TW201348371A - Composite film and temporary fixing sheet - Google Patents

Abstract

Provided is a composite film which exhibits adequate adhesive force when warmed and allows for an adequate reduction in adhesive force when cooled, and which is able to exhibit highly precise retention performance and favorable peelability when used in a temporary fixing sheet used in the process of manufacturing an electronic component. Also provided is a temporary fixing sheet including the composite film of such description. This composite film contains a urethane polymer and a vinyl-based polymer, wherein the urethane polymer is obtained using a reaction between a polyol compound and a polyisocyanate compound, the melting point and/or freezing point of the polyol compound being 15-75 DEG C, and the vinyl-based polymer is obtained by polymerizing a monomer component that includes a (meth)acrylic monomer having an amide group.

Description

Composite film and temporary fixing sheet

This invention relates to a composite membrane. In particular, the present invention relates to a composite film in which the adhesion varies significantly depending on temperature. Further, the present invention relates to a temporary fixing sheet comprising such a composite film. Such a temporary fixing sheet can be preferably used in the electronic component manufacturing step.

As an adhesive sheet used for processing an electronic component, a base layer including a polyester-based, a polyolefin-based, a vinyl chloride-based, an acrylic-based, a polyurethane-based, a rubber-based, or a fluorine-based material, and An adhesive sheet of an adhesive layer such as an acrylic, urethane, rubber or polyoxygen. Such an adhesive tape may be subjected to heat treatment, cooling treatment, light irradiation or the like in such a manner that it exhibits sufficient adhesion at a certain point in time and does not exhibit adhesiveness at other points.

In the field of electronic components in recent years, miniaturization or precision of the components themselves is required. For example, ceramic capacitors, ceramic resistors, and ceramic inductors, which are one of ceramic electronic components, are represented by "0603" or "0402". The miniaturization or the high capacity obtained by the high layering of far more than several hundred layers becomes remarkable.

In particular, in the manufacturing steps of ceramic capacitors, high processing precision is required in order to achieve miniaturization or precision. An example of a manufacturing procedure of a ceramic capacitor is exemplified by:

(1) Electrode printing step on raw sheet

(2) Lamination step

(3) Pressurization step

(4) Cutting step

(5) Heat stripping step

(6) External electrode coating and drying steps

Etc. However, in step (1), the precision of the electrode printing is required, the accuracy of the electrode position required in the step (2), etc., and the step (3) requires that the green sheet is deformed by pressurization to generate the electrode position. Various precisions are required for the prevention of the offset of the electrode position due to the offset, the cutting accuracy required in the step (4), and the like, and even if the accuracy of only one of the steps is poor, the product becomes poor, resulting in a defect. Reduced productivity.

In particular, the above steps (1) to (4) are usually carried out on a PET (Polyethylene Terephthalate) film or an adhesive sheet, especially in the cutting step of the above step (4). In terms of retention (fixation) of the green sheet, it is preferred to carry out the above steps (1) to (4) on the adhesive sheet. As the adhesive sheet used in such use, various heat-peelable adhesive sheets are disclosed.

Previously, the cutting step of the above step (4) was carried out by a dicing method using a rotary knife, but with the miniaturization of the size, the chopping method with a higher throughput than the cutting method was started. However, in the tangent method, the reattachment of the resulting wafer becomes a problem. The main reason is that, unlike the dicing method, in the dicing method, there is almost no gap between the wafers after the cutting, and therefore, the wafers which exhibit adhesiveness by the heat in the heating and peeling step of the step (5) occur again. Attached. Further, there is a case where a load is applied to the electronic component by the heating peeling step of the step (5), which adversely affects the product. Further, since heating is necessary, an additional device is required.

In view of such a problem, in recent years, in order to prevent wafer reattachment in the heat stripping step of the step (5), a temporary fixing sheet containing a side chain crystallizable polymer is proposed, which is at about 40 ° C. When the cutting is performed at about 100 ° C, the ceramic sheet is firmly held, and then cooled to room temperature without a heat treatment step, the adhesive layer can be lowered. The wafer is peeled off (for example, refer to Patent Documents 1 and 2). When the temporary fixing sheet is used, the heat treatment step after the cutting can be omitted, so that the wafer reattachment caused by the step can be reduced.

However, with the miniaturization of the wafer, it is also required to have a higher cutting precision in the cutting step of the step (4) while preventing the wafer from being reattached, and the above-mentioned polymer containing the side chain crystallized. Temporarily fixing the sheet does not achieve a high cutting accuracy.

Further, the temporary fixing sheet containing the side chain-crystallizable polymer can be removed by cooling to remove the adhesive force. However, in order to remove the adhesive force, it is necessary to introduce a large amount of crystalline material, and there is a problem that the degree of freedom in design is lost. In addition, in order to perform the peeling at room temperature, it is necessary to make the crystal melting temperature of the crystalline material to be room temperature or higher, and it is necessary to heat the material when preparing the temporarily fixed sheet, and the handling property is deteriorated, and the operation is performed. Difficult problem.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent No. 3387497

Patent Document 2: Japanese Patent No. 3485412

An object of the present invention is to provide a composite film which exhibits sufficient adhesion when heated, and which has a sufficiently low adhesion when cooled, and which is used for temporarily fixing a sheet used in an electronic component manufacturing step. It exhibits high-precision retention and good peelability. Further, the present invention provides a temporary fixing sheet comprising such a composite film.

