JP2005067050A - Ceramic green sheet with resin film, ceramic green sheet and method for producing the same - Google Patents

Abstract

Disclosed are a ceramic green sheet with a resin film, a ceramic green sheet, and a method for producing the same, which can suppress the occurrence of tearing and cracking due to adhesion to a mold or the like and can be easily handled.
A ceramic green sheet with a resin film in which a ceramic green sheet containing an inorganic powder and at least a resin is formed on one main surface of a resin film is a resin film side main of the ceramic green sheet. The volume ratio of the resin in the thickness up to 1 μm from the surface of the surface 3a is 1.5 times or less of the volume ratio of the resin in the thickness up to 1 μm of the surface of the main surface 3b on the other side of the ceramic green sheet. .
[Selection] Figure 1

Description

  TECHNICAL FIELD The present invention relates to a ceramic green sheet with a resin film, a ceramic green sheet, and a method for producing the same, and in particular, a ceramic green sheet with a resin film and a ceramic used for forming an insulating layer of a ceramic multilayer circuit board having excellent dimensional accuracy and easy handling. The present invention relates to a green sheet and a manufacturing method thereof.

  Conventionally, ceramic green sheets used as ceramic multilayer substrates and ceramic packages on which electrical elements such as semiconductor elements are mounted are tape-shaped on a paper carrier sheet by a so-called tape molding method such as a doctor blade method or an extrusion molding method. Has been formed.

  This paper carrier sheet has a large surface roughness of the carrier sheet, so that the ceramic green sheet can be easily peeled off from the carrier sheet, and the strength of the carrier sheet increases the strength of the ceramic green sheet. Since it can hold | maintain, the dimensional accuracy of the peeled ceramic green sheet becomes high.

  The surface of the peeled ceramic green sheet that is in contact with the carrier sheet is roughened to reflect the surface state of the carrier sheet. As a result, the ceramic green sheet is in contact with a processing mold, table, or the like. It has the feature that it is easy to handle.

  However, in recent years, with the increase in integration, functionality, and miniaturization of semiconductor elements, the ceramic green sheet has been thinned, and it is necessary to form a thin ceramic green sheet of, for example, 200 μm or less, particularly 120 μm or less. It has become.

  When an attempt is made to form such a thin ceramic green sheet on a paper carrier sheet, there arises a problem that the variation in thickness increases. Therefore, in order to improve the thickness accuracy, a polyethylene terephthalate (PET) film is used as a carrier sheet, a thin ceramic green sheet is formed on the PET film, then punched into a desired shape, formed into a wiring, and laminated under pressure. Things have been done.

  However, a thin ceramic green sheet produced using a PET film contains a resin and a plasticizer as additives, and has high adhesion to the PET film made of resin, and peels the ceramic green sheet from the PET film. There is a problem that it is easily deformed and the accuracy of the substrate dimensions and wiring dimensions is deteriorated, and the ceramic green sheet is broken and broken (for example, see Patent Document 1).

Therefore, by forming a silicone release layer on the surface of the PET film, which is a carrier sheet, the peel strength when the ceramic green sheet peels from the carrier sheet is reduced, and it is proposed to improve the above problems that occur during peeling. (For example, refer to Patent Document 2).
JP-A-4-221889 JP 2000-25163 A

  However, although the ceramic green sheet described in Patent Document 2 can be easily peeled off from the carrier sheet due to the effect of the silicone release layer, the high adhesion strength of the ceramic green sheet itself has not been improved yet. In the subsequent punching process, wiring formation process and pressure lamination process, the ceramic green sheet main surface on the side in contact with the resin film adheres to the mold, etc. There is a problem that handling is not easy because the dimension and wiring dimension accuracy are lowered, and tears and cracks occur.

  In the conventional ceramic green sheet with a PET film, the present inventors have significantly different amounts of resin between the main surface on the PET film side of the ceramic green sheet and the other main surface. The amount of resin on the PET film side main surface of the sheet is excessive compared to the other main surface, and for this reason, the main surface on the PET film side of the ceramic green sheet is found to have excessive adhesion. It was. In addition, the amount of resin on the PET film side main surface of the ceramic green sheet and the amount of resin on the other main surface are likely to fluctuate and are excessive not only on the main surface on the PET film side of the ceramic green sheet but also on the other main surface. There was a case where it had a strong adhesive force.

