifically, for example can be by under reduced pressure (for example, 1kPa), heat under the pressing pressure of temperature 100 ℃～200 ℃, 1 second～90 seconds, 1MPa～20MPa, pressure treatment, make above-mentioned resin combination semicure to B scalariform state.

In addition, by 2 coatings, dried resin sheets being fitted and carried out above-mentioned heating, pressure treatment during to B scalariform state at semicure, thereby utilize the curable resin composition of aftermentioned method manufacture to demonstrate more high thermoconductivity.Now, need to be by coated face (face up during coating, the opposing face of the face joining with PET film) laminating each other, the two sides of resin sheet becomes more smooth thus.

The thickness of above-mentioned B rank sheet material can suitably be selected according to object, for example, can be made as 50 μ m～500 μ m, from thermal conductivity, electrical insulating property and flexual viewpoint, considers, is preferably 80 μ m～300 μ m.In addition, one side also can be by carrying out hot pressing and make 2 layers of above resin sheet being stacked on one side.

In the situation that using the solvent-laden resin combination of bag to form above-mentioned B rank sheet material, the viewpoint that forms the worry of bubble when producing exhaust when solidifying is considered, solvent survival rate in the sheet material of above-mentioned B rank is preferably and is less than or equal to 2.0 quality %, more preferably be less than or equal to 1.0 quality %, be more preferably less than or equal to 0.8 quality %.

Above-mentioned solvent survival rate is obtained as follows: B rank sheet material is cut out to 40mm square, in being preheated to the thermostatic bath of 190 ℃ dry 2 hours, according to the quality change before and after now dry, obtain.

Above-mentioned B rank sheet material is excellent aspect mobility.Specifically, the amount of flow of above-mentioned B rank sheet material is preferably 130%～210%, and more preferably 150%～200%.The index of melt fluidity when this amount of flow is thermo-compressed.If amount of flow is more than or equal to 130%, can fully obtain imbedibility, in addition, if be less than or equal to 210%, can suppress the generation because of the excessive burr causing that flows.

Above-mentioned amount of flow is calculated as follows: the area change rate with the B rank sheet material before and after pressing when the thick B rank sheet material stamping-out of 200 μ m being become the square and sample that obtains of 10mm press 1 minute under atmospheric pressure, under the condition of 180 ℃ of temperature, pressing pressure 15MPa calculates.Area change rate is obtained as follows: with the scanner that is more than or equal to 300DPI, obtain the profile projection image of sample, utilize image analysis software (Adobe Photoshop) to carry out after binary conversion treatment, according to the velocity of variation of area (pixel count), obtain.

Amount of flow (%)=(area of the B rank sheet material after pressing)/(area of the B rank sheet material before pressing)

In addition, above-mentioned resin sheet can be also that above-mentioned resin combination is cured and processes the curable resin composition forming.The resin sheet consisting of curable resin composition can be manufactured by the resin sheet of its uncured state or B rank sheet material being cured process.The method of above-mentioned solidification treatment can suitably be selected according to the object of the formation of resin combination, curable resin composition etc., but is preferably heating, pressure treatment.

For example, can by the resin sheet of its uncured state or B rank sheet material 100 ℃～250 ℃ heating 1 hour～10 hours, preferably at the resin sheet of 130 ℃～230 ℃ heating 1 hour～obtain being formed by curable resin composition for 8 hours.In addition, while preferably apply the pressure of 1MPa～20MPa, carry out above-mentioned heating.

In addition, the example of method as manufacture with the resin sheet being formed by curable resin composition of excellent heat conductivity, there is following method: first, under the state that the mode of joining at the alligatoring face of take with the one side Copper Foil (thickness 80 μ m～120 μ m) that is alligatoring face is clamped B rank sheet material, under the pressing pressure of temperature 130 ℃～230 ℃, 3 minutes～10 minutes, pressure 1MPa～20MPa, heat, pressure treatment, make B rank sheet material and Copper Foil bonding.Then,, 130 ℃～230 ℃ heating 1 hour～8 hours, utilize etch processes to remove the Copper Foil part of the resulting resin sheet with Copper Foil, the resin sheet that obtains being formed by curable resin composition.

< prepreg >

Prepreg of the present invention has fiber base material and forms with being immersed in the above-mentioned resin combination in above-mentioned fiber base material.By being this formation, form the prepreg of thermal conductivity and insulativity excellence.In addition, the resin combination thixotropy that contains Alpha-alumina filler improves, and therefore can suppress the sedimentation of the second filler in painting process described later, dipping process.Therefore, can be suppressed at the generation of the deep or light distribution of the second filler on the thickness direction of prepreg, result is to access the prepreg of thermal conductivity and insulativity excellence.

As the fiber base material that forms prepreg, so long as normally used fiber base material is just not particularly limited when manufacturing the plywood of metal-foil-clad, multi-layer printed circuit board, conventionally use the fiber base materials such as woven cloths, non-woven.

