JP5358355B2 - Resin composition and method for producing metal resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and a metal resin laminate at low cost, by which sufficient delamination resistance can be ensured between a resin layer and a metal layer. <P>SOLUTION: The resin composition is characterized in that an organic resin is compounded with porous silica and the percentage of the porous silica in the organic resin ranges from 0.15 to 25 wt.%. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a resin composition and a method for producing a metal resin laminate obtained by laminating a metal layer on a resin substrate using the resin composition.
This resin composition is suitably used as a material for printed circuit boards, for example.

A resin composition used as a material for a printed circuit board is required to have physical properties such as mechanical strength, heat resistance, and a low coefficient of thermal expansion.
In order to satisfy such requirements, it has been proposed to blend an inorganic porous material in an organic resin (Patent Document 1).
In the Example of patent document 1, 46.6 weight% or 31.1 weight% of mesoporous silica as an inorganic porous body is mix | blended with respect to the thermosetting resin.

JP 2007-138095 A

As a characteristic required for a printed circuit board, there is a case where a base made of a resin composition and a metal layer are sufficiently adhered to each other and are difficult to peel off.
The present inventors have studied the resin composition from such a viewpoint, and it is difficult to peel between the resin layer and the metal layer without adding mesoporous silica to the amount introduced in the prior art. I realized that I can secure.
In other words, since mesoporous silica is expensive, reducing its blending amount is beneficial in terms of providing an inexpensive resin composition and thus an inexpensive printed board.

The first aspect of the present invention has been made to solve the above problems. That is,
Porous silica is mix | blended in organic resin, The ratio of the said porous silica with respect to the said organic resin is 0.15 to 25 weight% or less, The resin composition characterized by the above-mentioned.
According to the resin composition defined in the first aspect defined in this manner, the organic resin is removed from the surface of the substrate made of the resin composition to expose the porous silica, and a metal layer is laminated on the surface. Then, the exposed porous silica interferes with the metal layer and becomes an anchor between the substrate made of the resin composition and the metal layer. Thereby, the peeling resistance of the base body and the metal layer made of the resin composition is improved.
Here, when the blending ratio of the porous silica is less than 0.15% by weight, the amount of the porous silica serving as an anchor is insufficient, and the peel resistance improvement is insufficient. Further, when blending more than 25% by weight of porous silica into an organic resin, it takes time to disperse the porous silica.
In addition, the compounding quantity of a more preferable porous silica is 1-20 weight%, More preferably, it is 5-15 weight%.

Since the organic resin is contained in the pores of the porous silica compounded in the substrate made of the resin composition, even when the organic resin component is removed from the substrate surface by chemical etching or the like, the organic resin that has entered the pores is not Difficult to be affected by etching. Therefore, many porous silicas exposed on the surface of the substrate are strongly fixed to the resin composition of the substrate.
On the other hand, since the organic resin component around the porous silica is removed, it is considered that the porous silica itself protrudes like a ridge from the surface. When the metal layer is laminated on the surface of the substrate in such a state, the exposed porous silica is embedded in the metal layer, and further, the material of the metal layer wraps around the pores of the porous silica, thereby providing an anchor effect.

The second aspect of the present invention is defined as follows. That is,
In the resin composition defined in the first aspect, the porous silica is mesoporous silica.
Here, mesoporous silica refers to porous silica having an average pore diameter of 1.5 to 50 nm.
By adopting mesoporous silica, the peel resistance is stabilized. This is presumably because mesoporous silica has a large pore volume and the partition walls of each pore are nano-sized and uniformly arranged.

