JP5383251B2 - Colored adhesive sheet for green sheet processing protection - Google Patents

Description

The present invention relates to a colored pressure-sensitive adhesive sheet for protecting green sheet processing, which is protected during processing of a green sheet (unfired ceramic sheet).

Ceramic sheets are used for wiring boards applied to semiconductor element storage packages on which semiconductor elements such as ICs and LSIs that are becoming increasingly integrated are mounted, hybrid integrated circuit devices on which various electronic components are mounted, and the like. As a typical manufacturing method of this ceramic sheet, there is a tape forming method called a green sheet method. In this molding method, a slurry composed of a ceramic powder, an organic binder, and a dispersion solvent is first formed into a sheet by a doctor blade method, a calendering method, an extrusion method, and the like, and then dried to volatilize the dispersion solvent and form a green sheet. obtain. Subsequently, the green sheet is punched into a predetermined shape (punching), subjected to a molding process such as cutting, and then fired to decompose and remove the organic binder and to sinter the ceramic powders together. Through these processes, a ceramic sheet can be obtained from the green sheet.

The green sheet containing the organic binder has flexibility, and in the punching process, the green sheet may be damaged or deformed. In order to prevent these scratches and deformations, it has been proposed to use a protective adhesive sheet on the green sheet during the punching process (see, for example, Patent Document 1).
The protective adhesive sheet described in Patent Document 1 has a configuration in which a releasable adhesive resin layer is provided on the surface of a polyester film substrate having a low specific gravity polyester layer. It is described that having such a configuration is excellent in any of heating dimensional stability, punching workability, and workability.

JP-A-9-279102

As described above, the protective adhesive sheet of Patent Document 1 can be used on the green sheet during the punching process. When the protective adhesive sheet is laminated on the green sheet and then subjected to a punching process, burrs may occur.

The burr will be described with reference to FIG. 1A and 1B are views showing a laminate subjected to a punching process, in which FIG. 1A is a side view of a laminate 30 in which a protective adhesive sheet 20 is laminated on a green sheet 10, and FIG. As shown in FIG. 1B, the stacked body 30 has holes 40 formed by a punching process. By this punching process, the green sheet 10 and the protective adhesive sheet 20 that are not cut or both of them exist as the burrs 41 in the holes 40.

Since the hole 40 is filled with a conductive paste formed by mixing a metal powder such as copper, silver, and gold, an organic binder, and an organic solvent, if the burr 41 is present in the hole 40, it is treated as a defective product. Become. Whether the product is defective or not can be inspected with a machine, visually (including microscopic observation) or both. However, the size of the hole 40 may be 50 to 200 μm, and the burr 41 is further smaller than the hole 40. Therefore, a good product may be judged as a defective product even in a machine inspection, and the yield is increased. Had a problem to decline. The problem cannot be solved by the protective pressure-sensitive adhesive sheet of Patent Document 1, and improvement has been demanded.

Then, an object of this invention is to provide the coloring adhesive sheet for green sheet processing protection which can detect the burr | flash and debris of a film accurately at the time of a punching process.

The present invention has solved the above problems by the following technical configuration.

(1) A pressure-sensitive adhesive sheet obtained by laminating a pressure-sensitive adhesive layer on a resin film, wherein at least one of the resin film and the pressure-sensitive adhesive layer contains a coloring component, and the a * value of the pressure-sensitive adhesive sheet is 20 to 90, b * value is -10 to 100 der is, green sheets processed protective colored adhesive sheet haze value of the pressure-sensitive adhesive sheet is characterized in der Rukoto 20% or more.
(2) The colored pressure-sensitive adhesive sheet for green sheet processing protection according to (1), wherein the coloring component is a pigment.
( 3 ) The colored pressure-sensitive adhesive sheet for green sheet processing protection according to (1), wherein the colored component is orange.
( 4 ) The colored adhesive sheet for green sheet processing protection according to (1) above, wherein the resin film has a tensile elongation of 10 to 100%.
( 5 ) The pressure-sensitive adhesive layer contains a pigment as a coloring component, and the adhesive strength of the pressure-sensitive adhesive layer containing the pigment is 0.01 to 3.0 N / 25 mm. The colored pressure-sensitive adhesive sheet for green sheet processing protection as described in 1.).
( 6 ) The colored adhesive sheet for green sheet processing protection according to (1), wherein the resin film is a polyethylene naphthalate resin film or a polyphenylene sulfide resin film.
( 7 ) The green sheet processing protection coloring according to any one of (1) to ( 6 ) above, wherein a protective film is adhered on the adhesive layer constituting the adhesive sheet. Adhesive sheet.

