JP2011037036A - Release sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a release sheet which can form a through-hole in high dimensional accuracy and high positional accuracy in a resin sheet in which a through-hole is to be formed. <P>SOLUTION: The release sheet is attached provisionally to the resin sheet in which the through-hole is to be formed, used to form the through-hole in the resin sheet in which the through-hole is to be formed, and has a base material film, a first resin layer which is formed on a surface of the base material film opposite to the surface which is attached provisionally to the resin sheet in which the through-hole is to be formed and composed mainly of a resin material, and a second resin layer which is formed on a side of the base material film which is attached provisionally to the resin sheet in which the through-hole is to be formed and composed mainly of a resin material. The softening temperature (A) measured by a thermomechanical analysis (measurement condition: in nitrogen; the temperature rising speed 5°C/min) of the base material film is at least 180°C, and the 10% mass reduction temperature (B) measured by a thermogravimetric analysis (measurement condition: in nitrogen; the temperature rising speed 5°C/min) of the first resin layer is 180-280°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a release sheet.

  Conventionally, a method of directly irradiating a carbon dioxide laser to make a through hole is known (see, for example, Patent Document 1). However, in this method, adhesion of processing waste to the surface layer, the hole shape is not circular, and there is no hole. There was a problem such as.

JP-A-61-99596

  The objective of this invention is providing the release sheet which can form a through-hole with high dimensional accuracy and position accuracy with respect to the resin sheet which should form a through-hole.

Such an object is achieved by the present inventions (1) to (2) below.
(1) A release sheet that is temporarily attached to a resin sheet in which a through hole is to be formed, and is used to form a through hole in the resin sheet in which the through hole is to be formed,
A base film;
A first resin layer which is provided on a surface opposite to a surface temporarily attached to a resin sheet on which the through-hole of the base film is to be formed, and is mainly composed of a resin material;
Provided on the surface side temporarily attached to the resin sheet to form the through hole of the base film, and having a second resin layer mainly composed of a resin material,
The softening temperature A measured by thermomechanical analysis of the base film (measuring condition: in nitrogen, heating rate 5 ° C./min) is 180 ° C. or higher,
Mold release, wherein 10% mass reduction temperature B measured by thermogravimetric analysis (measuring condition: in nitrogen, temperature rising rate 5 ° C./min) of said first resin layer is 180-280 ° C. Sheet.
(2) The release sheet according to (1), wherein the softening temperature A is 180 to 500 ° C.

  ADVANTAGE OF THE INVENTION According to this invention, the release sheet which can form a through-hole with high dimensional accuracy can be provided with respect to the resin sheet which should form a through-hole.

It is a longitudinal section showing a suitable embodiment of a release sheet of the present invention.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
<Release sheet>
First, a preferred embodiment of the release sheet of the present invention will be described.

  The release sheet of the present invention is temporarily attached to a resin sheet in which a through hole is to be formed by thermocompression bonding, and is used to form a through hole in the resin sheet. Examples of the resin sheet on which the through hole is to be formed include resin sheets such as a thermoplastic resin sheet and an adhesive resin sheet.

FIG. 1 is a longitudinal sectional view showing a preferred embodiment of the release sheet of the present invention.
As shown in FIG. 1, the release sheet 1 includes a base film 10 and a first surface provided on a surface opposite to a surface temporarily attached to a resin sheet on which a through hole of the base film 10 is to be formed. The resin layer 11 and the second resin layer 12 provided on the surface side temporarily attached to the resin sheet on which the through hole of the base film 10 is to be formed are provided.

  The release sheet of the present invention is provided on the surface side opposite to the surface temporarily attached to the resin sheet on which the through hole of the base film is to be formed, and the first resin layer 11 mainly composed of a resin material And a second resin layer 12 which is provided on the surface side temporarily attached to the resin sheet on which the through hole of the base film is to be formed and is mainly composed of a resin material. Measurement condition: softening temperature A measured by nitrogen in a temperature rising rate of 5 ° C./min is 180 ° C. or higher, and thermogravimetric analysis of the first resin layer (measuring condition: temperature rising rate of 5 ° C. in nitrogen) 10% mass reduction temperature B measured by / min) is characterized by 180 to 280 ° C.