The composite film of the present invention contains a urethane polymer and a vinyl polymer, and the urethane polymer uses a polyol compound and a polyisocyanate compound. The polyol compound has a melting point and/or a freezing point of 15 ° C to 75 ° C. The ethylene polymer is obtained by polymerizing a monomer component containing a (meth)acrylic monomer having a mercapto group. .

In a preferred embodiment, the urethane polymer comprises a (meth) acrylonitrile-terminated urethane polymer.

In a preferred embodiment, the composite membrane of the present invention comprises a support substrate.

The temporary fixing sheet of the present invention comprises the composite film of the present invention.

In a preferred embodiment, the temporary fixing sheet is used in an electronic component manufacturing step.

In a preferred embodiment, the temporary fixing sheet is used for cutting of the laminated ceramic sheet.

The method for cutting a laminated ceramic sheet of the present invention uses the above-mentioned temporarily fixed sheet.

The electronic component of the present invention is obtained by the above cutting method.

According to the present invention, it is possible to provide a composite film which exhibits sufficient adhesive force if heated, and if it is cooled, the adhesive force is sufficiently lowered, and is used for temporarily fixing the sheet used in the electronic component manufacturing step. It exhibits high-precision retention and good peelability. Further, a temporary fixing sheet comprising such a composite film can be provided.

Since the use of the crystalline material is not required in the production of the composite film of the present invention, the workability in the production of the composite film of the present invention is improved, the productivity is excellent, and the heating step is not required.

The temporary fixing sheet of the present invention can be preferably used as a temporary fixing sheet for processing electronic parts such as ceramic electronic parts. For example, in the case of use in the cutting and cutting step in the high temperature environment of the laminated ceramic sheet, since the temporarily fixed sheet of the present invention has high adhesion in a high temperature environment, the wafer peeling during operation can be prevented. ,From It can be cut with higher precision. Further, when the temporary fixing sheet of the present invention is cooled, the adhesive force is sufficiently lowered, so that the wafer can be favorably peeled off by merely cooling to room temperature without undergoing a heat treatment step, thereby preventing wafer reattachment.

Further, since the temporary fixing sheet of the present invention can be stretched by stretching, the gap between the wafers can be caused by stretching after the cutting step, whereby the reattachment of the wafer can be further reduced.

1‧‧‧ Temporary fixed sheet

2‧‧‧Base

3‧‧‧Laminated ceramic sheets

4‧‧‧铡

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a step of using a temporary fixing sheet of the present invention to cut a laminated ceramic sheet.

In the present specification, the term "(meth)acrylic acid" means acrylic acid and/or methacrylic acid; the term "(meth)acrylate" means acrylate and/or methacrylate; The term "acryloyl" refers to an acryl group and/or a methacryl group.

"Composite film"

The composite film of the present invention contains a urethane polymer and a vinyl polymer. Here, the "containing a urethane polymer and a vinyl polymer" may be contained by blending a urethane polymer and a vinyl polymer, or may be an aminocarboxylic acid. When the ester polymer and the vinyl polymer are combined and contained, it may be a case where both of them are coexistent. The urethane polymer in the composite film of the present invention may be used alone or in combination of two or more. The ethylene-based polymer in the composite film of the present invention may be used alone or in combination of two or more.

The composite film of the present invention contains a urethane polymer and a vinyl polymer obtained by a reaction of a polyol compound and a polyisocyanate compound, and the melting point of the polyol compound The solidification point is 15 ° C to 75 ° C, and the ethylene-based polymer is obtained by polymerizing a monomer component containing a (meth)acrylic monomer having a mercapto group.

If a urethane polymer is produced using a polyol compound having a melting point and/or a freezing point of 15 ° C to 75 ° C, crystallization of the polyol compound can be observed in the obtained urethane polymer. Melting behavior. Further, when a vinyl polymer is produced using a (meth)acrylic monomer having a mercapto group, the urethane polymer forms a phase-separated structure with the ethylene polymer, and the urethane polymerization tends to be easily exhibited. The crystallization of matter melts. Therefore, the obtained composite film can significantly change the adhesion depending on the temperature, thereby exhibiting an excellent cooling peeling function. Specifically, when the composite film of the present invention is heated, it exhibits sufficient adhesion, and if it is cooled, the adhesion is sufficiently lowered. The composite film of the present invention preferably exhibits a sufficient adhesive force when heated to 40 ° C or higher, and thereafter, when cooled to a temperature lower than room temperature, the adhesive strength is sufficiently lowered.

As described above, when the composite film of the present invention is heated to 40 ° C or higher, it exhibits sufficient adhesion, and if it is cooled to a temperature lower than room temperature, the adhesion is sufficiently lowered, which is as follows: After being attached to a PET film having a thickness of 25 μm in a temperature environment of ° C, the adhesive force at a stretching speed of 300 mm/min and a peeling angle of 180° is preferably 0.20 N/10 mm or more. Preferably, it is 0.25 N/10 mm or more, and more preferably 0.30 N/10 mm or more; thereafter, after cooling to a temperature of 25 ° C, the stretching speed is 300 mm/min and the peeling angle is 180°. The adhesive force at the time of peeling is preferably 0.10 N/10 mm or less, more preferably 0.08 N/10 mm or less, further preferably 0.06 N/10 mm or less.