According to the present invention, it is possible to provide a colored pressure-sensitive adhesive sheet for green sheet processing protection capable of accurately detecting burrs and debris of a film during punching.
Further, according to the invention described in claim 5, it is possible to provide a colored adhesive sheet for protecting green sheet processing that hardly generates burrs and debris of the film during punching or cutting of the green sheet.
Furthermore, according to the invention described in claim 6, when the colored adhesive sheet for protecting green sheet processing is peeled from the green sheet, no adhesive residue is generated, and the colored adhesive sheet is peelable without damaging the green sheet surface. Can be provided.

It is a figure which shows the laminated body which performed the punching process, Comprising: (a) The side view of the laminated body by which the protective adhesive sheet was laminated | stacked on the green sheet, (b) It is a top view.

The present invention is a pressure-sensitive adhesive sheet obtained by laminating a pressure-sensitive adhesive layer on a resin film, wherein at least one of the resin film and the pressure-sensitive adhesive layer contains a coloring component (colored pressure-sensitive adhesive sheet for green sheet processing protection ( Hereinafter, it is referred to as an adhesive sheet. The pressure-sensitive adhesive sheet used in the present invention includes a pressure-sensitive adhesive tape and a pressure-sensitive adhesive film.
Another layer may be provided between the resin film and the adhesive layer, or another layer may be provided on the adhesive layer. Moreover, you may have the adhesion layer on both surfaces of the resin film. In the present invention, an adhesive layer is preferably provided directly on the resin film.

The pressure-sensitive adhesive sheet of the present invention preferably has an a * value of 20 to 90 and a b * value of -10 to 100, more preferably an a * value of 25 to 85 and a b * value of 0 to 95. It is particularly preferred that the a * value is 30 to 80 and the b * value is 10 to 90.
Since the green sheet mainly has white color, light green color, etc., by making the a * value and b * value within the range, it becomes easy to distinguish the color between the green sheet and the adhesive sheet, and the burr visibility is improved. . If at least one of the a * value and the b * value is out of the range, it is difficult to distinguish the colors of the green sheet and the adhesive sheet.
Specific examples of colors that satisfy the above a * value range and b * value range include orange and red.

The pressure-sensitive adhesive sheet of the present invention preferably has a haze value of 20% or more, more preferably 25% or more, and particularly preferably 30% or more. Although the upper limit of a haze value is not specifically limited, For example, it is 100%. By setting the haze value to 20% or more, light incident on the pressure-sensitive adhesive sheet is likely to be scattered, and the color of the pressure-sensitive adhesive sheet becomes bright. Thereby, the visibility of burrs is improved, and it becomes easy to detect the residue of the film.
When the haze value is less than 20%, the amount of transmitted light increases (scattered light decreases), so that the color of the pressure-sensitive adhesive sheet tends to be transparent, and the green sheet and the pressure-sensitive adhesive sheet may be difficult to distinguish.

Hereinafter, it demonstrates focusing on the material which comprises the adhesive sheet of this invention.

<Coloring ingredients>
As the coloring component used in the pressure-sensitive adhesive sheet of the present invention, pigments and dyes can be used. You may mix and use a pigment and dye.
As the pigment, those having an average particle diameter of 0.01 to 5 μm, more preferably 0.01 to 2 μm are preferably used. Illustrative pigments suitable for use in the present invention are as follows. Isoindolinone, anthraquinone, dioxazine, azo, naphthol, quinophthalone, azomethine, benzimidazolone, perinone, pyrazolone, pyranthrone, quinacridone, perylene, phthalocyanine, selenium and the like. Preferred examples include azo and quinacridone red pigments, pyrazolone orange pigments, azo and quinophthalone yellow pigments, and most preferred pigments include azo pigments, quinacridone pigments, Examples include pyrazolone pigments. These pigments can also be used by mixing as appropriate in order to adjust to the target hue.
Examples of the dye include direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and the like. The target coloring can be performed.
Among the above pigments and dyes, those exhibiting a red color include, for example, Shinkasha Red Y RT-759D manufactured by Sumitomo Chemical Co., and those exhibiting a yellow color include, for example, Seika First Yellow manufactured by Dainichi Seika Kogyo Co., Ltd. 2700. As an example of orange, there is Pelican First Orange GR manufactured by Dainichi Seika Kogyo Co., Ltd. The orange can be colored to any color by appropriately mixing red and yellow pigments and dyes. May be.
Said pigment and dye should just be contained in at least one of the resin film which comprises an adhesive sheet, and an adhesion layer.

