MULTILAYER FILM AND METHOD FOR PRODUCING SAME

Abstract

A laminated film including a resin layer on at least one side of a resin base film, the resin layer being present at least one surface, wherein the X-ray absorption near edge structure (XANES) spectrum at the carbon K absorption edge at the resin layer surface satisfies I(15)I(90)0.1 when the angle formed between the incident X-ray and the resin layer surface is defined as , and the spectral intensity at 293.5 eV obtained by the partial electron yield method is defined as I(). Provided is a laminated film as a release film to be used in an application that is carried out by coating the film with a coating liquid including a solvent, drying and solidifying the coating liquid, and then peeling off the solidified coating, which laminated film shows excellent applicability and an excellent peeling property, and does not show delamination of the surface layer even after a heating process.

Claims

1. A laminated film comprising a resin layer on at least one side of a resin base film, the resin layer being present at least one surface, wherein in an XAFS spectrum measured for the resin layer surface by the partial electron yield method, an X-ray absorption near edge structure (XANES) spectrum at the carbon K absorption edge satisfies I(15)I(90)0.1 when the angle formed between the incident X-ray and the resin layer surface is defined as , and the spectral intensity at 293.5 eV is defined as I().

2. The laminated film according to claim 1, wherein the surface elastic modulus of the resin layer as measured by AFM is not less than 1 GPa.

3. The laminated film according to claim 1, comprising a resin layer placed on at least one side of a resin base film, the laminated film having a tape peel strength of not more than 3.0 N/19 mm, and having a domain size of not more than 500 nm as observed in a modulus mapping image by AFM.

4. A laminated film comprising a resin layer placed on at least one side of a resin base film, the laminated film having a tape peel strength of not more than 3.0 N/19 mm, and having a domain size of not more than 500 nm as observed in a modulus mapping image by AFM.

5. The laminated film according to claim 4, wherein the surface elastic modulus of the resin layer as measured by AFM is not less than 1 GPa.

6. The laminated film according to claim 1, wherein the resin layer has a water contact angle of not less than 85 to not more than 110.

7. The laminated film according to claim 1, wherein in an XAFS spectrum measured for the resin layer surface by the partial electron yield method, an X-ray absorption near edge structure (XANES) spectrum at the carbon K absorption edge satisfies [I(15)0.1]/I(90)>1 when the angle formed between the incident X-ray and the resin layer surface is defined as , and the spectral intensity at 293.5 eV is defined as I().

8. The laminated film according to claim 1, wherein when the surface of the resin layer is analyzed by time-of-flight secondary ion mass spectrometry, the ratio of the peak intensity of the fragment derived from polydimethylsiloxane (P) to the peak intensity of the fragment detected at the highest intensity (K) (P/K) [] is less than 0.01.

9. The laminated film according to claim 1, wherein the resin layer comprises a long-chain alkyl resin as a release agent (A), and wherein when the long-chain alkyl resin is heated from 25 C. to 200 C. at 20 C./min and then cooled from 200 C. to 50 C. at 20 C./min using a differential scanning calorimeter (DSC), the exothermic peak temperature (Tc) in the cooling process is not less than 30 C.

10. The laminated film according to claim 1, wherein the resin layer is formed from a coating agent composition comprising: a release agent (A); and at least one resin or compound selected from epoxy resins, oxazoline compounds, carbodiimide compounds, polyester resins, acrylic resins, and urethane resins (B).

11. The laminated film according to claim 1, wherein the resin layer has a film thickness of more than 10 nm and less than 200 nm.

12. The laminated film according to claim 1, wherein the resin base film is a polyester film.

13. A method of producing the laminated film according to claim 1, the method comprising: applying a coating agent composition comprising: a release agent (A); and at least one resin or compound selected from epoxy resins, oxazoline compounds, carbodiimide compounds, polyester resins, acrylic resins, and urethane resins (B); to at least one side of the resin base film; subsequently drawing the film in a uniaxial direction; and then heating the film to not less than 150 C., to allow formation of the resin layer.

14. The laminated film according to claim 1, for use in an application that is carried out by applying a ceramic slurry to the surface of the resin layer, solidifying the ceramic slurry, and then peeling off the solidified ceramic slurry.

Description

EXAMPLES

[0182] The laminated film according to embodiments of the present invention is described below in detail based on particular Examples. However, the present invention is not limited to these Examples.

Reference Example 1

[0183] Long-chain alkyl group-containing resin a1 was obtained through the following Step (I) and Step (II).

Step (I):

[0184] In a 25-mL pressure-resistant glass ampule for polymerization, methyl methacrylate (MMA) (manufactured by Kanto Chemical Co., Inc.), ,-azobisisobutyronitrile (AIBN) (manufactured by Kanto Chemical Co., Inc.) as a polymerization initiator, cumyl dithiobenzoate (CDB) as a RAFT agent, and toluene as a solvent were placed such that their weights (g) were as follows: MMA/CDB/AIBN/toluene=2.92/0.03/0.007/2.27. Subsequently, the mixed solution in the ampule was degassed twice by the freeze-degassing method, and then the ampule was sealed, followed by heating the ampule in an oil bath at 100 C. for 18 hours to obtain a reaction liquid containing a polymer (I-1).