Further, in the present invention, in the case of "film", the concept of both the film and the sheet is included. Further, in the present invention, in the case of "sheet", the concept of both the sheet and the film is included.

The urethane polymer is obtained by using a reaction of a polyol compound and a polyisocyanate compound. That is, the urethane polymer can be obtained by using a raw material containing a polyol compound and a polyisocyanate compound, and reacting the polyol compound with the polyisocyanate compound.

The reaction of the polyol compound with the polyisocyanate compound can be carried out by any suitable method employed in the manufacture of the urethane polymer. The urethane polymer is obtained, for example, by mixing and stirring a polyol compound and a polyisocyanate compound, and it is preferred to add a polyisocyanate compound so that the isocyanate group is excessive with respect to the hydroxyl group in the polyol compound. Further, in the reaction, an organic solvent (for example, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and a catalyst (for example, tin chloride) which do not have an active hydrogen capable of reacting an isocyanate group may be added as needed. An organic metal catalyst such as an organotin compound; an organic base such as a tertiary amine compound; an organic acid such as acetic acid or acrylic acid;

The ratio of the polyol compound to the polyisocyanate compound is preferably a polyol compound: polyisocyanate compound = 1:1.0 to 1:2.0 in terms of a molar ratio, more preferably a polyol compound: a polyisocyanate compound. It is preferably formulated with a polyol compound: polyisocyanate compound = 1:1.1 to 1:1.5. By incorporating the ratio of the above polyol compound to the above polyisocyanate compound within the above range, the strength of the composite film of the present invention can be prevented from being lowered, and the elongation and strength of the composite film of the present invention can be imparted.

The molecular weight of the urethane polymer can be appropriately set depending on the purpose, and the number average molecular weight (Mn) is preferably 5,000 or more, more preferably 10,000 or more.

As the polyol compound, a polyol compound having a melting point and/or a freezing point of 15 to 75 ° C is selected. Examples of such a polyol compound include a polyol compound containing a crystal component, which exhibits crystallization and melting behavior depending on temperature changes. Further, in the present invention, the melting point and/or freezing point of the polyol compound can be confirmed according to the manufacturer's catalog or MSDS (Material Safety Data Sheet). Further, in the present invention, the "melting point" and the "freezing point" can be treated in the same manner as the physical property value of the specific polyol compound, and when only one physical property value is described in the catalogue or the like, the value can be used. When selecting a specific polyol compound, it is not necessary to confirm the "melting" The physical properties of both the "point" and the "freezing point".

Examples of such a polyol compound include a polyester polyol (a polycondensate of a dibasic acid such as adipic acid, azelaic acid or sebacic acid), and a polyether polyol (making epoxy B). Addition polymerization of an alkane or tetrahydrofuran, etc.), polyacrylate polyol, polycarbonate polyol, polyolefin polyol, polybutadiene polyol and hydride, polyisoprene polyol and hydride A phenolic polyol, an epoxy polyol, a caprolactone polyol, a polyfluorene polyol, or the like. Further, examples of the polyol compound include copolymer polyols such as polyester-polyether polyols.

As the polyol compound, among the above-exemplified examples, a polyester polyol, a polyether polyol, and a polycarbonate diol are preferable. Specific examples of the polyester polyol are commercially available as "Nipporan 4002", which is a polyethylene adipate diol, and "Nipporan" as a polybutylene adipate diol. 4009", the product name "Nipporan 164" (manufactured by Nippon Polyurethane Industry Co., Ltd.) or the like as polyhexamethylene adipate diol. Specific examples of the polyether polyol are commercially available as "PTMG 1000" (melting point (Tm): 17 ° C) and "PTMG 1300" as polytetramethylene ether glycol (PTMG). (melting point (Tm): 18 ° C), "PTMG 1500" (melting point (Tm): 18 ° C), "PTMG 1800" (melting point (Tm): 20 ° C), "PTMG 2000" (melting point (Tm): 20 ° C) ), "PTMG 3000" (melting point (Tm): 21 ° C) (above, manufactured by Dia Chemical Co., Ltd.), and the like. Specific examples of the polycarbonate diol are commercially available as "Nipporan 981" (melting point (Tm): 42 ° C) as a 1,6-hexane diester carbonate (Nippon Polyurethane Industry Limited) Company manufacturing) and so on.

The polyol compound may be used alone or in combination of two or more.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl xylene diisocyanate, and benzene. Dimethylene diiso Cyanate ester, naphthalene diisocyanate, trimethylhexamethylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, cyclohexane diisocyanate, methylene bis(4-phenylmethane) diisocyanate, six Methylene diisocyanate, dimer acid diisocyanate, hydrogenated toluene diisocyanate, hydrogenated benzene dimethylene diisocyanate, leucine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) triphosphate, etc. .