As the coloring component of the pressure-sensitive adhesive sheet of the present invention, a pigment is preferably used. By using the pigment, the color of the pressure-sensitive adhesive sheet becomes bright and the color unevenness of the pressure-sensitive adhesive sheet hardly occurs.

<Resin film>
Examples of the resin film include cyclic polyolefin resins such as polyethylene resins, polypropylene resins and norbornene resins, polystyrene resins such as syndiotactic polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-. Styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester such as polyethylene terephthalate or polyethylene naphthalate Resins, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane Tan industrial resins, acetals - Le resins, cellulose - a scan-based resin or the like can be used that the resin material. The resin film which comprises this invention can use what formed said resin material using 1 type (s) or 2 or more types, for example.
The resin film made of the above materials may be used alone, or two or more layers may be laminated using an adhesive or the like.

The resin film used in the present invention preferably has a tensile elongation of 10 to 100%, more preferably 30 to 100%. By setting it in this range, the occurrence of burrs and film residue is reduced during punching, and the yield is improved.
If it is less than 10%, the film is difficult to stretch during punching and cutting, and there is a problem in that film residue is likely to occur.
If it exceeds 100%, the film tends to stretch during punching and cutting, and burrs are likely to occur.

The thickness of the resin film usually used as a protective film is about 3 to 100 μm. Although the tensile elongation varies depending on the thickness of the resin film, a polyethylene naphthalate resin film or a polyphenylene sulfide resin film is preferably used because the tensile elongation can easily fall within the above range regardless of the thickness. be able to.

Further, the resin film may be formed by blending an ultraviolet absorber or a light stabilizer. In addition, as a pretreatment for improving the coating property of the adhesive layer to the resin film, the surface of the resin film is subjected to physical treatment such as alkali treatment, corona treatment, flame treatment, plasma treatment, and sputtering treatment, polyester-based, An easy adhesive such as acrylic or polyurethane can be applied.

As a method for forming a resin film, an extrusion method, a cast molding method, a T-die method, or the like can be used.
When a colored component is contained in the resin film, if the resin film is formed (before molding as a resin film), the resin film is prepared by melting and stretching, and the colored component is added together with the resin component at the time of melting. Just do it. After the formation of the resin film, the resin film may be dipped into the paint in which the coloring component is dispersed, and the coloring component is allowed to penetrate into the resin film. In addition, when creating a resin film by radiation such as heat, ultraviolet rays, electron beams, etc., if a colored component is blended in a paint together with a resin component, the paint is applied on a suitable substrate, and then cured by radiation. Good.

<Adhesive layer>
As the resin component constituting the adhesive layer, there is re-peelability and it is not particularly limited as long as there is no adhesive residue at the time of peeling. For example, acrylic, rubber, polyvinyl ether, silicone, urethane And polyester resin components can be used. A cross-linking agent may be added to these resin components to form an adhesive layer. Examples of the crosslinking agent include isocyanate compounds, aluminum chelates, aziridinyl compounds, and epoxy compounds. What is necessary is just to mix | blend about 0.01-20 mass parts about the compounding quantity of a crosslinking agent when the total solid of a resin component is 100 mass parts.

The adhesive force of the pressure-sensitive adhesive layer is preferably 0.01 to 3.0 N / 25 mm, more preferably 0.01 to 2.8 N / 25 mm with respect to the green sheet, and 0.01 to 2.5 N. / 25 mm is particularly preferable. By setting the amount within this range, the adhesive force with the green sheet can be suitably maintained, and no adhesive residue is generated when the pressure-sensitive adhesive sheet is peeled from the green sheet.
If it is less than 0.01 N / 25 mm, the adhesive force with the green sheet may be insufficient, and the pressure-sensitive adhesive sheet is likely to be displaced during punching or cutting.
If it exceeds 3.0 N / 25 mm, the adhesive strength with the green sheet increases, so that adhesive residue may be generated when the adhesive sheet is peeled from the green sheet, and the surface of the green sheet may be roughened.

By increasing the thickness of the adhesive layer, the adhesive strength with SUS and the green sheet is improved (when compared with the same component), but the range of 1 to 20 μm is common.