  Accordingly, an object of the present invention is to provide a ceramic green sheet with a resin film that is easy to handle without tearing or stretching, a ceramic green sheet, and a method for producing the same.

  The ceramic green sheet with a resin film according to the present invention is a ceramic green sheet with a resin film formed by forming a ceramic green sheet containing an inorganic powder and at least a resin on one main surface of the resin film. The volume ratio of the resin in the thickness up to 1 μm from the surface of the main surface on the resin film side is 1.5 times or less of the volume ratio of the resin in the thickness up to 1 μm on the surface of the main surface on the other side of the ceramic green sheet. And

  Moreover, as for the ceramic green sheet with a resin of this invention, it is desirable that the glass transition point of resin is -20-0 degreeC.

  In the ceramic green sheet with a resin film of the present invention, the amount of plasticizer in the ceramic green sheet is preferably 0.5% by mass or less.

  Moreover, as for the ceramic green sheet with a resin film of this invention, it is desirable that resin is acrylic acid ester or methacrylic acid ester.

  In the ceramic green sheet with a resin film of the present invention, the resin film is preferably a PET (polyethylene terephthalate) film.

  Moreover, as for the ceramic green sheet with a resin film of this invention, it is desirable for the surface roughness of the main surface of the side which contacts the ceramic green sheet of a resin film to be Ra: 0.8 micrometer or less.

  Such a ceramic green sheet with a resin film is excellent in handleability because the ceramic green sheet does not adhere to the mold, and even a thin ceramic green sheet is supported by the resin film. is there.

  The ceramic green sheet of the present invention is a ceramic green sheet containing an inorganic powder and at least a resin, the surface roughness of at least one main surface is Ra: 0.8 μm or less, and one of the main ceramic green sheets The volume ratio of the resin at a thickness of 1 μm from the surface of the surface is 1.5 times or less of the volume ratio of the resin at a thickness of 1 μm from the surface of the main surface on the other side of the ceramic green sheet. .

  Moreover, as for the ceramic green sheet of this invention, it is desirable that the glass transition point of resin is -20-0 degreeC.

  In the ceramic green sheet of the present invention, the amount of plasticizer in the ceramic green sheet is preferably 0.5% by mass or less.

  Moreover, as for the ceramic green sheet of this invention, it is desirable that resin is acrylic acid ester or methacrylic acid ester.

  Such a ceramic green sheet is excellent in handleability because the ceramic green sheet does not adhere to the mold.

  The method for producing a ceramic green sheet with a resin film according to the present invention includes a slurry preparation step of preparing a slurry by mixing at least an inorganic powder, a resin having a glass transition point of -20 to 0 ° C., and a solvent, and the slurry. Forming a ceramic green sheet which is formed on one main surface of the resin film and volatilizes the solvent of the slurry.

  Moreover, the method for producing a ceramic green sheet with a resin film of the present invention comprises mixing at least an inorganic powder, a resin having a glass transition point of -20 to 0 ° C., a solvent, and a plasticizer of 0.5% by mass or less. It is desirable to have a slurry preparation process for preparing the slurry.

  Moreover, the manufacturing method of the ceramic green sheet of this invention comprises the process of peeling a resin film from the ceramic green sheet with a resin film produced with the manufacturing method demonstrated above.

  By producing the ceramic green sheet in this way, it is possible to suppress the generation of tears and cracks due to adhesion to a mold or the like, and it is possible to easily produce a ceramic green sheet that is easy to handle.