The mesh of above-mentioned fiber base material is not particularly limited.From the viewpoint of thermal conductivity and insulativity, consider, mesh is preferably more than or equals 5 times of median size (D50) of above-mentioned the second filler.In addition,, in the situation that the size distribution curve of above-mentioned the second filler has a plurality of peaks, be more preferably more than or equal to the mesh of 5 times of the corresponding particle diameter in peak of particle diameter maximum.

The material of fiber base material is not particularly limited.Specifically can enumerate the inorganic fibres such as glass, aluminum oxide, boron, sial glass, silica glass, Tyranno, silicon carbide, silicon nitride, zirconium white; Organic fibre and their mixed systems such as aromatic polyamide, polyether-ether-ketone, polyetherimide, polyethersulfone, carbon, Mierocrystalline cellulose.Wherein, preferably use the woven cloths of glass fibre.Thus for example in the situation that using prepreg to form printing distributing board, can access there is bendability, the printing distributing board of at random bending.And then also can reduce to follow the dimensional change of the printing distributing board of temperature variation in manufacturing process, moisture absorption etc.

The thickness of above-mentioned fiber base material is not particularly limited.From giving better flexual viewpoint, consider, be more preferably less than or equal to 30 μ m, from the viewpoint of dipping property, consider, be preferably and be less than or equal to 15 μ m.The lower limit of the thickness of fiber base material is not particularly limited, and is generally 5 μ m left and right.

In above-mentioned prepreg, the pickup of above-mentioned resin combination (containing ratio) is preferably 50 quality %～99.9 quality % with respect to the total mass of fiber base material and resin combination.

Above-mentioned prepreg can be manufactured as follows: the above-mentioned resin combination that is modulated into varnish shape with above-mentioned similarly operation is immersed in fiber base material, by the 80 ℃～heat treated of 150 ℃, removes at least a portion of organic solvent.

In addition, the method that resin combination is immersed in fiber base material is not particularly limited.For example, can enumerate the method for utilizing coating machine to be coated with.In detail, can enumerate the vertical coating method of mentioning after making fiber base material slip in resin combination and on support membrane, after coating resin composition, press horizontal coating method that fiber base material floods etc.From suppressing the viewpoint of the segregation of the second filler in fiber base material, consider, be preferably horizontal coating method.

Above-mentioned prepreg also can, by utilizing the hot-pressing processing of press, roll-type laminating machine (roll laminator) etc. before stacked or stickup, will be used after surface smoothing in advance.The method of enumerating in the manufacture method of the method for hot-pressing processing and above-mentioned B rank sheet material is same.In addition, about the treatment condition such as Heating temperature, vacuum tightness and pressing pressure of the hot-pressing processing of above-mentioned prepreg, also with the heating of above-mentioned B rank sheet material, pressure treatment in the condition enumerated same.

In the situation that using the solvent-laden resin combination of bag to make above-mentioned prepreg, solvent survival rate in above-mentioned prepreg is preferably and is less than or equal to 2.0 quality %, more preferably be less than or equal to 1.0 quality %, be more preferably less than or equal to 0.8 quality %.

Above-mentioned solvent survival rate is obtained as follows: prepreg is cut out to 40mm square, in being preheated to the thermostatic bath of 190 ℃ dry 2 hours, according to the quality change before and after now dry, obtain.

< plywood >

Plywood in the present invention has by adhesives and is configured in above-mentioned by the semicure resin combination layer on adhesives or curable resin composition layer.Above-mentioned semicure resin combination layer and curable resin composition layer are the semicure resin combination layer of at least a kind and the curable resin composition layers in resin combination layer, above-mentioned resin sheet and the above-mentioned prepreg forming from the freely above-mentioned resin combination of choosing.By thering is semicure resin combination layer or the curable resin composition layer being formed by above-mentioned resin combination, thus the plywood of formation heat conductivity and insulativity excellence.

As above-mentioned, by adhesives, can enumerate tinsel, metal sheet etc.In the above-mentioned one side that can be only attached to above-mentioned semicure resin combination layer or curable resin composition layer by adhesives, also can be attached on two sides.

As above-mentioned tinsel, be not particularly limited, can from normally used tinsel, suitably select.Specifically can enumerate goldleaf, Copper Foil, aluminium foil etc., conventionally use Copper Foil.As the thickness of above-mentioned tinsel, so long as 1 μ m～200 μ m is just not particularly limited, can select suitable thickness according to the electric power using etc.

In addition, as above-mentioned tinsel, also can use the composite foil of take nickel, nickel-phosphorus, nickel-tin alloy, nickel-ferro alloy, lead, Lead-tin alloy etc. as middle layer and being provided with the 3-tier architecture of the copper layer of 0.5 μ m～15 μ m and the copper layer of 10 μ m～150 μ m on its two surface; Or by aluminium and the compound 2 layers of structure composite paper tinsel of Copper Foil.

Above-mentioned metal sheet preferably metallic substance high by thermal conductivity, that thermal capacity is large forms.Alloy of specifically can illustration copper, using in aluminium, iron and lead frame etc.

The thickness of slab of above-mentioned metal sheet can suitably be selected according to purposes.For example, above-mentioned metal sheet can be selected material according to object as follows: the in the situation that of preferential lightweight, processibility, select aluminium, select copper in the situation that of preferential thermal diffusivity.