From the viewpoint of peel resistance, the mesoporous silica in the amount specified in the first aspect may be added to the organic resin, but the printed circuit board is required to have high mechanical strength and heat resistance and a low coefficient of thermal expansion. The
As a result of studying from this point of view, it was found that high mechanical strength and heat resistance and a low thermal expansion coefficient can be secured while maintaining peeling resistance by blending true spherical silica with organic resin together with mesoporous silica.
That is, the third aspect of the present invention is defined as follows. That is, in the resin composition defined in the second aspect, spherical silica is further blended in the organic resin, and the total blending ratio of the mesoporous silica and the spherical silica is based on the organic resin. And 30 to 900% by weight or less.
When the total blending amount of mesoporous silica and true spherical silica (sometimes referred to as inorganic filler) is less than 30% by weight, it is difficult to ensure a low coefficient of thermal expansion, and when the total blending amount exceeds 900% by weight. , Each of which is not preferable because the mechanical strength may decrease.
A more preferable blending amount of the inorganic filler is 30 to 300% by weight, and further preferably 100 to 200% by weight.

Here, according to the study by the present inventors, it is preferable that the average particle diameter of the true spherical silica is 0.2 to 5 μm, and the average particle diameter of the mesoporous silica is 0.2 to 1.0 μm ( Fourth aspect).
The organic resin is at least one selected from epoxy resins, phenol resins, polyurethanes, polyimides, unsaturated polyesters, vinyl triazines, crosslinkable polyphenylene oxides, and curable polyphenylene ethers (fifth aspect).
Furthermore, the present invention provides a substrate formed with the resin composition according to any one of the first to fifth aspects, removing an organic resin contained in the resin composition from the surface of the substrate, and the surface of the substrate. A metal resin laminate, and a method for producing a metal resin laminate (seventh aspect). Here, plating etc. can be mentioned as a metal layer.

It is a graph which shows the relationship between the temperature in 0 to 240 degreeC, and the dimensional change amount of a resin molding. It is a graph which shows the relationship between the temperature in 0 to 50 degreeC, and the amount of dimensional changes of a resin molding.

In the resin composition of the present invention, porous silica is dispersed in an organic resin serving as a matrix. And organic resin penetrate | invades in the small pore which exists in porous silica. For this reason, the contact area between the porous silica and the organic resin is extremely increased, the interaction between the porous silica and the organic resin is increased, and mechanical properties such as elasticity and strength are improved. Moreover, since the porous silica has a smaller thermal expansion coefficient than the organic resin, the thermal expansion coefficient itself of the resin composition as a whole is also reduced due to the influence of the small thermal expansion coefficient. Furthermore, when the surface of the molded body (base) made of this resin composition is treated with an etching solution to etch the organic resin component, porous silica appears on the surface to be etched of the molded body. Since the organic resin component has entered the pores of the porous silica, the porous silica is firmly fixed to the molded body.
When a metal layer is laminated on such a surface to be etched, the exposed porous silica interferes with the metal layer, making it difficult to peel off the metal layer. For example, when copper plating is applied to the surface to be etched, the plating solution flows into the pores of the porous silica and deposits a metal material in the pores. Therefore, a strong anchor effect can be obtained.
As described above, the porous silica can be arbitrarily selected in terms of its shape, particle diameter, average pore diameter, and the like as long as it is exposed to the etched surface of the molded body and has an anchor effect on the metal layer. In the examples, mesoporous silica is used as the porous silica.
In addition, when laminating | stacking metal films, such as copper foil, to a base | substrate, the base | substrate opposing surface of a metal film can be roughened, both can be bonded together, and it can also be thermocompression-bonded.

  Other inorganic fillers may be added together with the porous silica. Examples of such inorganic fillers include silica, calcium carbonate, talc, mica, carbon, glass fiber, titanium oxide, alumina, and aluminum hydroxide that are frequently used for organic resins. Above all, the true spherical metal oxide particles obtained by burning the metal can be easily obtained in a uniform particle size (that is, monodispersed), and therefore have the closest packing structure in the organic resin. This is preferable because the effect of improving the mechanical characteristics can be easily obtained.

  In addition to the epoxy resin, phenolic resin, polyurethane, etc., the organic resin used as the matrix includes polyimide, unsaturated polyester, vinyltriazine, crosslinkable polyphenylene oxide, curable polyphenylene ether, etc. that are excellent in heat resistance. Can be used.