  The ceramic green sheet with a resin film according to the present invention is a ceramic green sheet with a resin film formed by forming a ceramic green sheet containing an inorganic powder and at least a resin on one main surface of the resin film. The volume ratio of the resin in the thickness up to 1 μm from the surface of the main surface on the resin film side is 1.5 times or less of the volume ratio of the resin in the thickness up to 1 μm on the surface of the main surface on the other side of the ceramic green sheet. And

  The volume ratio of the resin in the thickness up to 1 μm from the resin film side main surface of the ceramic green sheet is 1.5 times or less the volume ratio of the resin in the thickness up to 1 μm of the surface of the main surface on the other side of the ceramic green sheet. In addition to being able to reduce the peel strength between the resin film and the ceramic green, it is possible to reduce fluctuations in the amount of resin on the front and back surfaces of the ceramic green sheet, and to reduce fluctuations in the adhesion between the front and back surfaces of the ceramic green sheet. The mold releasability with the resin film and the mold can be increased, and the generation of tears and cracks due to adhesion of the ceramic green sheet that has been in contact with the resin film to the mold or the like can be suppressed. In addition, by holding the ceramic green sheet on the resin film, even if the ceramic green sheet is so thin that it is difficult to handle by itself, a ceramic green sheet having excellent handleability can be provided.

Moreover, as for the ceramic green sheet with a resin of this invention, it is desirable that the glass transition point of resin is -20-0 degreeC. The glass transition point (T _g ) represents the softening point of the resin. When the glass transition point (T _g ) increases, the sheet becomes hard and problems such as punching cracks during processing occur. On the other hand, if it becomes smaller, the ceramic green sheet becomes soft, and problems such as adhesion of the mold occur. Therefore, by setting the glass transition point of the resin to −20 ° C. or more, the adhesiveness of the resin is lowered, the adhesion of the ceramic green sheet can be reduced, and the ceramic green sheet is damaged due to adhesion to the resin resin or the mold. To reduce. Moreover, by making it 0 degrees C or less, sufficient softness | flexibility can be provided to a ceramic green sheet, and the crack at the time of processes, such as punching, can be reduced.

  In the ceramic green sheet with a resin film of the present invention, the amount of plasticizer in the ceramic green sheet is preferably 0.5% by mass or less. By setting the amount of plasticizer with a large ability to impart adhesion to the resin to 0.5% by mass or less, the adhesion of the front and back surfaces of the ceramic green sheet can be controlled within an appropriate range, and the ceramic green sheet is peeled off. Property can be improved, and the occurrence of mold adhesion can be suppressed.

  The above-mentioned plasticizer has a function of enhancing the plasticity of the slurry or the ceramic green sheet and suppressing the cracking and deformation of the ceramic green sheet when the ceramic green sheet is punched or formed with a wiring pattern. Examples thereof include DBP (dibutyl phthalate) and DOP (dioctyl phthalate).

  Moreover, as for the ceramic green sheet with a resin film of this invention, it is desirable that resin is acrylic acid ester or methacrylic acid ester. As a resin, in order to complete a series of processes from debinding to porcelain sintering in a non-oxidizing atmosphere, generally used butyral resin has sufficient porcelain characteristics due to the influence of residual carbon. Although it cannot be obtained and porcelain swells and cracks occur, by using acrylic ester and / or methacrylic ester as the resin, it is possible to ensure good thermal decomposability of the resin during firing, and Since the influence can be eliminated, porcelain free from blistering and cracking can be obtained.For example, when producing a wiring board, the influence of residual carbon can be eliminated, so that the appearance is excellent and the electrical characteristics hardly fluctuate. Can provide the body.

  In the ceramic green sheet with a resin film of the present invention, the resin film is preferably a PET (polyethylene terephthalate) film.

  Examples of other resin films include PEN (polyethylene-2-6-naphthalate) and PMT (polyethylene terephthalate).

  Moreover, as for the ceramic green sheet with a resin film of this invention, it is desirable for the surface roughness of the main surface of the side which contacts the ceramic green sheet of a resin film to be Ra: 0.8 micrometer or less.

  Thus, by making the surface roughness of the resin film 0.8 μm or less, the surface roughness of the main surface on the resin film side of the ceramic green sheet can be made 0.8 μm or less. When wiring is formed on the surface with a conductive paste, the shape of the wiring can be sharpened and bleeding of the conductive paste can be suppressed, so that fine wiring can be formed and the spacing between wirings can be reduced. A wiring board having a high wiring density can be provided. In addition, since the outline of the wiring can be formed sharply, the disconnection of the wiring can be effectively prevented even when a fine wiring is formed.