As the polyisocyanate compound, among the above-exemplified examples, hydrogenated dimethylene diisocyanate is preferred.

The polyisocyanate compound may be used alone or in combination of two or more.

The urethane polymer preferably comprises a (meth) acrylonitrile-terminated urethane polymer. The (meth)acrylonyl terminal urethane polymer is a compound having two or more acryloyl or methacrylinyl groups in one molecule and having a urethane bond in a repeating structural unit. .

In the case where the urethane polymer contains a (meth) acrylonitrile-terminated urethane polymer, the (meth) acryl-yl-terminated urethane in the urethane polymer The content ratio of the polymer is preferably from 50% by weight to 100% by weight, more preferably from 70% by weight to 100% by weight, still more preferably from 90% by weight to 100% by weight, particularly preferably from 95% by weight to 100% by weight, Most preferably it is substantially 100% by weight.

The (meth)acrylonitrile-terminated urethane polymer is preferably a polyurethane-based monomer obtained by reacting a hydroxyl group-containing acrylic monomer with a polyol compound and a polyisocyanate compound. Obtained by carrying out the reaction. In the reaction, an organic solvent (for example, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and a catalyst (for example, tin chloride, an organotin compound) which do not have an active hydrogen capable of reacting an isocyanate group may be added as needed. The reaction is carried out by an organic metal catalyst, an organic base such as a tertiary amine compound, or an organic acid such as acetic acid or acrylic acid.

Examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). C Ethyl (4-hydroxymethylcyclohexyl)methyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane II Methyl) acrylate, pentaerythritol tri(meth) acrylate, and the like. The hydroxyl group-containing acrylic monomer may be used alone or in combination of two or more.

The amount of the hydroxyl group-containing acrylic monomer to be used is preferably from 0.1% by weight to 10% by weight, and more preferably from 0.1% by weight to 5% by weight based on the polyurethane prepolymer.

The ratio of the above polyurethane prepolymer to the above hydroxyl group-containing acrylic monomer is preferably an isocyanate residue relative to the polyurethane prepolymer, and a hydroxyl group-containing acrylic monomer. The hydroxyl groups in the middle are added in equal amounts. Specifically, the polyol compound to be formulated in the production of the polyurethane prepolymer is preferably a polyol compound: a hydroxyl group-containing acrylic monomer = 1:0.08 in terms of a molar ratio. 1:0.5, more preferably a polyol compound: a hydroxyl group-containing acrylic monomer = 1: 0.1 to 1: 0.4. The effect of the present invention can be further exhibited by including the ratio of the above polyol compound to the above hydroxyl group-containing acrylic monomer in the above range.

The vinyl polymer can be obtained by polymerizing a vinyl monomer alone, or by performing polymerization after preparing a mixture of a urethane polymer and a vinyl monomer.

Further, in the case where the urethane polymer contains a (meth) acrylonitrile-terminated urethane polymer, there are also cases in which the urethane polymer is present in the presence of the urethane polymer. The vinyl monomer is polymerized, and the (meth) acrylonitrile group is polymerized with a vinyl group to obtain a vinyl polymer bonded to the (meth) propylene thiol terminal urethane polymer.

The vinyl polymer is obtained by polymerizing a monomer component containing a (meth)acrylic monomer having a mercapto group. The content ratio of the (meth)acrylic monomer having a mercapto group in the monomer component is preferably from 5% by weight to 99% by weight, more preferably from 15% by weight to 97% by weight, still more preferably 25% by weight. %~95% by weight. If the (meth)acrylic acid having a guanamine group is used When the content ratio of the monomer is within the above range, the composite film of the present invention exhibits sufficient adhesion when heated, and if it is cooled, the adhesive force is sufficiently lowered, and is used in the electronic component manufacturing step. In the case of temporarily fixing the sheet, it is possible to exhibit high-precision retention and good peelability.

Examples of the (meth)acrylic monomer having a guanamine group include N-methylol (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-n-butoxy Methyl (meth) acrylamide, N-(1,1-dimethyl-3- butyl butyl) (meth) acrylamide, N,N-dimethylaminopropyl (methyl a monosubstituted (meth) acrylamide such as acrylamide; N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, N,N-di - n-propyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N, N-di-isopropyl (meth) acrylamide, N, N - II N,N-disubstituted acrylamide such as n-butyl (meth) acrylamide, N,N-ethylmethyl (meth) acrylamide; N-(methyl) propylene fluorenyl N-(methyl)propenylpyrrolidone; N-(methyl)propenylpyridinium; N-(methyl)propenylpyrrolidine; N-(methyl)propenylpyridinium Pyridine; dimethylaminoethyl acrylate and the like. The (meth)acrylic monomer having a mercapto group may be used alone or in combination of two or more.

Any suitable vinyl monomer can be used as the monomer other than the (meth)acrylic monomer having a mercapto group as a monomer component constituting the vinyl polymer. These vinyl monomers may be used alone or in combination of two or more. As such a vinyl monomer, a (meth)acrylic monomer is preferable.