  Moreover, it is preferable to hydrophobize the surface hydroxyl group of the porous silica. As such a surface treating agent, any compound having a hydrophobic functional group and chemically bonding to a surface hydroxyl group can be used. Examples of such surface treatment agents include organic silicon compounds called silane coupling agents and silylating agents.

  Specifically, epoxy silanes such as γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylamino Examples include aminosilanes such as propyltrimethoxysilane, hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane, mercaptosilane, and the like.

Other examples include hexamethyldisilazane, trimethylchlorosilane, N-methyl-N-trimethylsilylacetamide, N-trimethylsilyldisilaamine, N-trimethylsilyldimethylamine, N-methyl-N-trimethylsilyl-trifluoroacetemide, Examples thereof include N, O-bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylimidazole and the like. Of the silylating agents, organosilazane is particularly preferred. Most preferred is hexamethyldisilazane. Hexamethyldisilazane (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is a disilazane H ₃ SiNHSiH ₃ in which H bonded to Si is replaced with a methyl group, and has explosive and corrosive properties like disilazane. And easy to handle. In addition, it is produced in a large amount as a surfactant at the time of photoresist application in the electronics industry, and is easily available and inexpensive.

The resin composition of the present invention obtained by dispersing porous silica in an organic resin can be arbitrarily shaped. When used as a printed circuit board, it is formed in a plate shape, but from the viewpoint of laminating a metal layer with a strong adhesion to a substrate composed of a resin composition, the shape of the substrate composed of a resin composition is not particularly limited. Needless to say. Moreover, a metal layer can be laminated | stacked entirely or partially on arbitrary surfaces in the base | substrate which consists of a resin composition.
(Embodiment)
Hereinafter, embodiments embodying the present invention will be described in detail.

<Preparation of mesoporous silica>
The pore walls of mesoporous silica are amorphous, and as a general production method, a sol-gel method using a surfactant as a template is used. However, mesoporous silica as a raw material is limited to mesoporous silica produced by the production method. Is not to be done. In the sol-gel method, when a surfactant is dissolved in an aqueous solution at a concentration equal to or higher than the critical micelle concentration, micelle particles having a certain size and structure are formed according to the type of the surfactant. When left standing for a while, the micelle particles take a packed structure and become a colloidal crystal. Here, when tetraethoxysilane or the like serving as a silica source is added to the solution and a trace amount of acid or base is added as a catalyst, the sol-gel reaction proceeds in the gaps between the colloidal particles to form a silica gel skeleton. Finally, when fired at a high temperature, the surfactant used as a mold is decomposed and removed to obtain pure mesoporous silica. By changing the type of the surfactant, the size and shape of the pores and the filling structure can be controlled. As typical ones, the MCM series using a small molecular cationic surfactant and the SBA series using a block copolymer are known.

  A specific method for producing mesoporous silica as a raw material is not particularly limited. However, as shown in JP-A-2006-248832, an inorganic material is mixed with an organic raw material and reacted, thereby causing an organic substance to react. A method of removing an organic substance from the obtained complex after forming a complex of an organic substance and an inorganic substance having an inorganic skeleton formed thereon as a template can be employed.

The inorganic raw material is not particularly limited as long as it is a substance containing silicon. Examples of the substance containing silicon include kanemite (NaHSi ₂ O ₅ · 3H ₂ O), sodium disilicate crystal (Na ₂ Si ₂ O ₅ ), macatite (NaHSi ₄ O ₉ · 5H ₂ O), and eyeraite (NaHSi). ₈ O ₁₇ · XH ₂ O), magadiite (Na ₂ HSi1 ₄ O ₂₉ · XH ₂ O), Kenyaite (Na ₂ HSi ₂₀ O ₄₁ · XH ₂ O), water glass (silicate soda), glass, amorphous silicic acid Examples thereof include silicon alkoxides such as sodium, tetraethoxysilane (TEOS), tetramethylammonium (TMA) silicate, and tetraethylorthosilicate. Examples of the substance containing silicon other than silicate include silica, silica oxide, and silica-metal composite oxide. You may use these individually or in mixture of 2 or more types.
Examples of the organic raw material include cationic, anionic, amphoteric and nonionic surfactants. You may use these individually or in mixture of 2 or more types.