  By having the above features, the through holes can be efficiently formed in the resin sheet in which the through holes are to be formed, and the through holes can be formed with high dimensional accuracy and position accuracy.

Hereinafter, each structure of the release sheet of this invention is demonstrated in detail.
The base film 10 has a function of supporting the first resin layer 11 and the second resin layer 12.

  As described above, the base film 10 has a softening temperature A measured by thermomechanical analysis (measurement conditions: in nitrogen, at a heating rate of 5 ° C./min) of 180 ° C. or higher, but 180 to 500 ° C. It is more preferable that it is 200-500 degreeC.

  Examples of the material constituting the base film 10 include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polysulfone, nylon, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyether imide, polyimide, and polyamide. It is made of acrylic resin or the like. Among the above, it is preferable to use a polyester resin (particularly, polyethylene terephthalate) from the viewpoint of ease of processing, durability, heat resistance, cost, and the like.

  The base film 10 is preferably a film stretched during film formation, and a biaxially stretched film is preferable. In particular, a biaxially stretched polyethylene terephthalate film is suitable.

  Although the average thickness of the base film 10 is not particularly limited, it is preferably 10 to 60 μm, and more preferably 12 to 50 μm.

The first resin layer 11 is mainly composed of a resin material.
As described above, the first resin layer 11 has a 10% mass reduction temperature B of 180 to 280 ° C. measured by thermogravimetric analysis (measurement conditions: in nitrogen, temperature rising rate 5 ° C./min). .

  As described above, the first resin layer 11 has a 10% mass reduction temperature B measured by thermogravimetric analysis (measurement condition: in nitrogen, temperature rising rate 5 ° C./min) of 180 to 280 ° C. More preferably, it is -270 degreeC, and it is further more preferable that it is 200-260 degreeC. Thereby, the effect of this invention can be made more remarkable.

  The resin material constituting the first resin layer 11 is excellent in adhesion to the base film 10 and does not cause blocking with the second resin layer 12 when stored in a roll shape. For example, although not particularly limited, it is preferably made of a material containing an alkyd resin or an epoxy resin as a main agent. Furthermore, when the resin material which comprises the 1st resin layer 11 is an alkyd resin or an epoxy resin, it is preferable that the alkyd resin or the epoxy resin is bridge | crosslinked.

  The alkyd resin is not particularly limited, and can be appropriately selected from known ones conventionally known as alkyd resins. This alkyd resin is a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid, and is a non-convertible alkyd which is modified with a condensate of a dibasic acid and a dihydric alcohol or a non-drying oil fatty acid. There are resins and convertible alkyd resins which are condensates of dibasic acids and trivalent or higher alcohols, and any of them can be used in the present invention.

  Examples of the polyhydric alcohol used as the raw material for the alkyd resin include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol, glycerin, trimethylolethane, A trihydric alcohol such as methylolpropane, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbit, or other polyhydric alcohols such as tetravalent or higher can be used, and one or more of these can be used. They can be used in combination.

  Examples of the polybasic acid include aromatic polybasic acids such as phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride, aliphatic saturated polybasic acids such as succinic acid, adipic acid, and sebacic acid, maleic acid, Diels such as aliphatic unsaturated polybasic acids such as maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct -The polybasic acid by an alder reaction etc. can be mentioned, Among these, it can use 1 type or in combination of 2 or more types.

  On the other hand, as the modifier, for example, octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, coconut oil, linseed oil, Kiri oil, castor oil, dehydrated castor oil, soybean oil, safflower oil and fatty acids thereof can be used, and one or more of these can be used in combination.

  In the present invention, the alkyd resin may be used alone or in combination of two or more.