In the present invention, the pressure-sensitive adhesive layer preferably contains a coloring component. As a result, it becomes possible to accurately detect burrs and film residue generated during processing, and when the adhesive sheet is peeled off from the green sheet, it is visually confirmed whether or not adhesive remains on the green sheet. Can be inspected. Moreover, it is preferable that the adhesion layer contains the pigment as a coloring component.
When the pressure-sensitive adhesive layer contains a pigment, the adhesive force is reduced as compared with a pressure-sensitive adhesive layer not containing a pigment. When the adhesive layer contains a pigment, the adhesive strength can be suitably maintained if the adhesive strength is within the range of 0.01 to 3.0 N / 25 mm.

When the adhesion layer contains a coloring component, when the total solid content of the resin component constituting the adhesion layer is 100 parts by mass, the blending amount of the coloring component is 5 to 30 parts by mass.
If it is less than 5 parts by mass, there is a problem that the color tone becomes thin and the visibility deteriorates.
If it exceeds 30 parts by mass, color unevenness occurs, visibility is deteriorated, and coloring components are easily transferred to the ceramic sheet.

As a manufacturing method in the case where a coloring component is contained in the adhesive layer, a resin component and a coloring component constituting the adhesive layer are mixed in an organic solvent, and then a Mayer bar coater, gravure coater, roll coater, reverse coater, lip coater What is necessary is just to apply | coat on a resin film with coating machines, such as a die coater.

It is preferable to laminate a protective film on the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet (on the opposite surface of the resin film) regardless of the presence or absence of coloring components. The presence of the protective film can prevent dust from adhering to the adhesive layer.
As the protective film, a film or paper subjected to a peeling treatment (for example, silicone treatment) can be used.

<Method for producing adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention can be formed by coating and drying a resin film in which a resin component constituting the pressure-sensitive adhesive layer is dissolved and dispersed in an organic solvent. When the coloring component is contained in the adhesive layer, the coloring component may be contained in the paint before being applied to the resin film. Moreover, when making a resin film contain a coloring component, it should just contain and shape | mold as a resin film previously. When other optional components are contained in the adhesive layer, they may be mixed when dissolved and dispersed in an organic solvent.
Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, 1,4-dioxane, tetrahydrofuran Several types and amounts such as ethyl acetate, ethanol, methanol, cyclohexanone, methyl cellosolve can be appropriately selected and used.
The paint is preferably prepared so that the solid content concentration is 5% by mass or more, and more preferably 10 to 50% by mass. If the solid content concentration is less than 5% by mass, the thickness of the adhesive layer tends to be non-uniform.

It is preferable that the pressure-sensitive adhesive layer constituting the present invention volatilizes the solvent by applying a coating for forming a pressure-sensitive adhesive layer to an organic film and then performing a heat treatment. For example, when toluene is used as the solvent, it is preferably heated to about 100 to 135 ° C. If the temperature at this time is less than 100 ° C., the solvent may not sufficiently volatilize. The drying time may be adjusted according to the drying temperature. For example, when the drying temperature is 100 ° C., about 10 minutes is sufficient.

EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited to these.

2. To 100 parts by mass of an adhesive resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Cooponyl 5767), 4.6 parts by mass of a yellow organic pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Seika First Yellow 2700); 0 parts by weight of red organic pigment (Ciba Specialty Chemicals, trade name: Shinkasha Red Y RT-759D) was added and stirred, and 130 parts by weight of toluene was added to adjust the viscosity. 5 parts by mass of Kogyo Co., Ltd., trade name: Coronate L) was added and stirred uniformly, and then the polyethylene terephthalate (PET) film having a thickness of 25 μm was subjected to a release treatment, and the thickness of the adhesive layer after drying Was coated and dried so as to be 4 μm. The pressure-sensitive adhesive layer surface was adhered to a polyethylene naphthalate (PEN) film (thickness 12 μm), which is a resin film, to obtain a pressure-sensitive adhesive sheet of the present invention.

A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the resin film was changed from a PEN film to a polyphenylene sulfide (PPS) film (thickness: 12 μm).

The pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that 100 parts by mass of the pressure-sensitive adhesive resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: COPONYEL 5065) was used.

A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the resin film was changed from a PEN film to a polyethylene terephthalate (PET) film (thickness 12 μm).

[Comparative Example 1]
An adhesive sheet was obtained in the same manner as in Example 1 except that the organic pigment added to the adhesive resin was 7.6 parts by mass of a blue organic pigment (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiton cyanine blue LBG).

[Comparative Example 2]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the organic pigment added to the pressure-sensitive adhesive resin was changed to 7.6 parts by mass of a green organic pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Cyanine Green 2GN).