  Furthermore, examples of the cationic surfactant used as a template include primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts. Among these, quaternary ammonium salts are included. Salts are preferred. Amine salts have poor dispersibility in the alkaline region, so that the synthesis conditions are used only in the acidic range, but the quaternary ammonium salts can be used in both cases where the synthesis conditions are acidic and alkaline. .

  The quaternary ammonium salt used as a template includes octyltrimethylammonium chloride, octyltrimethylammonium bromide, octyltrimethylammonium hydroxide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, Dodecyltrimethylammonium bromide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyltrimethylammonium Mhydroxide, behenyltrimethylammonium chloride, behenyltrimethylammonium bromide, behenyltrimethylammonium hydroxide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium hydroxide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium Examples thereof include alkyl (carbon number 8 to 22) trimethylammonium salt such as hydroxide. You may use these individually or in mixture of 2 or more types.

Examples of the anionic surfactant used as a template include carboxylate, sulfate ester salt, sulfonate salt and phosphate ester salt. Among them, soap, higher alcohol sulfate ester salt, higher alkyl ether sulfate Examples include ester salts, sulfated oils, sulfated fatty acid esters, sulfated olefins, alkylbenzene sulfonates, alkylnaphthalene sulfonates, paraffin sulfonates, and higher alcohol phosphate esters. You may use these individually or in mixture of 2 or more types.
Furthermore, examples of the amphoteric surfactant used as a template include sodium laurylaminopropionate, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. You may use these individually or in mixture of 2 or more types.

  Non-ionic surfactants used as templates include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin acid derivative, polyoxyethylene Examples include ether type compounds such as polyoxypropylene alkyl ether, polypropylene glycol, and polyethylene glycol, and nitrogen-containing types such as polyoxyethylene alkylamine. You may use these individually or in mixture of 2 or more types.

  When a surfactant is used as the organic raw material and pores are formed using the surfactant as a template, micelles can be used as the template. Also, by controlling the alkyl chain length of the surfactant, the diameter of the template can be changed and the diameter of the pores to be formed can be controlled. Furthermore, by adding a relatively hydrophobic molecule such as trimethylbenzene or tripropylbenzene together with a surfactant, the micelles expand and larger pores can be formed.

When mixing the inorganic raw material and the organic raw material, an appropriate solvent may be used. Although it does not specifically limit as a solvent, Water, alcohol, etc. are mentioned.
The mixing method of the inorganic raw material and the organic raw material is not particularly limited, but after adding ion-exchanged water having a weight ratio of 2 times or more to the inorganic raw material and stirring at 40 to 80 ° C. for 1 hour or longer, the organic raw material is added. Are preferably mixed. The mixing ratio of the inorganic raw material and the organic raw material is not particularly limited, but the ratio (weight ratio) of the inorganic raw material to the organic raw material is preferably 0.1: 1 to 5: 1, more preferably 0.1: 1 to 1. 3: 1.

The reaction between the inorganic raw material and the organic raw material is not particularly limited. However, the reaction is preferably performed at a pH of 11 or more for 1 hour or more, and after the pH is adjusted to 8.0 to 9.0, the reaction may be performed for 1 hour or more. preferable.
Examples of the method for removing the organic substance from the complex of organic substance and inorganic substance include a method in which the complex is collected by filtration, washed with water and dried, then baked at 400 to 600 ° C., and extracted with an organic solvent. .