  The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol A type epoxy resin ester, bisphenol F type epoxy resin, and bisphenol F type epoxy resin ester. A combination of more than one species can be used. Among these, it is preferable to use a bisphenol A type epoxy resin. Furthermore, it is preferable to use an epoxy resin having a hydroxyl group generated by a ring-opening reaction in the molecule. By selecting such an epoxy resin, the reactivity with a crosslinking agent described later can be improved, the film hardness after crosslinking is increased, and the adhesion with the substrate film can be improved.

  The crosslinking agent used to crosslink the main component such as the epoxy resin and alkyd resin is not particularly limited, and known resins such as amino resins such as melamine resin and urea resin, urethane resin, acrylic resin, phenol It can be suitably selected from resins and used. Among these, amino resins are preferable from the viewpoints of reactivity with epoxy resins or alkyd resins and adhesion to substrates. Specific examples of amino resins include melamine resins having hydroxyl groups or alkoxyl groups, urea resins, urea-melamine resins, guanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, ethyleneurea-formaldehyde resins, and the like. Can do. These crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  10-200 mass parts is preferable and, as for the mixture ratio of the crosslinking agent with respect to 100 mass parts of the said main ingredient, 20-100 mass parts is more preferable.

  In addition to the crosslinking agent, known acidic catalysts such as hydrochloric acid and p-toluenesulfonic acid can be used if desired.

  Such a first resin layer 11 may contain an antioxidant, a filler, a colorant, an ultraviolet ray inhibitor and the like.

  Moreover, it is preferable that the 1st resin layer 11 does not contain a silicone compound substantially. This prevents the silicone compound from transferring from the first resin layer 11 to the surface of the second resin layer 12 when the release sheet of the present invention is stored in the form of a roll. As a result, it is possible to prevent problems such as poor adhesion occurring in processed products using a resin sheet such as an adhesive resin sheet.

The expression “substantially free of a silicone compound” means that the amount of the silicone compound is preferably 500 μg / m ² or less, more preferably 100 μg / m ² or less.

  The content of the resin material in the first resin layer 11 is preferably 60 to 100% by mass, and more preferably 70 to 100% by mass.

  The average thickness of the first resin layer 11 is preferably about 0.1 to 5.0 μm, and more preferably about 0.3 to 3.0 μm. Thereby, while being able to form a through-hole in the resin sheet which should form a through-hole efficiently, a through-hole can be formed with high dimensional accuracy and position accuracy.

  The second resin layer 12 is a layer that is in contact with a resin sheet on which a through-hole to be used for forming a through-hole is to be formed, and is a layer mainly composed of a resin material.

  This 2nd resin layer 12 is a layer which contributes to joining (temporary attachment) with the release sheet 1 and the resin sheet which should form a through-hole, and specifically, the release sheet 1 is carried out by thermocompression bonding. And a layer having a function of joining the resin sheet to be formed with a through hole.

  As a resin material which comprises the 2nd resin layer 12 as mentioned above, it is excellent in adhesiveness with the base film 10, and is moderate adhesiveness and appropriate mold release with the resin sheet which should form a through-hole. Although it will not specifically limit if it has the property, It is preferable to comprise with the material containing an alkyd resin or an epoxy resin. Furthermore, when the resin material which comprises the 2nd resin layer 12 is an alkyd resin or an epoxy resin, it is preferable that the alkyd resin or the epoxy resin is bridge | crosslinked. Thereby, while being able to be easily joined with the resin sheet which should form a through-hole by thermocompression bonding, it can peel from the resin sheet which should form a through-hole easily after use. Moreover, the heat resistance and solvent resistance of the release sheet 1 can be made higher.

  As the material containing the alkyd resin or the epoxy resin, the same materials as those described as the resin material constituting the first resin layer 11 can be used.

  Such a second resin layer 12 may contain an antioxidant, a filler, a colorant, an ultraviolet ray inhibitor and the like.