Examples of such a (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ethyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, Lauryl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as ester, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic acid, crotonic acid, cis a carboxyl group-containing monomer such as butenedioic acid, fumaric acid or methylene succinic acid; an acid anhydride monomer such as maleic anhydride or methylene succinic anhydride; 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyl-containing monomer such as allyl alcohol; dimethylaminoethyl (meth)acrylate, (meth)acrylic acid a tertiary amino group-containing monomer such as diethylaminoethyl ester or dimethylaminopropyl (meth)acrylate; an epoxy group-containing monomer such as glycidyl methacrylate; 2-(meth)acryl a sulfonic acid group-containing monomer such as amidoxime-2-methylpropanesulfonic acid or a sulfopropyl (meth)acrylate; a phosphoric acid-containing monomer such as 2-hydroxyethyl (meth)acryloylphosphonium phosphate; N-(A) Acryloxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl-8-oxygen Amber quinone imine monomer such as octamethylmethylene succinimide; (meth) propylene A cyanoacrylate monomer such as a nitrile.

It is preferred to use at least one of (meth)acrylic acid as the (meth)acrylic monomer. In this case, the content ratio of the (meth)acrylic acid in the vinyl monomer is preferably from 1% by weight to 50% by weight, more preferably from 3% by weight to 30% by weight, still more preferably from 5% by weight to 10% by weight. weight%. When the content ratio of the (meth)acrylic acid in the vinyl monomer is within the above range, the composite film of the present invention exhibits a more sufficient adhesion when heated, and if it is cooled, the adhesion is more sufficient. The ground reduction and the use of the temporary fixing sheet used in the electronic component manufacturing step can exhibit higher precision retention and better peelability.

Examples of the vinyl monomer other than the (meth)acrylic monomer having a mercapto group as a monomer component constituting the vinyl polymer include a polyfunctional monomer, vinyl acetate, and N. - vinyl pyrrolidone, N-vinyl carboxamide, N-vinyl caprolactam, and the like. Examples of the polyfunctional monomer include hexanediol diacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate.

The content ratio of the urethane polymer to the vinyl polymer in the composite film of the present invention may be any suitable content ratio within the range in which the effects of the present invention can be exhibited. For example, a urethane polymer is polymerized with respect to a urethane polymer and a vinyl polymer. The content ratio of the total amount of the substances is preferably from 20% by weight to 80% by weight, more preferably from 30% by weight to 70% by weight, still more preferably from 40% by weight to 60% by weight, particularly preferably from 45% by weight to 55% by weight. %. When the content ratio of the urethane polymer to the total amount of the urethane polymer and the ethylene polymer is within the above range, in the composite film of the present invention, if it is heated, the performance is further improved. Adequate adhesion, if cooled, the adhesion is more fully reduced, and in the case of temporarily fixing the sheet used in the electronic component manufacturing step, the retention accuracy and the better peeling can be expressed. Sex.

"Manufacturing method of composite film"

The composite film of the present invention can be produced by any suitable method. The composite film of the present invention is preferably produced by forming a urethane polymer in the presence of a monomer component constituting the vinyl polymer, and further comprising the urethane polymer. A photopolymerization initiator is added to the mixture of the monomer components and applied to the support substrate, and any appropriate active energy ray (α-ray, β-ray, γ-ray, or the like is irradiated depending on the type of the photopolymerization initiator or the like. The composite film of the present invention is produced by hardening it by neutron rays, electron beams, ultraviolet rays, visible light, or the like. As the reaction conditions for irradiating the active energy ray, any suitable conditions generally employed in the polymerization by irradiation with an active energy ray can be employed.

Further, when a hydroxyl group-containing acrylic monomer is used in the formation of the urethane polymer, the polyol compound and the polyisocyanate compound can be reacted in the presence of a monomer component constituting the vinyl polymer. After forming the polyurethane prepolymer, a hydroxyl group-containing acrylic monomer is added and reacted with the polyurethane prepolymer, and a photopolymerization initiator is further added to the obtained mixture. And coating on a support substrate, and irradiating any appropriate active energy ray (α-ray, β-ray, γ-ray, neutron beam, electron beam, ultraviolet light, visible light, etc.) according to the type of photopolymerization initiator, etc. Thereby, the composite film of the present invention is produced by hardening it. As a reaction condition for irradiating the active energy ray, any suitable strip generally used in the polymerization by irradiation with an active energy ray may be employed. Pieces.

Specifically, for example, after the polyol compound is dissolved in a monomer component for constituting the vinyl polymer, a polyisocyanate compound is added, reacted with a polyol compound to adjust viscosity, and the obtained mixture is coated. After being coated on a support substrate, it is cured by ultraviolet irradiation or the like to produce a composite film of the present invention. Further, the cured product may be peeled off from the support substrate after curing to form a composite film of the present invention.

Examples of the support substrate include a polyolefin resin, a polycarbonate resin, a (meth)acrylic resin, a polyester resin, and a lowering agent. Organic materials such as olefin resin and polystyrene resin; inorganic materials such as glass, metal foil, paper, cloth, and non-woven fabric. The thickness of the support substrate can be any suitable thickness depending on the purpose.

When a peelable supporting substrate is used as the supporting substrate, the cured product can be formed on the peelable supporting substrate by performing the curing reaction on the peelable supporting substrate, and thereafter, the peeling can be performed by the peeling support substrate. The composite support substrate is peeled off to obtain a composite film of the present invention in the form of a substrate-free film.