In above-mentioned plywood, as semicure resin combination layer or curable resin composition layer, can be to have 1 layer from any the form in above-mentioned resin combination layer, above-mentioned resin sheet or above-mentioned prepreg, can be also by 2 layers of above stacked form having.In the situation that there is more than 2 layers semicure resin combination layer or curable resin composition layers, can be also the form with 2 layers of above above-mentioned resin combination layer, there is the form of 2 above above-mentioned resin sheets and there is any in the form of 2 above above-mentioned prepreg.And then, also can combine have in above-mentioned resin combination layer, above-mentioned resin sheet and above-mentioned prepreg any two or more.

Above-mentioned plywood for example can form resin combination layer by being coated with above-mentioned resin combination on by adhesives, and it is heated and pressure treatment, makes above-mentioned resin combination layer semicure or solidifies simultaneously with closely sealed and obtain by adhesives.Or, can by prepare above-mentioned by adhesives on the material that obtains of stacked above-mentioned resin sheet or above-mentioned prepreg, it is heated and is pressurizeed, make above-mentioned resin sheet or above-mentioned prepreg semicure or solidify simultaneously with closely sealed and obtain by adhesives.

Above-mentioned resin combination layer, resin sheet and prepreg semicure or curing curing are not particularly limited.For example, be preferably heating and pressure treatment.The Heating temperature of heating and pressure treatment is not particularly limited.Be generally the scope of 100 ℃～250 ℃, be preferably the scope of 130 ℃～230 ℃.In addition, the pressurized conditions of heating and pressure treatment is not particularly limited.Be generally the scope of 1MPa～20MPa, be preferably the scope of 1MPa～15MPa.In addition,, when heating and pressure treatment, preferably use vacuum pressing.

The thickness of plywood is preferably and is less than or equal to 500 μ m, more preferably 100 μ m～300 μ m.If thickness is less than or equal to 500 μ m, pliability is excellent, produces crack in the time of can being suppressed at bending machining, in the situation that thickness is less than or equal to 300 μ m, more can see this tendency.In addition,, in the situation that thickness is more than or equal to 100 μ m, operability is excellent.

< is with resin cured matter, the metal substrate > of tinsel

As an example of above-mentioned plywood, can enumerate and can be used in the resin cured matter with tinsel and the metal substrate of making printing distributing board described later.

The above-mentioned resin cured matter with tinsel is used 2 tinsels as being formed by adhesives in above-mentioned plywood.Specifically, a side tinsel, above-mentioned curable resin composition layer and the opposing party's tinsel is stacked and form in this order.

Form the tinsel of the above-mentioned resin cured matter with tinsel and the detailed content of curable resin composition layer as mentioned before.

In addition, said metal substrates is used tinsel and metal sheet as being formed by adhesives in above-mentioned plywood.Specifically, said metal substrates is stacked and form in this order by above-mentioned tinsel, above-mentioned curable resin composition layer and above-mentioned metal sheet.

Form the tinsel of said metal substrates and the detailed content of curable resin composition layer as mentioned before.

As above-mentioned metal sheet, be not particularly limited, can from normally used metal sheet, suitably select.Specifically can enumerate aluminium sheet, iron plate etc.The thickness of metal sheet is not particularly limited.From the viewpoint of processibility, consider, thickness is preferably more than or equals 0.5mm and be less than or equal to 5mm.

In addition, from the viewpoint of boosting productivity, consider, above-mentioned metal sheet is preferably made and is installed on after electronic unit with the size larger than desired size, cuts into use size.Therefore it is excellent that the metal sheet, using in metal substrate is desirably in cutting processing aspect.

In the situation that using aluminium as above-mentioned metal sheet, can select aluminium or using alloy that aluminium is principal constituent as material.The alloy that aluminium or the aluminium of take are principal constituent can obtain many kinds of substance according to its chemical constitution and heat-treat condition.Wherein, the preferred selected kind that is easy to the high and excellent strength of the processibilities such as cutting.

< printing distributing board >

Printing distributing board of the present invention is laminated metal sheet, curable resin composition layer and wiring layer in this order.Above-mentioned curable resin composition layer is the curable resin composition layer of at least a kind in resin combination layer, above-mentioned resin sheet and the above-mentioned prepreg forming from the freely above-mentioned resin combination of choosing.By thering is the curable resin composition layer being formed by above-mentioned resin combination, thus the printing distributing board of formation heat conductivity and insulativity excellence.

Above-mentioned printing distributing board can carry out circuit by the tinsel with at least one party in the resin cured matter of tinsel to already described or the tinsel in metal substrate and process to manufacture.Circuit processing for above-mentioned tinsel, can be suitable for the common method by means of photoetching.

As the optimal way of above-mentioned printing distributing board, can enumerate with the paragraph 0064 of TOHKEMY 2009-214525 communique, the same printing distributing board of the printing distributing board of recording in the paragraph 0056～0059 of TOHKEMY 2009-275086 communique.