  Further, it is preferable that the second resin layer 12 does not substantially contain a silicone compound. This prevents the silicone compound from transferring from the release sheet of the present invention to a resin sheet such as an adhesive resin sheet bonded to the release film. As a result, it is possible to prevent problems such as poor adhesion occurring in processed products using a resin sheet such as an adhesive resin sheet.

  Further, as the resin material constituting the second resin layer 12, it is preferable to use a resin material having a value close to the coefficient of thermal expansion of the first resin layer 11, and the same kind of material may be used. Is preferably used. Thereby, when the release sheet is heat-laminated to the resin sheet on which the through hole is to be formed, the release sheet can be prevented from warping, and the position accuracy and dimensional accuracy of perforation can be made higher.

  The content of the resin material in the second resin layer 12 is preferably 60 to 100% by mass, and more preferably 70 to 100% by mass.

  The average thickness of the second resin layer 12 is preferably about 0.1 to 5.0 μm, and more preferably about 0.3 to 3.0 μm. Thereby, while being able to form a through-hole in the resin sheet which should form a through-hole efficiently, a through-hole can be formed with high dimensional accuracy and position accuracy.

  Thus, by providing the first resin layer 11 and the second resin layer 12 on both surfaces of the base film 10, the heat resistance can be improved even for a thin base, and dimensional stability It is possible to obtain a release sheet excellent in the above.

<< Method for producing release sheet >>
Next, a method for manufacturing the release sheet as described above will be described.

First, the base film 10 is prepared (base film preparation process).
Next, a first coating liquid for forming the first resin layer 11 on one surface of the base film 10 is used by using a known coating apparatus such as a gravure coater, a bar coater, or a doctor blade coater. The first resin layer 11 is formed by heating and curing at a temperature of about 80 to 150 ° C. for several tens of seconds to several minutes (first resin layer forming step).

  In the 1st coating liquid, the material and solvent which comprise the 1st resin layer 11 as mentioned above are included.

  The solid content concentration of the first coating liquid is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. Thereby, the applicability | paintability of a 1st coating liquid can be made high.

  Examples of the solvent used for the first coating liquid include toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), heptane, hexane, cyclohexanone, and ethyl acetate.

  Next, a second coating liquid for forming the second resin layer 12 on the other surface of the base film 10 is used by using a known coating apparatus such as a gravure coater, a bar coater, or a doctor blade coater. The second resin layer 12 is formed by heating and curing at a temperature of about 80 to 150 ° C. for several tens of seconds to several minutes (second resin layer forming step). Thereby, the release sheet 1 (release sheet of the present invention) is obtained.

  The 2nd coating liquid contains the material and solvent which comprise the 2nd resin layer 12 as mentioned above.

  The resin material contained in the second coating liquid is preferably the same as the resin material contained in the first coating liquid described above. Thereby, the warp by the heat | fever of the release sheet 1 finally obtained can be prevented easily, and a through hole is formed with higher dimensional accuracy and position accuracy in a resin sheet in which the through hole is to be formed. Can do.

  Moreover, it is preferable that the wetting index by JIS-K6768 of the base film surface which forms the 2nd resin layer 12 is 30 mN / m or more, and it is more preferable that it is 40-70 mN / m.

  The solid content concentration of the second coating liquid is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. Thereby, the viscosity of a 2nd coating liquid can be made more suitable, and the coating property of a 2nd coating liquid can be made higher.

  Examples of the solvent used for the second coating liquid include toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), heptane, hexane, cyclohexanone, and ethyl acetate.

  The preferred embodiments of the release sheet and the manufacturing method thereof of the present invention have been described above, but the present invention is not limited to these.

  For example, in the above-described embodiment, the second resin layer is formed after the first resin layer is formed. However, the present invention is not limited to this, and the second resin layer may be formed first. Good.

<Laser processing method>
As a method of performing laser processing using the release sheet of the present invention, a step of temporarily attaching the release sheet of the present invention to a resin sheet on which a through hole is to be formed, and by irradiating the laser, the through hole is formed. And a step of forming a through hole in the resin sheet to be formed.