  The ceramic green sheet of the present invention is a ceramic green sheet containing an inorganic powder and at least a resin, the surface roughness of at least one main surface is Ra: 0.8 μm or less, and one of the main ceramic green sheets The volume ratio of the resin at a thickness of 1 μm from the surface of the surface is 1.5 times or less of the volume ratio of the resin at a thickness of 1 μm from the surface of the main surface on the other side of the ceramic green sheet. .

  By setting the surface roughness of the ceramic green sheet to 0.8 μm or less in this way, for example, when wiring is formed on the surface of the ceramic green sheet with a conductive paste, the shape of the wiring is sharply formed. In addition, since the bleeding of the conductor paste can be suppressed, fine wiring can be formed, the distance between the wirings can be reduced, and a wiring board having a high wiring density can be provided. In addition, since the outline of the wiring can be formed sharply, the disconnection of the wiring can be effectively prevented even when a fine wiring is formed.

  Furthermore, by making the volume ratio of the resin on the front and back surfaces of the ceramic green sheet within the above range, the adhesion force on the front and back surfaces of the ceramic green sheet can be made substantially equal, and can be controlled to an appropriate adhesion force. Excessive adhesion to the mold during processing can be suppressed, and the ceramic green sheet can be prevented from being torn or deformed. Therefore, it is possible to provide a ceramic green sheet that can provide a wiring board with excellent handling and excellent dimensional accuracy. .

  Moreover, as for the ceramic green sheet of this invention, it is desirable that the glass transition point of resin is -20-0 degreeC. By setting the glass transition point of the resin to −20 ° C. or more, the adhesiveness of the resin is lowered, the adhesion of the ceramic green sheet can be reduced, and the damage of the ceramic green sheet due to adhesion to the resin resin or the mold is reduced. . Moreover, by making it 0 degrees C or less, sufficient softness | flexibility can be attached to a ceramic green sheet, and a crack can be reduced at the time of processes, such as stamping.

  In the ceramic green sheet of the present invention, the amount of plasticizer in the ceramic green sheet is preferably 0.5% by mass or less. By setting the amount of plasticizer with a large ability to impart adhesion to the resin to 0.5% by mass or less, the adhesion of the front and back surfaces of the ceramic green sheet can be controlled within an appropriate range, and the ceramic green sheet is peeled off. Therefore, it is possible to provide a ceramic green sheet that can improve the property, suppress the occurrence of mold adhesion, have excellent handleability, and provide a wiring board with excellent dimensional accuracy.

  Moreover, as for the ceramic green sheet of this invention, it is desirable that resin is acrylic acid ester or methacrylic acid ester. As a resin, in order to complete a series of processes from debinding to porcelain sintering in a non-oxidizing atmosphere, generally used butyral resin has sufficient porcelain characteristics due to the influence of residual carbon. Can not be obtained, but porcelain swells and cracks occur, but by using acrylic acid ester and / or methacrylic acid ester as resin, good thermal decomposability of resin during firing can be ensured, and residual carbon With this, you can make a package that does not swell or crack porcelain.

  The method for producing a ceramic green sheet with a resin film according to the present invention includes a slurry preparation step of preparing a slurry by mixing at least an inorganic powder, a resin having a glass transition point of -20 to 0 ° C., and a solvent, and the slurry. Forming a ceramic green sheet which is formed on one main surface of the resin film and volatilizes the solvent of the slurry. By producing the ceramic green sheet with a resin film in this way, it is possible to suppress the occurrence of tears and cracks due to adhesion to a mold or the like, and it is possible to easily produce a ceramic green sheet with a resin film that is easy to handle.

  Moreover, the method for producing a ceramic green sheet with a resin film of the present invention comprises mixing at least an inorganic powder, a resin having a glass transition point of -20 to 0 ° C., a solvent, and a plasticizer of 0.5% by mass or less. It is desirable to have a slurry preparation process for preparing the slurry. By controlling the glass transition point of the resin and the plastic material in this way, a ceramic green sheet with a resin film with a small difference in the amount of resin on the front and back surfaces of the ceramic green sheet can be produced.