  Reagents for chemically modifying mesoporous silica with hydrophobic functional groups are well known as chemical modifiers, silane coupling agents, titanium coupling agents, zirconia coupling agents, aluminum systems. Coupling agents, chromium coupling agents, zircoaluminum coupling agents, alcohols and the like can be used. Specific examples of silane coupling agents having a hydrophobic functional group include trialkoxymonoalkoxysilanes and derivatives in which hydrogen of the alkyl group is substituted with fluorine, trialkoxymonoalkenylsilanes, dialkyldisilazanes, diphenyls. Disilazane etc. are mentioned.

  In order to chemically modify mesoporous silica with a hydrophobic functional group using the above-described chemical modifier, the method generally used for each chemical modifier may be performed. For example, in the case of a silane coupling agent, water is added to the coupling agent to hydrolyze it, then a catalyst such as alcohol and acetic acid is added and dissolved in a solvent to prepare a solution, and the filler is immersed in this solution. The surface treatment may be performed.

<Inorganic filler other than mesoporous silica>
When adding inorganic filler in combination with mesoporous silica, silica, calcium carbonate, talc, mica, carbon, glass fiber, titanium oxide, alumina, hydroxylation, which are inorganic fillers frequently used for organic resins Aluminum etc. are mentioned. Above all, the true spherical metal oxide particles obtained by burning the metal can be easily obtained in a uniform particle size (that is, monodispersed), and therefore have the closest packing structure in the organic resin. This is preferable because the effect of improving the mechanical characteristics can be easily obtained. Metal oxide powder obtained by burning metal is metal powder such as silicon, aluminum, magnesium, zirconium, titanium, etc., aluminum powder and silicon powder prepared in mullite composition, magnesium powder and aluminum prepared in spinel composition A chemical flame is formed in an atmosphere containing oxygen together with a carrier gas using a metal powder mixture such as powder, cordierite composition, aluminum powder, magnesium powder, silicon powder, etc., and the target silica (SiO ₂ ) is contained in this chemical flame Metal oxides such as alumina (Al ₂ O ₃ ), titania (TiO ₂ ) and zirconia (ZrO ₂ ), and ultrafine particles of composite oxide are obtained. The metal oxide powder obtained by burning the metal is preferably a true spherical particle having an average particle size of 0.2 to 5 μm.

<Mixing of organic resin and inorganic filler>
When mixing and manufacturing mesoporous silica and inorganic fillers other than mesoporous silica and an organic resin as a matrix, examples of the mixing method include the following methods.
(1) A method in which an organic resin is kneaded with a kneader or the like while being melted, extruded and cooled.
(2) A method of mixing a prepolymer, mesoporous silica and an inorganic filler other than mesoporous silica, then adding a curing agent, further kneading, and solidifying.
(3) A method in which an organic resin is dissolved in a solvent, an inorganic filler other than mesoporous silica and mesoporous silica is mixed, and the solvent is evaporated to dryness.

Hereinafter, examples that further embody the present invention will be described in detail.
Example 1

<Preparation of epoxy resin composition and molded article thereof>
65 parts by weight of Admafine SO-25R (trade name) (manufactured by Admatechs Co., Ltd.), a spherical silica, 5 parts by weight of trimethylsilylated mesoporous silica (PC700G-PT made by Admatech Co., Ltd.), and methyl ethyl ketone (MEK) 30 parts by weight was mixed and dispersed with a disperser. Further, 37.7 parts by weight of an epoxy resin (Bisphenol A & F Toto Kasei ZX1059) and its curing agent (Ethacure 100 manufactured by Toto Kasei) were added at 1% by weight to the whole and mixed. Thereafter, the solvent was removed by distillation under vacuum heating to obtain a silica-dispersed epoxy resin composition. In this resin composition, Admafine and surface-modified mesoporous silica were uniformly primary dispersed without aggregation in the epoxy resin.
Further, this silica-dispersed epoxy resin composition was put into a cylindrical container (diameter 5 cm, height 1 cm) and the organic solvent was volatilized (conditions: 120 ° C., 3 hours), whereby the circle of Example 1 was obtained. A plate-like epoxy resin molding was obtained.