  Specifically, a step of heating and laminating the release sheet of the present invention on both surfaces of a resin sheet on which a through-hole is to be formed, usually at a temperature of 50 to 150 ° C., and a through-hole using a carbon dioxide laser or the like Forming a through hole in a resin sheet to be formed.

  Through such a laser processing method, the through hole can be formed in the resin sheet in which the through hole is to be formed with high dimensional accuracy and position accuracy.

Next, specific examples of the present invention will be described.
[1] Production of release sheet

Example 1
Bisphenol A type epoxy resin ester resin solution having a hydroxyl group as the main agent (solid content concentration 60% by mass): 100 parts by mass, methylated melamine resin as a crosslinking agent (solid content concentration 100% by mass): 40 parts by mass, Carbon pigment dispersion (solid content concentration 18% by mass): 15 parts by mass and 5 parts by mass of p-toluenesulfonic acid methanol solution (solid content concentration 50% by mass) as a catalyst were added and stirred, and the solid content concentration 15 masses. % Of the first coating solution was prepared.

  On the other hand, bisphenol A type epoxy resin ester resin solution having a hydroxyl group as a main agent (solid content concentration 60% by mass): 100 parts by mass, methylated melamine resin as a crosslinking agent (solid content concentration 100% by mass): 40 parts by mass And 5 parts by mass of a p-toluenesulfonic acid methanol solution (solid content concentration: 50% by mass) as a catalyst, and diluted and mixed with a toluene / MEK mixed solvent (toluene: MEK = 50% by mass: 50% by mass). Thus, a second coating solution having a solid content concentration of 30% by mass was prepared.

  Next, a first coating liquid is applied to a biaxially stretched polyethylene terephthalate (PET) film (film surface wetting index: 43 mN / m) as a base film using a Myer bar # 4, The film was dried at 150 ° C. for 40 seconds to form a first resin layer having a thickness of 0.8 μm.

Next, contrary to the surface on which the first resin layer of the PET film is formed, the second coating liquid is applied using a Myer bar # 4 and dried at 150 ° C. for 40 seconds to obtain a thickness of 0. An 8 μm second resin layer was formed.
A release sheet was obtained by the above process.

(Example 2)
Stearic acid-modified alkyd resin solution (solid content concentration: 60% by mass) as a main agent: 100 parts by mass, methylated melamine resin as a crosslinking agent (solid content concentration: 100%): 40 parts by mass, and p-toluene as a catalyst Add 10 parts by mass of sulfonic acid methanol solution (solid content concentration 50% by mass), dilute and mix with toluene / MEK mixed solvent (toluene: MEK = 50% by mass: 50% by mass) and solid content concentration 30% by mass. A release sheet was prepared in the same manner as in Example 1 except that the second coating solution was prepared.

(Example 3)
A release sheet was prepared in the same manner as in Example 1 except that the contents of the main agent and the crosslinking agent in the first coating solution were changed as shown in Table 1.

Example 4
Instead of a 25 μm thick biaxially stretched polyethylene terephthalate (PET) film, a 25 μm thick biaxially stretched nylon film was used as the base film, and the first coating liquid of Example 1 and the second example of Example 2 were used. A release sheet was produced in the same manner as in Example 1 except that the coating liquid No. 2 was used.

(Comparative Example 1)
A release sheet was prepared in the same manner as in Example 1 except that a polypropylene film with a thickness of 30 μm was used instead of a biaxially stretched polyethylene terephthalate (PET) film with a thickness of 25 μm.

(Comparative Example 2)
A release sheet was produced in the same manner as in Example 1 except that the first resin layer was not formed.

(Comparative Example 3)
A release sheet was produced in the same manner as in Example 1 except that the second resin layer was not formed.

  Table 1 shows the components of the first resin layer and the second resin layer, the contents thereof, and the like in each of the above Examples and Comparative Examples.