Step (II):

[0185] To the reaction liquid in the ampule, docosyl acrylate, AIBN as a polymerization initiator, and toluene as a solvent were added such that their weights (g) were as follows: docosyl acrylate/AIBN/toluene=1.37/0.003/1.3. After carrying out freeze-degassing twice, the ampule was sealed, and heated at 100 C. for 48 hours. Thereafter, the polymerization solution was added dropwise to a 20-fold mass of hexane, and the resulting mixture was stirred to allow precipitation of solids. The obtained solids were filtered, and dried under vacuum at 40 C. overnight, to obtain a long-chain alkyl group-containing resin (a block copolymer comprising an alkyl group having 22 carbon atoms (which is referred to as long-chain alkyl group-containing resin a1)).

[0186] The obtained long-chain alkyl group-containing resin a1 was emulsified as follows to prepare an aqueous resin emulsion. In a homomixer having a capacity of 1 L, 375 g of water was placed, and then 45 g of polyoxyethylene nonylphenyl ether, 30 g of polyoxyethylene polyoxypropylene glycol, 200 g of long-chain alkyl group-containing resin a1, and 150 g of toluene were sequentially added thereto, followed by heating the resulting mixture to 70 C. and uniformly stirring the mixture. The mixed liquid was then transferred into a pressure homogenizer, and emulsified. Thereafter, toluene was removed by evaporation with heating under reduced pressure.

Reference Example 2

[0187] In a four-necked flask, 200 parts of xylene and 600 parts of octadecyl isocyanate were placed, and the resulting mixture was heated with stirring. From the time point when the reflux of xylene began, 100 parts of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 88 mol % was added thereto in small portions at 10-minute intervals for about 2 hours. After the completion of the addition of polyvinyl alcohol, the reflux was further carried out for 2 hours, and the reaction was stopped. The reaction mixture was cooled to about 80 C., and then added into methanol. As a result, precipitation of the reaction product as a white precipitate occurred. The precipitate was separated by filtration, and then 140 parts of xylene was added thereto, followed by heating the resulting mixture to allow complete dissolution, and adding methanol again thereto to allow precipitation. After repeating this operation several times, the precipitate was washed with methanol, and subjected to dry grinding, to obtain a long-chain alkyl group-containing resin (comprising polymethylene as the backbone, and an alkyl group having 18 carbon atoms as a side chain (which is referred to as long-chain alkyl group-containing resin a2)). The resin was diluted with water to 20 mass %.

Reference Example 3

[0188] Long-chain alkyl group-containing resin a3 was obtained as follows. In a stainless-steel reaction container, methyl methacrylate (), hydroxyethyl methacrylate ((), and octadecyl methacrylate () were placed at a mass ratio of ()/()/()=94/1/5. As an emulsifier, 2 parts by mass of sodium dodecylbenzene sulfonate was added to a total of 100 parts by mass of () to (), and the resulting mixture was stirred to prepare Mixed Liquid 1. Subsequently, a reaction apparatus equipped with a stirrer, a reflux condensing tube, a thermometer, and a dropping funnel was provided. In the reaction apparatus, 60 parts by mass of the Mixed Liquid 1, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were placed, and the resulting mixture was heated to 60 C., to prepare Mixed Liquid 2. The Mixed Liquid 2 was maintained under the condition with heating at 60 C. for 20 minutes. A mixture of 40 parts by mass of Mixed Liquid 1, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate was prepared, to prepare Mixed Liquid 3. Subsequently, Mixed Liquid 3 was added dropwise to Mixed Liquid 2 using the dropping funnel for 2 hours, to prepare Mixed Liquid 4. Thereafter, the Mixed Liquid 4 was maintained under the condition with heating at 60 C. for 2 hours, and then cooled to not more than 50 C. The liquid was then transferred to a container equipped with a stirrer and decompression equipment. To the liquid, 60 parts by mass of 25% aqueous ammonia and 900 parts by mass of pure water were added. While the resulting mixture was heated to 60 C., isopropyl alcohol and unreacted monomers were recovered under reduced pressure, to obtain a long-chain alkyl group-containing resin (comprising methacrylate as the backbone, and an alkyl group having 18 carbon atoms as a side chain (which is referred to as long-chain alkyl group-containing resin a3)) dispersed in pure water.

Reference Example 4

[0189] Synthesis was carried out by the same production method as in Reference Example 1 except that octadecyl acrylate was used instead of docosyl acrylate, to obtain a long-chain alkyl group-containing resin (a block copolymer comprising an alkyl group having 18 carbon atoms (which is referred to as long-chain alkyl group-containing resin a4)). The resin was prepared into an aqueous resin emulsion in the same manner as in Reference Example 1.