(Comparative Example 1)
70 parts by weight of Admafine SO-25R (trade name) (manufactured by Admatechs Co., Ltd.), which is true spherical silica, was mixed with 30 parts by weight of methyl ethyl ketone (MEK) and dispersed with a disperser. Then, 37.7 parts by weight of the same epoxy resin as in Example 1 and its curing agent (Ethacure 100 manufactured by Toto Kasei) were added at 1% by weight to the whole and mixed. Thereafter, the solvent was removed by vacuum heating distillation, and the silica-dispersed epoxy resin composition was added and further mixed. In this resin composition, Admafine was uniformly dispersed primarily without aggregation in the epoxy resin.
Further, in the same manner as in Example 1, a predetermined amount of this silica-dispersed epoxy resin composition was put into a cylindrical mold and the organic solvent was volatilized to obtain a disk-shaped epoxy resin molded body of Comparative Example 1. .

Production of metal resin laminate and adhesion strength test After copper plating was performed on the epoxy resin molded bodies of Example 1 and Comparative Example 1 obtained as described above, an adhesion strength test of the copper plating layer was performed. The details of the test method are as follows.
That is, the surface of the epoxy resin molded body was pretreated with a pretreatment agent containing an alkali agent, etched with a chromic acid etching solution, then immersed in a Pd catalyst solution to impart a Pd catalyst to the surface, and washed with water. . The electroless copper plating treatment was applied to a thickness of 1 μm, washed with water, and further subjected to electrolytic copper plating to a thickness of 20 μm, which was used as a test piece for measuring adhesion strength. For the adhesion strength test, a tensile tester (model number AGS-100NM manufactured by SIMADZU) was used. The measurement conditions were a measurement width of 10 mm and a pulling speed of 50 mm / min.

その結果、表１に示すように、実施例１の樹脂組成物は、真球状シリカであるアドマファイン６５重量部に対して、メソポーラスシリカを僅か５重量部加えただけであるにもかかわらず、メソポーラスシリカを加えなかった比較例１と比較して密着強度が約１．３倍となった。これは、メソポーラスシリカの細孔内に入り込んだエポキシ樹脂のアンカー効果によるものと考えられる。

As a result, as shown in Table 1, the resin composition of Example 1 was obtained by adding only 5 parts by weight of mesoporous silica to 65 parts by weight of Admafine, which is true spherical silica. The adhesion strength was about 1.3 times that of Comparative Example 1 in which no mesoporous silica was added. This is thought to be due to the anchor effect of the epoxy resin that has entered the pores of the mesoporous silica.

In addition, in the resin composition of Example 1, since the amount of mesoporous silica added is as small as about 7.1% by weight with respect to the whole inorganic filler, the viscosity does not increase so much when the organic resin composition is prepared, and molding is also possible. It becomes easy.
This also shows that a small amount of mesoporous silica may be dispersed in the resin composition in order to improve the peel resistance.
According to the study by the present inventors, when the mesoporous silica is dispersed in the organic resin, the blending ratio of the mesoporous silica with respect to the total organic component of the organic resin and the organic solvent is 0.15 to 8% by weight. preferable. Similarly, the total blending amount of mesoporous silica and Admafine (that is, blending amount of inorganic filler) with respect to the total organic component is preferably 30 to 300% by weight.

(Example 2)
In Example 2, a resin composition containing 20% by weight of mesoporous silica in an epoxy resin is prepared. That is, the mesoporous silica used in Example 1 was added to the epoxy resin (Bisphenol A & F Toto Kasei ZX1059) and mixed with a disperser, and further a curing agent (Etoto Kasei Ethacure 100) was added at 1% by weight to the whole and mixed. In the same manner as in Example 1, a predetermined amount was placed in a cylindrical mold and cured at 170 ° C. for 2 hours. The amount of hydrophobized mesoporous silica used in Example 1 was 20% by weight. Thus, a disk-shaped epoxy resin molded body of Example 2 was obtained.