  Moreover, the manufacturing method of the ceramic green sheet of this invention comprises the process of peeling a resin film from the ceramic green sheet with a resin film produced with the manufacturing method demonstrated above.

  By producing the ceramic green sheet in this way, it is possible to suppress the generation of tears and cracks due to adhesion to a mold or the like, and it is possible to easily produce a ceramic green sheet that is easy to handle.

  The ceramic green sheet with a resin film of the present invention is formed by forming a ceramic green sheet 3 containing an inorganic powder and at least a resin on one main surface of a resin film 1 as shown in FIG. The volume ratio of the resin in the thickness from the resin film side main surface 3a of the green sheet 3 to 1 μm and the volume ratio of the resin in the thickness of the other main surface 3b of the ceramic green sheet 3 to 1 μm are 1.5 or less. It is controlled to prevent the ceramic green sheet 3 from adhering to a mold, an apparatus or a table during processing, and to prevent the ceramic green sheet 3 from being cracked or damaged. Thus, the dimensional accuracy of the printed wiring board can be improved.

  As the resin film 1 used for the ceramic green sheet 5 with a resin film of the present invention, a PET film is suitably used because it is inexpensive and excellent in smoothness and heat resistance.

  Further, in order to reduce the surface roughness of the main surface 3a on the resin film side of the ceramic green sheet 3 and improve the smoothness, for example, to form fine lines and the like, the ceramic green sheet 3 on the ceramic green sheet 3 side of the resin film 1 is provided. The surface roughness of the main surface is preferably Ra: 0.8 μm or less, more preferably 0.6 μm or less, and particularly preferably 0.5 μm or less.

  Further, in order to keep the adhesion of the ceramic green sheet 3 properly, the plastic material of the ceramic green sheet 3 is preferably 0.5% by mass or less, and further by 0.1% by mass or less, Even if there is a change, an appropriate adhesive force can be maintained.

  The plasticizer is used to increase the plasticity of the slurry or ceramic green sheet 3, and typical examples include DBP (dibutyl phthalate boiling point: 340 ° C) and DOP (dioctyl phthalate boiling point: 386 ° C). Preferably used.

In the present invention, it is desirable to use a resin having a glass transition point (T _g ) of −20 to 0 ° C. as a binder used for the ceramic green sheet 3. If the glass transition point (T _g ) is lower than −20 ° C., the adhesiveness of the resin becomes high, and the adhesive strength of the ceramic green sheet 3 becomes too high. Therefore, the ceramic green sheet 3 due to adhesion to the resin film 1 or the mold. Damage increases. Moreover, since the softness | flexibility of the ceramic green sheet 3 will fall and harden | cure when it is higher than 0 degreeC, a crack generate | occur | produces at the time of processes, such as stamping. In order to obtain a ceramic green sheet 3 having both mold releasability and high processability and high dimensional accuracy, the glass transition point (T _g ) of the resin is particularly preferably −15 to −5 ° C.

  Such a resin significantly reduces the amount of organic components unevenly distributed in the vicinity of the contact surface with the resin film 1 when producing a thin ceramic green sheet 3, and as a result, exhibits excellent mold release properties. It becomes possible.

  The resin used in the present invention is preferably a monomeric polymer or a plurality of types of copolymers. When the resin is a polymer of a monomer of one kind of resin, there is an effect that stable tape characteristics can be obtained because the resin is uniform. Moreover, when it is multiple types of copolymers, there exists an effect that the intensity | strength and elongation of a tape can be adjusted arbitrarily by combining resin with various glass transition points.

In particular, a plurality of resins having individual glass transition points (T _g ) in the range of −60 ° C. to 100 ° C. are selected, and monomers having these various glass transition points (T _g ) are selected. by copolymerizing it may be a glass transition point of the entire resin (T _g) to -20 to 0 ° C.. Such a copolymer can ensure the flexibility of the ceramic green sheet 3 and can effectively reduce the adhesion to the mold.

  The resin is preferably a polymer of acrylic acid ester and / or methacrylic acid ester monomer excellent in thermal decomposability or a copolymer of both. In order to complete the process from debinding to sintering of porcelain in a non-oxidizing atmosphere in a series of continuous processes, it is not possible to obtain sufficient porcelain characteristics due to the influence of residual carbon in commonly used butyral resins. This is because porcelain swells and cracks occur.