< power semiconductor arrangement >

Power semiconductor arrangement of the present invention comprises: the semiconductor module that metal sheet, soldering-tin layer and semi-conductor chip are laminated in this order; Radiating component; And the cured article that is configured in the resin sheet of the above-mentioned metal sheet of above-mentioned semiconductor module and the sheet-like formed body of the conduct resin combination of the present invention between above-mentioned radiating component.

Above-mentioned power semiconductor arrangement only semiconductor module part seals with sealing material etc., also can power semiconductor modular integral body with mold pressing resin etc., have carried out mold pressing.Below, use accompanying drawing, an example of above-mentioned power semiconductor arrangement is described.

Figure 11 is the summary sectional view of an example that the formation of power semiconductor arrangement is shown.In Figure 11, the cured article 102 that disposes resin sheet between the metal sheet 106 of the semiconductor module that metal sheet 106, soldering-tin layer 110 and semi-conductor chip 108 are laminated in this order and heat radiation basal substrate 104, semiconductor module partly seals with sealing material 114.

In addition, Figure 12 is the summary sectional view of another example that the formation of power semiconductor arrangement is shown.In Figure 12, between the metal sheet 106 of the semiconductor module that metal sheet 106, soldering-tin layer 110 and semi-conductor chip 108 are laminated in this order and heat radiation basal substrate 104, dispose the cured article 102 of resin sheet, semiconductor module and heat radiation basal substrate 104 use mold pressing resins 112 have carried out mold pressing.

Like this, can be as shown in figure 11 as semiconductor module and the thermal diffusivity adhesive linkage dispelling the heat between basal substrate as the cured article of the resin sheet of the sheet-like formed body of resin combination of the present invention.In addition, as shown in figure 12 by the moulding of power semiconductor arrangement integral die in the situation that, also can be as the heat sink material between heat radiation basal substrate and metal sheet.

Embodiment

Below, by embodiment, illustrate the present invention, but the present invention is not limited to these embodiment.In addition, unless otherwise specified, " part " and " % " is quality criteria.

Show the material and the abbreviation thereof that in the making of resin combination, use below.

(the first filler)

HIT-70[Alpha-alumina, Sumitomo Chemical (strain) system, median size: 150nm]

AA-04[Alpha-alumina, Sumitomo Chemical (strain) system, median size: 400nm]

(the second filler)

HP-40[boron nitride, water island alloy iron (strain) system, median size: 18 μ m]

FAN-f30[aluminium nitride, Furukawa electronics (strain) system, median size: 30 μ m]

FAN-f05[aluminium nitride, Furukawa electronics (strain) system, median size: 5 μ m]

(the 3rd filler)

ShapalH[aluminium nitride, Tokuyama (strain) system, median size: 0.6 μ m]

(thermosetting resin)

Following Resin A (with reference to No. 4619770 communique of Japanese Patent)

[changing 22]

Following resin B (with reference to No. 4619770 communique of Japanese Patent)

[changing 23]

Following resin C (with reference to TOHKEMY 2011-74366 communique)

[changing 24]

Following resin D (with reference to TOHKEMY 2011-74366 communique)

[changing 25]

(solidifying agent)

CRN[pyrocatechol Resorcinol phenolic varnish (feed ratio: 5/95) resin, Hitachi change into industry (strain) and make, contain 50% pimelinketone]

The synthetic method > of < CRN

In the removable flask of the 3L with stirrer, water cooler, thermometer, add Resorcinol 627g, pyrocatechol 33g, 37% formaldehyde 316.2g, oxalic acid 15g, water 300g, in oil bath heat be on one side warming up to 100 ℃ on one side.104 ℃ of left and right, reflux, under reflux temperature, sustained reaction is 4 hours.Then, on one side dephlegmate make the temperature in flask be warming up to 170 ℃ on one side.When keeping 170 ℃, sustained reaction is 8 hours.After reaction, under reduced pressure carry out 20 minutes concentrated, remove water in system etc., obtain the bakelite C RN as target.

In addition, for resulting CRN, utilize FD-MS to confirm structure, result can confirm general formula (II-1)～(II-4) represented part-structure and all exist.

In addition can think, under above-mentioned reaction conditions, the initial compound with the represented part-structure of general formula (II-1) that generates, it further carries out dehydration reaction, thereby generate, has general formula (II-1)～compound of at least 1 represented part-structure in (II-4).

For resulting CRN, carry out as follows the mensuration of Mn, Mw.

The mensuration of Mn and Mw is used the high performance liquid chromatograph L6000 processed of (strain) Hitachi and the data analysis device C-R4A processed of (strain) Shimadzu Seisakusho Ltd. to carry out.Analyze and use eastern Cao (strain) G2000HXL processed and G3000HXL with GPC post.Sample solution concentration is 0.2 quality %, and moving phase is used tetrahydrofuran (THF), with 1.0ml/min flow velocity, measures.Use polystyrene standard sample making typical curve, use this typical curve, with polystyrene conversion value, calculate Mn and Mw.

For resulting CRN, carry out as follows the mensuration of hydroxyl equivalent.