(Comparative Example 2)
Comparative Example 2 is a resin composition in which Admafine SO-25R (trade name) (manufactured by Admatex Co., Ltd.), which is a spherical silica, is blended in an epoxy resin so as to be 20% by weight. It was prepared by the same method as 2.

(Comparative Example 3)
Comparative Example 3 was a resin composition cured with a curing agent without adding a filler to an epoxy resin, and was prepared by the same method as Example 2 except that no filler was added.

-Measurement of thermal expansion coefficient-
The thermal expansion coefficient of the epoxy resin compositions of Example 2 and Comparative Examples 2 to 4 obtained as described above was measured with a thermomechanical measurement device (Q400EM manufactured by TA INSTRUMENTS). The probe shape was a standard expansion probe. The results are shown in FIGS. 1 and 2 and Table 2.

  As shown in Table 2, the thermal expansion coefficient at 175 ° C. to 195 ° C. of the epoxy resin composition of Example 2 is 145.0 μm / m · ° C., whereas in Comparative Example 2, it is 163.7 μm / m · ° C. In Comparative Example 3, it was 188.5 μm / m · ° C., and it was found that the epoxy resin composition of Example 2 was significantly lower. The thermal expansion coefficient at 0 ° C. to 50 ° C. was 56.16 μm / m · ° C. in Example 2 and 53.50 μm / m · ° C. in Comparative Example 2, which was almost the same thermal expansion coefficient. Comparative Example 3 containing no filler was as high as 64.22 μm / m ° C. From the above results, it was found that the epoxy resin composition of Example 2 containing mesoporous silica has a low coefficient of thermal expansion in a wide temperature range of 0 to 195 ° C. This is because the epoxy resin penetrates into the pores present in the mesoporous silica contained in the epoxy resin composition of Example 2, thereby increasing the contact area between the mesoporous silica and the epoxy resin, and the coefficient of thermal expansion. It is thought that this is because of approaching silica.

  The present invention is not limited to the description of the embodiments and examples of the invention described above. Various modifications are also included in the present invention as long as those skilled in the art can easily conceive without departing from the scope of the claims.

  The resin composition of this invention can be used suitably as fillers, such as a printed circuit board and an insulated substrate for IC.

Claims (5)

In an organic resin and porous silica is blended, the ratio of the porous silica to the organic resin Ri from 0.15 to 25 wt% der, the porous silica is mesoporous silica, to the organic resin of spherical Silica is further blended, and the total blending ratio of the mesoporous silica and the spherical silica is 30 to 900% by weight with respect to the organic resin. A metal resin laminate in which an organic resin contained in the composition is removed by etching, and a metal layer is laminated on the surface of the substrate on which the mesoporous silica is exposed. 2. The metal resin laminate according to claim 1 , wherein the true spherical silica has an average particle size of 0.2 to 5 μm, and the mesoporous silica has an average particle size of 0.2 to 1.0 μm. . Wherein porous silica is metal-resin laminate according to claim 1 or 2, characterized in that, being a hydrophobic treatment. The organic resin is an epoxy resin, phenol resin, polyurethane, polyimide, unsaturated polyester, vinyl triazine, according to any of the crosslinkable polyphenylene oxide and a curable polyphenylene claim ether at least one is selected from 1-3 Metal resin laminate. Porous silica is blended in the organic resin, the ratio of the porous silica to the organic resin is 0.15 to 25% by weight, the porous silica is mesoporous silica, and the organic resin is a spherical silica. Is further blended, and the total blending ratio of the mesoporous silica and the true spherical silica is 30 to 900% by weight with respect to the organic resin to form a base, and from the surface of the base An organic resin contained in the resin composition is removed by etching, and a metal layer is laminated on the surface of the substrate on which the mesoporous silica is exposed .

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