[Comparative Example 3]
An adhesive sheet was obtained in the same manner as in Example 1 except that the organic pigment added to the adhesive resin was 7.6 parts by mass of a yellow organic pigment (trade name: Seika First Yellow 2700, manufactured by Dainichi Seika Kogyo Co., Ltd.). .

[Comparative Example 4]
6.7 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: R550) and 0.9 parts by weight of red organic pigment (Ciba Specialty Chemicals, trade name: Shinkasha Red Y) are added to the adhesive resin. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that RT-759D) was used.

Table 1 shows the materials and blending amounts used in the above Examples and Comparative Examples.

The PET film (25 μm) subjected to the peeling treatment was peeled off from the pressure-sensitive adhesive sheets obtained in the above Examples and Comparative Examples, and the following tests were performed. In addition, about the tensile elongation, the tensile elongation test piece was created for the used resin film according to JISK7127, and it measured using the tensile testing machine (the Toyo Seiki Co., Ltd. make, STRograph VG).
The adhesive strength was measured using a tensile tester (Toyo Seiki Co., Ltd., Strograph VG) in accordance with JIS Z0237.
The color tone a * value and b * value were measured from the resin film side using a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Color Meter ZE2000).
About the measurement of haze, it measured using the haze meter (Nippon Denshoku Industries make, Haze Meter NDH2000) from the resin film side.
Regarding the adhesive residue, the green sheet with the adhesive sheet attached was punched and cut, and after the adhesive sheet was peeled off, the presence or absence of adhesive residue on the green sheet was confirmed. The case where no adhesive residue was generated was indicated by ◯, and the case where the adhesive residue was generated was indicated by ×.
Regarding processability, the green sheet with the adhesive sheet attached was punched and cut, peeled off the adhesive sheet, and then the occurrence of burrs and debris on the green sheet was confirmed. A sample in which no burrs or scum was generated was marked with ◯, and a sample with burrs or scum was marked with x.
Regarding the detectability, the green sheet with the adhesive sheet attached was intentionally generated with burrs, and the ease of detecting the generated burrs with a defect detector and visual observation was confirmed. What was detected was marked with ◯, what could not be detected, or what was not detected was marked with ×.
Table 2 shows the results obtained by the above method. In Table 2, “orange” in the color column indicates orange.

As shown in Table 2, it was confirmed that the pressure-sensitive adhesive sheets of Examples 1 to 4 had excellent detectability even when burrs were intentionally generated.
In addition, the adhesive sheets of Examples 1, 2, and 4 did not generate adhesive residue when peeled from the green sheet, and could be peeled without damaging the surface of the green sheet, thereby suppressing processing defects.
Furthermore, the pressure-sensitive adhesive sheets of Examples 1, 2, and 3 were excellent in workability because they did not generate burrs or debris on the green sheet when punching or cutting.
In addition, the pressure-sensitive adhesive sheets of Examples 1 and 2 were excellent in all of adhesive residue, processability and detectability.

As described above, according to the present invention, it is possible to provide a colored adhesive sheet for green sheet processing protection that can accurately detect burrs and debris of a film during punching.

10 green sheet 20 protective adhesive sheet 30 laminate 40 hole 41 burr

Claims (7)

An adhesive sheet obtained by laminating an adhesive layer on a resin film, wherein at least one of the resin film and the adhesive layer contains a coloring component, and the a * value of the adhesive sheet is 20 to 90, and the b * value There Ri der -10 to 100, green sheets processed protective colored adhesive sheet haze value of the pressure-sensitive adhesive sheet is characterized in der Rukoto 20% or more.   The colored pressure-sensitive adhesive sheet for green sheet processing protection according to claim 1, wherein the colored component is a pigment.   The colored adhesive sheet for green sheet processing protection according to claim 1, wherein the colored component is orange.   The colored adhesive sheet for green sheet processing protection according to claim 1, wherein the resin film has a tensile elongation of 10 to 100%.   2. The adhesive layer according to claim 1, wherein the adhesive layer contains a pigment as a coloring component, and the adhesive force of the adhesive layer containing the pigment is 0.01 to 3.0 N / 25 mm. Colored adhesive sheet for green sheet processing protection.   The colored adhesive sheet for green sheet processing protection according to claim 1, wherein the resin film is a polyethylene naphthalate resin film or a polyphenylene sulfide resin film. The colored adhesive sheet for green sheet processing protection according to any one of claims 1 to 6 , wherein a protective film is stuck on the adhesive layer constituting the adhesive sheet.

Images