  Moreover, the softening temperature A of the base film used in each of the above Examples and Comparative Examples was measured using a thermomechanical analyzer (measuring condition: in nitrogen, heating rate 5 ° C./min), The 10% mass reduction temperature B of the first resin layer was measured using a thermogravimetric analyzer (measuring condition: in nitrogen, at a heating rate of 5 ° C./min), the softening temperature A of the base film, the first Table 2 shows the 10% mass reduction temperature B of the resin layer.

[2] Evaluation [2-1] Evaluation of warpage after lamination of release sheet Adhesive resin sheet (fiber assembly) as a resin sheet in which through-holes are to be formed using the release sheets prepared in each Example and Comparative Example The sheet was impregnated with a semi-cured epoxy resin) and laminated with a 19.6 N roller at 130 ° C. so that the second resin layer side was in contact with the adhesive resin sheet.

  The adhesive resin sheet on which the release sheet was laminated was visually observed to evaluate the occurrence of warpage.

  Those in which warpage did not occur or were within an allowable range were evaluated as acceptable “◯”, and those in which warpage was greatly generated were evaluated as unacceptable “x”.

[2-2] Evaluation of Peeling Force From the adhesive resin sheet obtained by laminating the release sheets of Examples and Comparative Examples prepared in [2-1], test pieces each having a width of 30 mm and a length of 150 mm were collected. Next, in accordance with JIS-Z0237, the peeling force between the adhesive resin sheet and the release sheet is 100 mm / 180 ° in a 180 ° direction using a tensile tester in an atmosphere of 23 ° C. and 50% RH. It was measured by peeling at a rate of minutes.

  When the peel force measured above is 50 mN / 30 mm or more, cohesive failure of the adhesive resin sheet may occur. Therefore, 50 mN / 30 mm or more is rejected as “x”, and less than 50 mN / 30 mm is passed as “good”. evaluated.

[2-3] Dimensional accuracy of through-holes formed in resin sheet in which through-holes are to be formed The release sheet prepared in each example and each comparative example is bonded to an adhesive resin sheet, and the second resin layer side is adhesive. Lamination was performed with a 19.6 N roller at 130 ° C. so as to contact the resin sheet.

  The carbon dioxide laser is used to irradiate the laser from the first resin layer side of the release sheet to provide 10 through holes (target value: φ100 μm), and the actual size of each through hole formed in the adhesive resin sheet The average value was obtained by measurement.

Deviation (%) of the measured actual size from the target value was calculated and evaluated according to the following criteria.
A: Deviation from the target value was 10% or less.
○: Deviation from the target value was greater than 10% and 20% or less.
Δ: Deviation from the target value was greater than 20% and 30% or less.
X: The deviation from the target value was larger than 30%.
These results are shown in Table 3.

  As is apparent from Table 3, the release sheet of the present invention has good releasability from the resin sheet where the through hole is to be formed without causing warpage even when the resin sheet in which the through hole is to be formed is thermally laminated. Furthermore, it was possible to form the through hole with high dimensional accuracy and position accuracy. On the other hand, in the comparative example, a result satisfying all was not obtained.

DESCRIPTION OF SYMBOLS 1 Release sheet 10 Base film 11 1st resin layer 12 2nd resin layer

Claims (2)

A release sheet that is temporarily attached to a resin sheet in which a through hole is to be formed, and is used to form a through hole in the resin sheet in which the through hole is to be formed,
A base film;
A first resin layer that is provided on a surface opposite to the surface temporarily attached to the resin sheet on which the through-hole of the base film is to be formed, and is mainly composed of a resin material;
Provided on the surface side temporarily attached to the resin sheet to form the through hole of the base film, and having a second resin layer mainly composed of a resin material,
The softening temperature A measured by thermomechanical analysis of the base film (measuring condition: in nitrogen, heating rate 5 ° C./min) is 180 ° C. or higher,
Mold release, wherein 10% mass reduction temperature B measured by thermogravimetric analysis (measuring condition: in nitrogen, temperature rising rate 5 ° C./min) of said first resin layer is 180-280 ° C. Sheet.   The release sheet according to claim 1, wherein the softening temperature A is 180 to 500 ° C.

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