Hydroxyl equivalent utilizes Acetyl Chloride 98Min.-potassium hydroxide volumetry to measure.In addition, with regard to the judgement of titration end point, because the color of solution is dark-coloured, therefore do not utilize the development process by means of indicator, and utilize potential difference titration to carry out.Specifically, the hydroxyl of measuring resin after chloroacetylation, is used to its superfluous reagent of water decomposition, the acetic acid generating with the titration of potassium hydroxide/methanol solution in pyridine solution.About resulting CRN, below being shown in.

It is to contain to comprise 35% monomer component (Resorcinol) as the resol of the solidifying agent (hydroxyl equivalent 62, number-average molecular weight 422, weight-average molecular weight 564) of low molecular dilution agent, described resol is the mixture with the compound of at least 1 represented part-structure in general formula (II-1)～(II-4), and Ar is for carrying out R in comfortable above-mentioned general formula (II-a) ¹¹=hydroxyl, R ¹²=R ¹³1 of=hydrogen atom, the group of 2-dihydroxy-benzene (pyrocatechol) and from the group of 1,3-dihydroxy-benzene (Resorcinol).

(additive)

TPP: triphenylphosphine [curing catalyst]

KBM-573:3-phenyl amino propyl trimethoxy silicane [silane coupling agent, SHIN-ETSU HANTOTAI's chemical industry (strain) system]

(solvent)

CHN: pimelinketone

(supporter)

PET film [rattan lumber industry (strain) system, 75E-0010CTR-4]

Copper Foil [Furukawa (strain) system, thickness: 80 μ m, GTS level]

(embodiment 1)

The making > of < resin combination

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, thermosetting resin (Resin A) 10.22 quality %, solidifying agent (CRN) 6.30 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.56 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate the first filler with respect to the ratio of the total volume of the first filler, the second filler, thermosetting resin and solidifying agent, result is 0.26 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 74 volume %.

The making > of < B rank sheet material

Use applicator (applicator) that the epoxy resin varnish of above-mentioned making be take after mode that dried thickness is 200 μ m is coated on PET film, 100 ℃ dry 10 minutes.Then, by vacuum pressing, carry out hot pressing (press temperature: 180 ℃, vacuum tightness: 1kPa, pressing pressure: 15MPa, treatment time: 60 seconds), with the form of the resin sheet of semicure resin combination, obtain B rank sheet material.

The evaluation > of < amount of flow

By B obtained above rank sheet material, (thickness: after PET film 200 μ m) is peelled off, stamping-out becomes 10mm square, is used press, under atmospheric pressure, in temperature: pressurize 1 minute under 180 ℃, the condition of pressing pressure: 15MPa and crush.With the scanner that is more than or equal to 300DPI, obtain the profile projection image that crushes sample, utilize image analysis software (Adobe Photoshop) to carry out after binary conversion treatment, according to the velocity of variation of the area (pixel count) before and after crushing, evaluate amount of flow.

< is with the making > of the resin cured matter of Copper Foil

After the PET film of B obtained above rank sheet material is peelled off, with 2 Copper Foils with its uneven surface respectively the mode relative with B rank sheet material clamp, by vacuum pressing, carry out vacuum compressing (temperature: 180 ℃, vacuum tightness: 1kPa, pressing pressure: 15MPa, treatment time: 8 minutes).Then, under atmospheric pressure, 140 ℃ of heating 2 hours, 165 ℃ of heating 2 hours, and then 190 ℃ of heating 2 hours, obtain the resin cured matter with Copper Foil.

The mensuration > of < thermal conductivity

(resin sheet cured article)

The Copper Foil etching of the resin cured matter with Copper Foil obtained above is removed, with the form of curable resin composition, obtain resin sheet cured article.Resulting resin sheet cured article is cut out to 10mm square, by graphite spray (Graphite Spray) carry out after Darkening process, use xenon flicker method (LFA447nanoflash processed of NETZSCH company) evaluation thermal diffusivity.According to this value, utilize amassing of Archimedes's method density of measuring and the specific heat that utilizes DSC (DSC Pyris1 processed of Perkin Elmer company) to measure, obtain the thermal conductivity of resin sheet cured article.

Show the result in table 1.

In addition,, according to the thermal conductivity of resin sheet cured article obtained above, use following formula to convert and obtain resin thermal conductivity partly in resin sheet cured article.

1-ν=[(λ mix-λ res)/(λ res-λ fil)] * (λ res/ λ mix) (wherein, x=1/ (1+ χ))

Show the result in table 1.

λ mix: the thermal conductivity of resin sheet (W/mK)

λ res: the thermal conductivity (W/mK) of resin part in resin sheet

λ fil: in resin sheet, the thermal conductivity (W/mK) of filler part (is made as 60, in the situation that the mixture of boron nitride and aluminum oxide is made as 60, is made as 130 in the situation that of aluminium nitride in the situation that the second filler is boron nitride.)

ν: the volume fraction of filler (volume %)

χ: the form parameter of filler (is made as 3.1, is made as 2.2 in the situation that of aluminium nitride in the situation that the second filler is boron nitride.)