The thickness of the composite film of the present invention is preferably from 0.1 μm to 1000 μm, more preferably from 1 μm to 500 μm, even more preferably from 5 μm to 100 μm, particularly preferably 10 μm, in terms of the thickness of the support substrate. 80 μm.

In the production of the composite film of the present invention, in order to avoid polymerization inhibition by oxygen, the exfoliated substrate may be further placed on the mixture applied to the support substrate.

When the composite film of the present invention is produced, any suitable solvent may be added to adjust the viscosity. Examples of such a solvent include ethyl acetate, toluene, chloroform, and dimethylformamide.

Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxydiphenyl ketone, 4-methyldiphenyl ketone, and 2,4,6-trimethyldiphenyl ketone. , mazinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, benzoin dimethyl ketal, Diphenyl oxime, diethyl hydrazine, 1-chloroindole, 2-chloroindole, 2-ethyl hydrazine, 2,2-dimethoxy-1,2-diphenylethane-1-one , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Polinylacetone-1,2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1, 2-hydroxy-2-methyl-1-phenyl-1-propanone, diethyl-9-oxosulfur Isopropyl-9-oxosulfur Low molecular weight polymerization initiator such as 2,4,6-trimethylbenzyldiphenyl-phosphine oxide; oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl) a polymerization initiator such as phenyl]acetone} which has been oligomerized.

The photopolymerization initiator may be used alone or in combination of two or more.

The content of the photopolymerization initiator can be any appropriate amount which is usually used in photopolymerization.

When manufacturing the composite film of the present invention, any suitable additives may be used as needed. Examples of such an additive include an ultraviolet absorber, a softener (plasticizer), a filler, an anti-aging agent, an adhesion-imparting agent, a pigment, a dye, a decane coupling agent, and the like.

Temporary Fixed Sheet

The temporary fixing sheet of the present invention comprises the composite film of the present invention. The temporary fixing sheet of the present invention may be composed only of the composite film of the present invention, and may also comprise the composite film of the present invention and any other suitable members. In the case where the temporary fixing sheet of the present invention is composed only of the composite film of the present invention, the supporting substrate may or may not be included.

The thickness of the temporary fixing sheet of the present invention is preferably from 0.1 μm to 1000 μm, more preferably from 1 μm to 500 μm, even more preferably from 5 μm to 100 μm, particularly preferably 10, in terms of the thickness of the support substrate. Mm~80 μm.

The temporary fixing sheet of the present invention can be used as an adhesive sheet for temporarily fixing, storing, and transporting various adherends, and the use thereof is not particularly limited, and is particularly suitable for the electronic component manufacturing step.

The temporary fixing sheet of the present invention can be preferably applied to the use of laminated ceramic sheet cutting.

Hereinafter, a method of cutting a laminated ceramic sheet using the temporary fixing sheet of the present invention will be described with reference to Fig. 1 .

In Fig. 1, one of the temporary fixing sheets 1 of the present invention (in the case of a non-supporting substrate) is bonded to the susceptor 2, and the other surface is attached to the laminated ceramic sheet 3. Further, the sheet may be peeled off by temporarily fixing the surface area layer of the sheet 1 before the bonding. The cutting step of the laminated ceramic sheet 3 is carried out in a high temperature environment (for example, 60 to 100 ° C) for the purpose of improving the cutting accuracy. Since the temporary fixing sheet of the present invention has excellent adhesion in a high-temperature environment, the laminated ceramic sheet 3 can be firmly fixed to the susceptor 2 before and after the cutting step. In particular, since no bulging or deformation occurs at the time of cutting, it is possible to prevent the positional displacement of the laminated ceramic sheet 3 due to the insertion of the trowel 4 at the time of cutting, and it is possible to accurately cut accurately. After the cutting is completed, the object to be processed (the laminated ceramic sheet 3 after cutting) can be removed from the temporary fixing sheet 1 of the present invention. After the cut-off laminated ceramic sheet 3 is recovered by any appropriate method, the temporary fixing sheet 1 of the present invention can be peeled off from the susceptor 2 by peeling or the like.

[Examples]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited by the examples. In the following examples and comparative examples, the term "parts" means "parts by weight", and when it is described as %, it means % by weight.

<80 °C adhesion>

The film obtained in the examples and the comparative examples (the film obtained in Examples 1 to 5 and Comparative Examples 3 to 4 was peeled off to form a "hardened layer/supporting substrate (PET film)". The film formed is cut into a strip having a width of 10 mm and a length of 140 mm, and is attached to a PET film (width: 20 mm) having a thickness of 25 μm on a hot plate at 80 ° C according to JIS Z 0237. After being placed at 80 ° C on a variable angle peeling tester with a flat table, after standing for 3 minutes, peeling was performed at a tensile speed of 300 mm/min and a peeling angle of 180°, and the load was measured at this time. weight.

<25°C adhesion>

The film obtained above was attached to a PET film in the same manner as the measurement of the adhesive force at 80 ° C, placed on a hot plate at 80 ° C for 10 minutes, cooled to 25 ° C, and placed on a variable angle peel tester to The measurement was carried out at a measurement temperature of 25 ° C, a tensile speed of 300 mm/min, and a peeling angle of 180°, and the load at this time was measured.