  For example, as the above-mentioned resin, as monomers, MMA (methyl methacrylate), EA (ethyl acrylate), nBMA (n-butyl methacrylate, iBMA (i-butyl methacrylate), 2EHMA (2-ethylhexyl methacrylate), or Examples thereof include LMA (lauryl methacrylate), etc. Examples of the polymer include polymers of acrylic acid esters and / or methacrylic acid esters using the above-mentioned monomers. It has characteristics and is effective in reducing variation in magnetic properties due to residual carbon during firing and peeling between layers.

  The ceramic powder is not particularly limited, but the main component is titanate which is useful for built-in functions such as commonly used aluminum oxide, aluminum nitride, silicon nitride, capacitor, etc. which are excellent in insulation, heat conduction and strength. The ceramic powder is preferably. By using the ceramics, it is possible to produce a wiring board having excellent mechanical characteristics and a wiring board having excellent dielectric characteristics.

  Moreover, it is preferable that it is a low-temperature-sinterable ceramic powder containing glass powder. Thus, by including glass powder in the ceramic, it is possible to synthesize ceramics that can be fired at low temperature. As a result, for example, low-temperature sinterable mixed powder containing glass powder that is advantageous in terms of resistance reduction of the wiring layer In particular, it is possible to realize a wiring board in which the resistance of the wiring layer is reduced.

  The ceramic green sheet 3 is preferably composed of 87 to 92.6% by mass of such ceramic powder and 7.4 to 13% by mass of resin. The resin has a role as a binder and a plasticizer, and by setting it in the above range, the ceramic green sheet 3 can be prevented from cracking at the time of molding / drying and disconnection of the wiring layer, and at the same time, the filling ability of the ceramic powder can be improved. It can be improved and a stable firing shrinkage rate can be obtained. In addition, the ceramic green sheet 3 can be prevented from adhering to the mold. In particular, in order to prevent cracks generated in the ceramic green sheet 3 and effectively prevent disconnection of the wiring layer, the ceramic powder is preferably 88 to 92% by mass and the resin 8 to 12% by mass, and further the ceramic powder 89 to 91. The mass% and the resin 9-11 mass% are preferable.

  Next, the manufacturing method of the ceramic green sheet 5 with a resin film of the present invention will be described using alumina as an example.

  30 to 50 parts by mass of toluene as a solvent for mixing was added to 100 parts by mass of mixed powder made of 87 to 92.6% by mass of alumina powder having an average particle size of 1.3 μm and 7.4 to 13% by mass of resin. Using a ball mill, the amount of media used for pulverization and kneading is 50 to 200 parts by mass based on the powder.

Next, a slurry for forming the ceramic green sheet 3 is prepared at the above mixing ratio. At this time, the slurry viscosity at a shear rate of 40 s ⁻¹ may be adjusted with toluene so as to be 2 to 5 Pa · s.

  The clearance of the blade is adjusted so that the thickness of the ceramic green sheet 3 after drying the slurry is 25 to 200 μm, and the slurry is coated on the resin film by the doctor blade method. It is important that the resin film has a surface roughness Ra of 0.8 μm or less. By setting the surface roughness Ra of the resin film in the above range, the surface roughness Ra of the main surface of the ceramic green sheet 3 in contact with the resin film can be controlled to 0.1 to 0.9 μm.

  The obtained ceramic green sheet 3 is dried. Thereafter, if desired, the ceramic green sheet 3 can be cut into a predetermined size while the ceramic green sheet 3 is adhered to the resin film 1 to obtain a ceramic green sheet 5 with a resin film having a desired shape.

  Moreover, after fixing a resin film to a support frame etc. as needed, a hole is processed and a via | veer is produced. And it can use as the ceramic green sheet 3 by which the slurry for electrodes was printed, it filled also into the via | veer, and the electrode was formed.

  The ceramic green sheet 3 of the present invention can be easily produced by, for example, producing the ceramic green sheet 5 with a resin film described above and then peeling the ceramic green sheet 3 from the resin film. It is smooth, excellent in releasability, and has good adhesion.