(packless resin cured matter)

Make the mixture melting of the thermosetting resin, solidifying agent and the curing catalyst that use in the making of above-mentioned resin combination, with 2 aluminium sheets (thickness: 200 μ m) clamp, under atmospheric pressure, 140 ℃ of heating 1 hour, 165 ℃ of heating 1 hour, and then 190 ℃ of heating 1 hour, obtain the packless resin cured matter (thickness: approximately 150 μ m) with aluminium sheet.

The resin cured matter obtaining for peelling off aluminium sheet from the above-mentioned packless resin cured matter with aluminium sheet, use temperature ripple apparatus for thermal analysis (the ai-Phase mobile1u processed of ai-Phase company) is evaluated thermal diffusivity.According to this value, utilize the long-pending of density that aforesaid method obtains and specific heat, obtain the thermal conductivity of packless resin cured matter, using it as above-mentioned resin sheet cured article (curable resin composition) in the thermal conductivity of resin part.

Show the result in table 1.

The mensuration > of < insulation breakdown voltage

The Copper Foil etching of the resin cured matter with Copper Foil obtained above is removed, with the form of curable resin composition, obtain resin sheet cured article.Resulting resin sheet cured article is cut out and is more than or equal to the square size of 100mm as sample.Use YAMAYO tester (having) YST-243-100RHO processed, with the cylinder electrode of diameter 25mm, clamp, in rate of rise 500V/s, room temperature, atmosphere, measure insulation breakdown voltage, obtain mean value and the Schwellenwert of 5 above measuring points.

Show the result in table 1.

(embodiment 2)

The first filler (Alpha-alumina, HIT-70:0.45 volume % with AA-04:11.76 volume % mixture) 12.21 quality %, the second filler (boron nitride, HP-40) 58.53 quality %, thermosetting resin (Resin A) 10.22 quality %, solidifying agent (CRN) 6.30 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.56 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate the first filler with respect to the ratio of the total volume of the first filler, the second filler, thermosetting resin and solidifying agent, result is 7.5 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 65 volume %.

Except using epoxy resin varnish obtained above, operation similarly to Example 1, makes B rank sheet material and with the resin cured matter of Copper Foil, evaluates with above-mentioned similarly operation.

Show the result in table 1.

(embodiment 3)

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler 63.84 quality % (aluminium nitride, FAN-f30:49.02 volume % with FAN-f05:14.82 volume % mixture), the 3rd filler (aluminium nitride, ShapalH) 10.39 quality %, thermosetting resin (Resin A) 7.23 quality %, solidifying agent (CRN) 4.46 quality %, curing catalyst (TPP) 0.08 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 13.48 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of aluminum oxide is made as to 3.97g/cm ³, aluminium nitride density be made as 3.26g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate the first filler with respect to the ratio of the total volume of the first filler, the second filler, thermosetting resin and solidifying agent, result is 0.37 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 64 volume %.In addition, the total volume of the second filler and the 3rd filler is 74 volume % with respect to the ratio of above-mentioned total volume.

In addition, the median size of the second filler (D50) is 24 μ m.

Use epoxy resin varnish obtained above, the condition of the hot pressing by means of vacuum pressing is changed to press temperature: 150 ℃, vacuum tightness: 1kPa, pressing pressure: 1MPa, treatment time: 60 seconds, the condition of the vacuum compressing by means of vacuum pressing is changed to press temperature: 150 ℃, vacuum tightness: 1kPa, pressing pressure: 4MPa, treatment time: 5 minutes, in addition, operation similarly to Example 1, make B rank sheet material and with the resin cured matter of Copper Foil, evaluate with above-mentioned similarly operation.

Show the result in table 1.

(embodiment 4)

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, thermosetting resin (resin B) 10.22 quality %, solidifying agent (CRN) 6.30 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.56 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

Show the result in table 1.

(embodiment 5)

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, thermosetting resin (resin C) 10.34 quality %, solidifying agent (CRN) 6.05 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.69 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

Show the result in table 1.

(embodiment 6)

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, thermosetting resin (resin D) 10.42 quality %, solidifying agent (CRN) 5.90 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.76 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

Show the result in table 1.

(embodiment 7)

The first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 74.23 quality %, thermosetting resin (Resin A) 7.23 quality %, solidifying agent (CRN) 4.46 quality %, curing catalyst (TPP) 0.08 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 13.48 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate the first filler with respect to the ratio of the total volume of the first filler, the second filler, thermosetting resin and solidifying agent, result is 0.27 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 81 volume %.

Show the result in table 1.

(comparative example 1)

The second filler (boron nitride, HP-40) 70.61 quality %, thermosetting resin (Resin A) 10.26 quality %, solidifying agent (CRN) 6.34 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.61 quality % are mixed, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of boron nitride is made as to 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate the second filler with respect to the ratio of the total volume of the second filler, thermosetting resin and solidifying agent, result is 74 volume %.

Show the result in table 2.