<Sheet retention>

The film obtained in the examples and the comparative examples (the film obtained in Examples 1 to 5 and Comparative Examples 3 to 4 was peeled off to form a "hardened layer/supporting substrate (PET film)". The laminated film was placed as a temporary fixing sheet, and the laminated ceramic sheet (*1) was placed in an environment of 80 ° C for 5 minutes, and then cut into a wafer shape of 0402 (0.4 mm × 0.2 mm). Processing (* 2). The retention of the ceramic sheet at this time was evaluated by visual observation. Specifically, in the case where the ceramic sheet or the cut wafer is not peeled off or offset, the film can be processed as "○", and the case where the film can be processed with a slight offset is set to "△". In addition, the other cases are set to "X".

(* 1: How to make laminated ceramic sheets)

100 parts by weight of barium titanate (trade name "BT-03/high-purity perovskite", manufactured by Sigma Chemical Industry Co., Ltd.), and polyvinyl butyral (manufactured by Electric Chemical Industry Co., Ltd., trade name "PVB", Propylene glycol monoethyl ether dissolved product, 10% base) 100 parts by weight, bis(2-ethylhexyl) phthalate (manufactured by J-PLUS Co., Ltd., trade name "DOP"), 6 parts by weight, diglycerin oil 2 parts by weight of an acid ester (trade name "Rikemal 0-71-D (E)"), and 80 parts by weight of toluene were stirred and mixed to prepare a coating liquid for ceramic sheet production. Then, the coating liquid was applied to a separator coated with a polyxylene mold release agent on one side, and the coating liquid was applied to a thickness of 50 μm after drying, and then dried at 80 ° C for 5 minutes. The sheet was peeled off to obtain a ceramic sheet. Ten sheets of the ceramic sheet were laminated and pressed at a pressure of 300 kg/cm ² to obtain a laminated ceramic sheet.

(* 2: exact conditions)

Cutting device manufacturer: UHT Co., Ltd.

Cutting temperature: 80 ° C

Cutting depth (remaining amount from the table): approx. 75 μm

Cutting knife: thickness 100 μm, front end angle 15°

<wafer peelability>

The films obtained in Examples 1 to 5 and Comparative Example 3 (the film obtained in Examples 1 to 5 and Comparative Examples 3 to 4 were peeled off to form a "hardened layer/supporting substrate (PET). After the above-mentioned chopping and cutting process is performed as a temporary fixing sheet, the film is cooled at a temperature of 25° C. and a humidity of 65%, and the cut wafer is peeled off from the temporary fixing sheet. This was evaluated for wafer peelability. Specifically, the case where the sheet was easily peeled off from the temporary fixing of the sheet without being damaged or deformed by the wafer was evaluated as "○", and the case where the sheet was peeled off from the temporarily fixed sheet was evaluated as "△". The case where the peeling is completely impossible is evaluated as "X".

[Example 1]

47.5 parts by weight of N,N-dimethyl acrylamide (DMAA), 2.5 parts by weight of acrylic acid (AA), and a number average molecular weight of 1000 as a polyol compound are placed in a reaction vessel equipped with a cooling tube, a thermometer, and a stirring device. Poly(ethylene carbonate) diol (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Nipporan 981" (melting point (described on MSDS): 42 ° C)) 38.44 parts by weight, added as a polyisocyanate compound while stirring 9.33 parts by weight of hydrogenated benzene dimethylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) was reacted at 65 ° C for 5 hours to obtain a urethane polymer-acrylic monomer mixture. Thereafter, 2.23 parts by weight of hydroxyethyl acrylate (HEA) was charged and reacted at 65 ° C for 1 hour, whereby an acrylonitrile-terminated urethane polymer-acrylic monomer mixture was obtained. Further, add 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, trade name "Irgacure 651") as a photopolymerization initiator, 0.15 parts by weight, to obtain a mixture (1) . Further, the polyisocyanate compound and the polyol compound are used in an amount of NCO/OH (equivalent ratio) = 1.25.

The obtained mixture (1) was applied onto a PET film having a thickness of 100 μm so as to have a thickness of 50 μm after hardening. After covering the peeled PET spacer thereon, the surface of the coated PET separator was irradiated with ultraviolet light (illuminance 5 mW/cm ² , light quantity 1200 mJ/cm ² ) using a black light lamp to be hardened, thereby obtaining a single-sided inclusion. Film (1) of the peeled PET separator.

Various evaluation results are shown in Table 1.

[Embodiment 2]

Instead of using 47.5 parts by weight of N,N-dimethyl decylamine (DMAA) and 2.5 parts by weight of acrylic acid (AA), 12.5 parts by weight of DMAA, 35 parts by weight of acrylic acid (IBXA), AA was used. A film (2) comprising a peel-treated PET separator on one side was obtained in the same manner as in Example 1 except for 2.5 parts by weight.

Various evaluation results are shown in Table 1.