  Next, the manufacturing method of the ceramic green sheet 3 of the present invention will be described using alumina as an example.

  30 to 50 parts by mass of toluene as a solvent for mixing was added to 100 parts by mass of mixed powder made of 87 to 92.6% by mass of alumina powder having an average particle size of 1.3 μm and 7.4 to 13% by mass of resin. Using a ball mill, the amount of media used for pulverization and kneading is 50 to 200 parts by mass based on the powder.

It is important that the resin used here has a glass transition point (T _g ) of -20 to 0 ° C.

Next, a slurry for forming the ceramic green sheet 3 is prepared at the above mixing ratio. At this time, the slurry viscosity at a shear rate of 40 s ⁻¹ may be adjusted with toluene so as to be 2 to 5 Pa · s.

  The clearance of the blade is adjusted so that the sheet thickness after drying the slurry becomes a desired thickness, and the slurry is coated on the resin film by the doctor blade method.

  The obtained ceramic green sheet 3 is dried. Thereafter, the ceramic green sheet 3 is peeled off from the resin film as desired, and the ceramic green sheet 3 can be cut into a predetermined size to obtain the ceramic green sheet 3 having a desired shape.

  After preparing a slurry by mixing a resin having a glass transition point shown in Table 1 with toluene as a solvent with respect to an alumina powder having an average particle size of 1.3 μm, the resin film 1 has a thickness of about A 100 μm ceramic green sheet 3 was formed, and a ceramic green sheet 5 with a resin film was produced.

  In addition, the plasticizer shown in Table 1 was added as needed. The resin film 1 was a PET film having a surface roughness of Ra 0.6 μm.

  Next, the SUS plate having a thickness of 0.5 mm and the surface 3a of the ceramic green sheet 3 that was in contact with the resin film 1 were overlapped, heated to 55 ° C., and pressure-bonded at 3.4 MPa for 5 seconds. The sheet | seat 3 was peeled and the state was confirmed. Next, with the resin film 1 attached, the ceramic green sheet 3 is cut so that the length is 200 mm in both length and width, and a reference hole having a diameter of 1 mm is punched at a position 25 mm from the end of the ceramic green sheet 3. The surface roughness Ra of the surface 3a which contacted the resin film 1 and the other surface 3b was measured after producing and confirming the dimensional difference at the time of peeling from the resin film 1. FIG.

  The measurement of the resin volume difference between the front and back of the ceramic green sheet 3 was performed using Fourier transform infrared absorption spectroscopy (FT-IR). The resin film 1 is removed from the ceramic green sheet 5 with the resin film, and the binding peak of the resin is used by using the absorption peak on the front surface and the back surface of the ceramic green sheet 3 (using detection of information of about 1 μm region). The relative ratio of the resin was determined from the binding peak of the resin of the front surface: 3b and the rear surface: 3a of the ceramic green sheet 3.

  The surface roughness Ra of the ceramic green sheet 3 was measured using a stylus type surface roughness meter.

The dimensional difference is obtained by measuring the deviation of the hole position after the treatment with the length of the reference hole from the end of the ceramic green sheet 3 before peeling off from the resin film 1 and removing the resin film 1 with an optical microscope. The results are shown in Table 1.

  Sample No. in which the ratio of the amount of resin on the front and back surfaces of the ceramic green sheet 3 outside the scope of the present invention exceeds 1.5 times. In 1-8, 15, the dimensional difference at the time of peeling from the resin film 1 of the ceramic green sheet 3 is 0.0008% or more, and it turns out that dimensional accuracy is low. In particular, sample No. In 1, the adhesion to the mold was remarkable.

  On the other hand, Sample No. whose ratio of the amount of resin on the front and back surfaces of the ceramic green sheet 3 of the present invention is 1.5 times or less. In 9-14 and 16-35, adhesion to the resin film was not observed, and neither cracking nor deformation accompanying the adhesion occurred. Moreover, the dimensional difference at the time of peeling from the resin film 1 of the ceramic green sheet 3 is less than 0.0008%, and it turns out that a dimensional accuracy is high.