(comparative example 2)

Silica nanometer filler ((strain) Admatechs system, trade(brand)name: Admanano, the median size: 15nm) 0.25 quality %, the second filler (boron nitride, HP-40) 70.49 quality %, thermosetting resin (Resin A) 10.22 quality %, solidifying agent (CRN) 6.30 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.56 quality % mix, and to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish of the first filler will be replaced.

The density of silicon-dioxide is made as to 2.20g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate silica nanometer filler with respect to the ratio of the total volume of silica nanometer filler, the second filler, thermosetting resin and solidifying agent, result is 0.26 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 74 volume %.

Show the result in table 2.

(comparative example 3)

By Alpha-alumina filler (Sumitomo Chemical (strain) system, trade(brand)name: AA-07, median size: 700nm) 0.72 quality %, the second filler (boron nitride, HP-40) 66.82 quality %, thermosetting resin (Resin A) 12.65 quality %, solidifying agent (CRN) 3.90 quality %, curing catalyst (TPP) 0.13 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 11.81 quality % mix, and obtain epoxy resin varnish to wrap the form of solvent-laden resin combination.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate Alpha-alumina filler with respect to the ratio of the total volume of Alpha-alumina filler, the second filler, thermosetting resin and solidifying agent, result is 0.40 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 69 volume %.

Show the result in table 2.

(comparative example 4)

By gama-alumina Nano filling (large bright chemistry (strain) system, trade(brand)name: TM-300D, median size: 10nm) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, thermosetting resin (Resin A) 10.22 quality %, solidifying agent (CRN) 6.30 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.56 quality % mix, and obtain epoxy resin varnish to wrap the form of solvent-laden resin combination.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of Resin A and CRN be made as 1.20g/cm ³, calculate gama-alumina Nano filling with respect to the ratio of the total volume of gama-alumina Nano filling, the second filler, thermosetting resin and solidifying agent, result is 0.26 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 74 volume %.

Show the result in table 2.

(comparative example 5)

Using the first filler (Alpha-alumina, HIT-70) 0.45 quality %, the second filler (boron nitride, HP-40) 70.29 quality %, mix as the bisphenol A type epoxy resin of thermosetting resin (DIC (strain) system, trade(brand)name: EPICLON850, without mesomorphic group) 10.08 quality %, solidifying agent (CRN) 6.58 quality %, curing catalyst (TPP) 0.11 quality %, silane coupling agent (KBM-573) 0.07 quality % and solvent (CHN) 12.42 quality %, to wrap the form of solvent-laden resin combination, obtain epoxy resin varnish.

The density of aluminum oxide is made as to 3.97g/cm ³, boron nitride density be made as 2.18g/cm ³, and the density of the mixture of bisphenol A type epoxy resin and CRN be made as 1.20g/cm ³, calculate the first filler with respect to the ratio of the total volume of the first filler, the second filler, thermosetting resin and solidifying agent, result is 0.26 volume %.In addition, calculate the second filler with respect to the ratio of above-mentioned total volume, result is 74 volume %.

Show the result in table 2.

In addition, in table 1 and table 2, "-" represents not add.

[table 1]

[table 2]

By the alumina packing of nano-particles size and the thermosetting resin in molecule with mesomorphic group are combined, in embodiment 1～7, the resin sheet cured article of any all demonstrates high thermoconductivity.In addition,, in any in embodiment 1～7, the thermal conductivity of the resin cured matter being converted by resin sheet cured article demonstrates the value higher than the thermal conductivity of the resin cured matter of being obtained by packless resin cured matter.Proof thus, the thermosetting resin with mesomorphic group be take alumina packing and is brought into play higher order as core, and the heat conductivity of resin cured matter itself also improves.In addition,, with regard to any in embodiment 1～7, amount of flow, insulation breakdown voltage are all good.

Not adding the comparative example 1,2,4 of the alumina packing of nano-particles size compares with embodiment 1, the thermal conductivity of resin sheet cured article is lower, in addition, the thermal conductivity of the resin cured matter being converted by resin sheet cured article is compared with the thermal conductivity of the resin cured matter of being obtained by packless resin cured matter, and its value is lower.In addition, compare with embodiment 1, the comparative example 5 that uses the universal epoxy resin without mesomorphic group is also that the thermal conductivity of resin sheet cured article is lower.And then with regard to be more than or equal to 1nm and be less than the extraneous comparative example 3 of 500nm, amount of flow significantly reduces with regard to the particle diameter of the alumina packing as the first filler.

The disclosure integral body that No. 2012-090473rd, No. PCT/JP2011/075345th, international patent application and Japanese patent application is introduced in this specification sheets by reference.All documents, patent application and the technological standard in this specification sheets, recorded, and specifically and respectively recorded situation same degree that each document, patent application and technological standard be introduced into by reference by with reference to introducing in this specification sheets.

Claims

1. a resin combination, it comprises: the first filler, described the first filler in the size distribution of using laser diffractometry to measure, be more than or equal to 1nm and be less than in the scope of 500nm and there is peak, and comprise Alpha-alumina; The second filler, described the second filler in the size distribution of using laser diffractometry to measure, have peak in the scope of 1 μ m～100 μ m; And the thermosetting resin in molecule with mesomorphic group.