[Example 3]

Instead of using 47.5 parts by weight of N,N-dimethyl acrylamide (DMAA) and 2.5 parts by weight of acrylic acid (AA), 12.5 parts by weight of N,N-diethyl acrylamide (DEAA) and 35 parts by weight of IBXA were used. A film (3) comprising a peel-treated PET separator on one side was obtained in the same manner as in Example 1 except that 2.5 parts by weight of AA was used.

Various evaluation results are shown in Table 1.

[Example 4]

Instead of using 47.5 parts by weight of N,N-dimethyl acrylamide (DMAA) and 2.5 parts by weight of acrylic acid (AA), 12.5 parts by weight of N-isopropyl acrylamide (NIPAM), 35 parts by weight of IBXA, AA. A film (4) comprising a peel-treated PET separator on one side was obtained in the same manner as in Example 1 except for 2.5 parts by weight.

Various evaluation results are shown in Table 1.

[Example 5]

Instead of using 47.5 parts by weight of N,N-dimethyl decylamine (DMAA) and 2.5 parts by weight of acrylic acid (AA), 12.5 parts by weight of DMAA, 35 parts by weight of t-butyl acrylate, and AA 2.5 were used. A film (5) comprising a peel-treated PET separator on one side was obtained in the same manner as in Example 1 except for the parts by weight.

Various evaluation results are shown in Table 1.

[Comparative Example 1]

Ethylene-vinyl acetate copolymer (EVA) resin (manufactured by DuPont-Mitsui Chemical Co., Ltd., trade name "Evaflex P-1905", melting point 84 ° C) by T-die extrusion method, melt flow rate (melt flow) Rate) 2.5 g/10 min, filming in a thickness of 100 μm to form a film (C1).

Various evaluation results are shown in Table 1.

[Comparative Example 2]

A soft polyvinyl chloride film of vinyl chloride (manufactured by Mitsubishi Chemical Corporation MKV Co., Ltd., trade name "KM Film") having a thickness of 70 μm was used as the film (C2).

Various evaluation results are shown in Table 1.

[Comparative Example 3]

47.5 parts by weight of N,N-dimethyl acrylamide (DMAA), 2.5 parts by weight of acrylic acid (AA), and a number average molecular weight of 650 as a polyol compound are placed in a reaction vessel equipped with a cooling tube, a thermometer, and a stirring device. Polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG 650" (melting point value: 11 ° C)) 34.18 parts by weight, while adding hydrogenated benzene as a polyisocyanate compound while stirring 12.76 parts by weight of methylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) was reacted at 65 ° C for 5 hours to obtain a urethane polymer-acrylic monomer mixture. Thereafter, 3.05 parts by weight of hydroxyethyl acrylate (HEA) was introduced, The reaction was carried out at 65 ° C for 1 hour, whereby an acrylonitrile-terminated urethane polymer-acrylic monomer mixture was obtained. The subsequent operation was carried out in the same manner as in Example 1 to obtain a film (C3) comprising a peel-treated PET separator on one side.

Various evaluation results are shown in Table 1.

[Comparative Example 4]

The same procedure as in Example 1 was carried out, except that 47.5 parts by weight of N,N-dimethyl acrylamide (DMAA) and 2.5 parts by weight of acrylic acid (AA) were used, and 47.5 parts by weight of IBXA and 2.5 parts by weight of AA were used. A film (C4) comprising a peeled PET separator on one side was obtained.

Various evaluation results are shown in Table 1.

As shown in Table 1, it is understood that the composite film of the present invention and the temporary fixing sheet of the present invention exhibit sufficient adhesion when heated, and when cooled, the adhesive strength is sufficiently lowered, and high-precision retention and goodness can be exhibited. Peelability. In particular, in the case of use in the cutting and cutting step in the high-temperature environment of the laminated ceramic sheet, since the temporarily fixed sheet of the present invention has high adhesion in a high temperature environment, the wafer peeling during operation can be prevented. Therefore, the cutting can be performed with higher precision. Further, it is understood that when the temporary fixing sheet of the present invention is cooled, the adhesive force is sufficiently lowered, so that the wafer can be favorably peeled off only by cooling to room temperature without undergoing a heat treatment step, thereby preventing wafer reattachment.

1‧‧‧ Temporary fixed sheet

2‧‧‧Base

3‧‧‧Laminated ceramic sheets

4‧‧‧铡

Claims (8)

A composite film comprising a urethane polymer and a vinyl polymer, and the urethane polymer is obtained by reacting a polyol compound with a polyisocyanate compound, the melting point of the polyol compound And/or the freezing point is 15 to 75 ° C, and the ethylene-based polymer is obtained by polymerizing a monomer component containing a (meth)acrylic monomer having a mercapto group. The composite film of claim 1, wherein the urethane polymer comprises a (meth) acrylonitrile-terminated urethane polymer. A composite film according to claim 1 or 2, which comprises a support substrate. A temporary fixing sheet comprising the composite film according to any one of claims 1 to 3. A temporary fixed sheet of claim 4 for use in an electronic part manufacturing step. A temporary fixing sheet according to claim 5, which is used for cutting of a laminated ceramic sheet. A method of cutting a laminated ceramic sheet using a temporary fixing sheet as claimed in claim 5. An electronic component obtained by the cutting method of claim 7.