  As for the glass transition point, sample Nos. Having a low glass transition point of −25 ° C. 1, 8, 15, 22, and 29, the dimensional difference at the time of peeling tends to be large, and the glass transition point is as high as 5 ° C. In 7, 14, 21, 28, and 35, the flexibility of the ceramic green sheet 3 tends to be slightly impaired.

  On the other hand, sample Nos. With a glass transition point in the range of -20 to 0 ° C. In 2-6, 9-13, 16-20, 23-27, 30-34, the dimensional difference at the time of peeling and the flexibility of the ceramic green sheet 3 tend to be in harmony.

  Moreover, about the amount of plasticizers, what was made into the addition amount of 0.5 mass% or less in the combination of a present Example exists in the tendency which shows favorable dimensional accuracy.

  Although not shown in Table 1, the surface roughness Ra of the obtained ceramic green sheet 3 was a good value around 0.6 μm.

  The ceramic green sheet with a resin film and the ceramic green sheet are preferably used as, for example, an insulating layer and a dielectric layer when a wiring board having fine wiring is produced. Further, it is suitably used for a thin laminated dielectric.

It is sectional drawing explaining the ceramic green sheet with a resin film of this invention, and a ceramic green sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Resin film 3 ... Ceramic green sheet 3a ... Resin film side main surface 3b of the ceramic green sheet 3 ... Main surface 5 of the other side of the ceramic green sheet ... Ceramic green sheet with a resin film

Claims (13)

In a ceramic green sheet with a resin film formed by forming a ceramic green sheet containing an inorganic powder and at least a resin on one main surface of the resin film, the surface of the ceramic green sheet is 1 μm from the surface of the main surface on the resin film side. The ceramic green sheet with a resin film, wherein the volume ratio of the resin in the thickness is 1.5 times or less of the volume ratio of the resin in the thickness up to 1 μm of the surface of the other main surface of the ceramic green sheet. 2. The ceramic green sheet with a resin film according to claim 1, wherein the glass transition point of the resin is −20 to 0 ° C. 3. The ceramic green sheet with a resin film according to claim 1 or 2, wherein the amount of plasticizer in the ceramic green sheet is 0.5 mass% or less. Resin is acrylic ester or methacrylic ester, The ceramic green sheet with a resin film in any one of Claims 1 thru | or 3 characterized by the above-mentioned. The ceramic green sheet with a resin film according to any one of claims 1 to 4, wherein the resin film is a polyethylene terephthalate (PET) film. 6. The ceramic green sheet with a resin film according to claim 1, wherein the surface roughness of the main surface of the resin film on the side in contact with the ceramic green sheet is Ra: 0.8 [mu] m or less. In the ceramic green sheet containing the inorganic powder and at least the resin, the surface roughness of at least one main surface is Ra: 0.8 μm or less, and from the surface of one main surface of the ceramic green sheet to 1 μm. The ceramic green sheet, wherein a volume ratio of the resin in the thickness is 1.5 times or less of a volume ratio of the resin in a thickness of 1 μm from the surface of the other main surface of the ceramic green sheet. The ceramic green sheet according to claim 7, wherein the glass transition point of the resin is -20 to 0 ° C. The ceramic green sheet according to claim 7 or 8, wherein the amount of plasticizer in the ceramic green sheet is 0.5 mass% or less. The ceramic green sheet according to any one of claims 7 to 9, wherein the resin is an acrylic ester and / or a methacrylic ester. At least an inorganic powder, a resin having a glass transition point of −20 to 0 ° C., and a solvent are mixed to form a slurry, and the slurry is formed on one main surface of the resin film. Forming a ceramic green sheet that volatilizes a solvent, and a method for producing a ceramic green sheet with a resin film. It comprises a slurry preparation step of preparing a slurry by mixing at least an inorganic powder, a resin having a glass transition point of −20 to 0 ° C., a solvent, and a plasticizer of 0.5% by mass or less. The manufacturing method of the ceramic green sheet with a resin film of Claim 11. A method for producing a ceramic green sheet, comprising a step of peeling the resin film from the ceramic green sheet with a resin film produced by the method for producing a ceramic green sheet with a resin film according to claim 11.

Images