2. a resin combination, it comprises: the first filler, described the first filler is accumulated 50% corresponding median size D50 and is more than or equal to 1nm and is less than 500nm from the small particle size side of weight build-up size-grade distribution, and comprises Alpha-alumina; The second filler, it is 1 μ m～100 μ m that described the second filler is accumulated 50% corresponding median size D50 from the small particle size side of weight build-up size-grade distribution; And the thermosetting resin in molecule with mesomorphic group.

3. according to claim 1 or resin combination claimed in claim 2, the containing ratio of described the first filler is 0.1 volume %～10 volume % in cumulative volume.

4. according to the resin combination described in any one in claim 1～claim 3, described the second filler comprises nitride filler.

5. resin combination according to claim 4, described nitride filler comprises at least a kind that selects in the group that free boron nitride and aluminium nitride form.

6. according to the resin combination described in any one in claim 1～claim 5, the containing ratio of described the second filler is 55 volume %～85 volume % in cumulative volume.

7. according to the resin combination described in any one in claim 1～claim 6, described thermosetting resin is epoxy resin.

8. according to the resin combination described in any one in claim 1～claim 7, described mesomorphic group has the structure that 3 above six-membered ring groups connect with straight chain shape.

9. resin combination according to claim 7, described epoxy resin represents by following general formula (III) or (IV),

In general formula (III), Ar ¹, Ar ²and Ar ³identical or different separately, represent any any one the represented divalent group in following general formula, R ¹, R ², R ³, R ⁴, R ⁵and R ⁶identical or different separately, the alkyl of expression hydrogen atom or carbon number 1～18, Q ¹and Q ²identical or different separately, represent the straight chain shape alkylidene group of carbon number 1～9, the methylene radical that forms this straight chain shape alkylidene group can be replaced by the alkylidene group of carbon number 1～18, in addition also can be inserted with between this methylene radical-O-or-N (R ⁷)-, be at this, R ⁷the alkyl that represents hydrogen atom or carbon number 1～18,

At this, R represents the alkyl of hydrogen atom or carbon number 1～18 independently of one another, and a represents 1～8 integer, b, e and g represent 1～6 integer, c represents 1～7 integer, and d and h represent 1～4 integer, and f represents 1～5 integer, in addition, in above-mentioned divalent group, when R is while being a plurality of, whole R can represent identical group, also can represent different groups

10. according to the resin combination described in any one in claim 1～claim 9, it further comprises phenol novolac resin.

11. resin combinations according to claim 10, the compound that described phenol novolac resin comprises at least 1 represented structural unit in the group that has the free following general formula (I-1) of choosing and (I-2) form,

General formula (I-1) and (I-2) in, R ¹represent independently of one another alkyl, aryl or aralkyl, R ²and R ³represent independently of one another hydrogen atom, alkyl, aryl or aralkyl, m represents 0～2 integer independently of one another, and n represents 1～7 integer independently of one another.

12. according to the resin combination described in claim 10 or claim 11, and in described phenol novolac resin, the ratio that contains of the monomer consisting of the phenolic compound that forms described phenol novolac resin is 5 quality %～80 quality %.

13. 1 kinds of semicure resin combinations, it is the semicure thing of the resin combination described in any one in claim 1～claim 12.

14. 1 kinds of curable resin compositions, it is the cured article of the resin combination described in any one in claim 1～claim 12.

15. 1 kinds of resin sheets, it is the sheet-like formed body of the resin combination described in any one in claim 1～claim 12.

16. resin sheets according to claim 15, its amount of flow under semi-cured state is 130%～210%.

17. 1 kinds of prepreg, it has fiber base material and is immersed in the resin combination described in any one in the claim 1～claim 12 in described fiber base material.

18. 1 kinds of plywoods, it has by adhesives and is configured in describedly by the semicure resin combination layer on adhesives or curable resin composition layer, and described semicure resin combination layer or curable resin composition layer are semicure thing or the cured article of at least a kind in the group that forms of resin sheet described in resin combination, claim 15 or the claim 16 described in any one of selecting in free claim 1～claim 12 and the prepreg described in claim 17.

19. 1 kinds of metal substrates, tinsel, curable resin composition layer and metal sheet are laminated in this order, and described curable resin composition layer is resin sheet described in resin combination, claim 15 or the claim 16 described in any one being selected from claim 1～claim 12 and the cured article of at least a kind of the prepreg described in claim 17.

20. 1 kinds of printing distributing boards, metal sheet, curable resin composition layer and wiring layer are laminated in this order, and described curable resin composition layer is resin sheet described in resin combination, claim 15 or the claim 16 described in any one being selected from claim 1～claim 12 and the cured article of at least a kind of the prepreg described in claim 17.

21. 1 kinds of power semiconductor arrangements, it comprises: the semiconductor module that metal sheet, soldering-tin layer and semi-conductor chip are laminated in this order; Radiating component; And the cured article that is configured in the described metal sheet of described semiconductor module and the claim 15 between described radiating component or the resin sheet described in claim 16.