Reference Example 5

[0190] Synthesis was carried out by the same production method as in Reference Example 2 except that icosyl isocyanate was used instead of octadecyl isocyanate, to obtain a long-chain alkyl group-containing resin (comprising polymethylene as the backbone, and an alkyl group having 20 carbon atoms as a side chain (which is referred to as long-chain alkyl group-containing resin a5)).

Reference Example 6

[0191] Synthesis was carried out by the same production method as in Reference Example 2 except that dodecyl isocyanate was used instead of octadecyl isocyanate, to obtain a long-chain alkyl group-containing resin (comprising polymethylene as the backbone, and an alkyl group having 12 carbon atoms as a side chain (which is referred to as long-chain alkyl group-containing resin a6)).

Reference Example 7

[0192] Synthesis was carried out by the same production method as in Reference Example 2 except that octyl isocyanate was used instead of octadecyl isocyanate, to obtain a long-chain alkyl group-containing resin (comprising polymethylene as the backbone, and an alkyl group having 8 carbon atoms as a side chain (which is referred to as long-chain alkyl group-containing resin a7)).

Reference Example 8

[0193] Long-chain alkyl group-containing resin a8 was obtained through the following Step (I) and Step (II).

Step (I):

[0194] In a 25-mL pressure-resistant glass ampule for polymerization, 2-hydroxyethyl acrylate (HEA) (manufactured by Kanto Chemical Co., Inc.), ,-azobisisobutyronitrile (AIBN) (manufactured by Kanto Chemical Co., Inc.) as a polymerization initiator, cumyl dithiobenzoate (CDB) as a RAFT agent, and toluene as a solvent were placed such that their weights (g) were as follows: HEA/CDB/AIBN/toluene=0.35/0.03/0.007/2.27. Subsequently, the mixed solution in the ampule was degassed twice by the freeze-degassing method, and then the ampule was sealed, followed by heating the ampule in an oil bath at 100 C. for 18 hours to obtain a reaction liquid containing a polymer (I-8).

Step (II):

[0195] To the reaction liquid in the ampule, docosyl acrylate, AIBN as a polymerization initiator, and toluene as a solvent were added such that their weights (g) were as follows: docosyl acrylate/AIBN/toluene=4.65/0.003/1.3. After carrying out freeze-degassing twice, the ampule was sealed, and heated at 100 C. for 48 hours. Thereafter, the polymerization solution was added dropwise to a 20-fold mass of hexane, and the resulting mixture was stirred to allow precipitation of solids. The obtained solids were filtered, and dried under vacuum at 40 C. overnight, to obtain a long-chain alkyl group-containing resin (a block copolymer comprising an alkyl group having 22 carbon atoms (which is referred to as long-chain alkyl group-containing resin a8)). The obtained long-chain alkyl group-containing resin a8 was emulsified in the same manner as in Reference Example 1, to prepare an aqueous resin emulsion.

Reference Example 9

[0196] Synthesis was carried out in the same manner as in Reference Example 1 except that 4-hydroxybutyl acrylate (HBA) (manufactured by Kanto Chemical Co., Inc.) was used instead of HEA as the monomers in Step I, to obtain long-chain alkyl group-containing resin a9. The obtained long-chain alkyl group-containing resin a9 was emulsified by the same method as in Reference Example 1, to prepare an aqueous resin emulsion.

Reference Example 10

[0197] Synthesis was carried out in the same manner as in Reference Example 1 except that methoxytriethylene glycol methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of HEA as the monomers in Step I, to obtain long-chain alkyl group-containing resin a10. The obtained long-chain alkyl group-containing resin a10 was emulsified by the same method as in Reference Example 1, to prepare an aqueous resin emulsion.

Reference Example 11

[0198] Synthesis was carried out by the same production method as in Reference Example 8 except that octadecyl acrylate was used instead of docosyl acrylate, to obtain a long-chain alkyl group-containing resin (a block copolymer comprising an alkyl group having 18 carbon atoms (which is referred to as long-chain alkyl group-containing resin all)). The resin was prepared into an aqueous resin emulsion in the same manner as in Reference Example 1.

Reference Example 12

[0199] Synthesis was carried out by the same production method as in Reference Example 1 except that the weight of the HEA added was 0.16 g, and that the weight of the docosyl acrylate added was 4.84 g, to obtain long-chain alkyl group-containing resin a12. The resin was prepared into an aqueous resin emulsion in the same manner as in Reference Example 1.

Reference Example 13

[0200] An acrylic resin was obtained as follows. In a stainless-steel reaction container, methyl methacrylate (), hydroxyethyl methacrylate (), and urethane acrylate oligomers (Art Resin (registered trademark) UN-3320HA, manufactured by Negami Chemical Industrial Co., Ltd.; number of acryloyl groups, 6) () were placed at a mass ratio of ()/()/()=94/1/5. As an emulsifier, 2 parts by mass of sodium dodecylbenzene sulfonate was added with respect to a total of 100 parts by mass of () to (), and the resulting mixture was stirred to prepare Mixed Liquid 5. Subsequently, a reaction apparatus equipped with a stirrer, a reflux condensing tube, a thermometer, and a dropping funnel was provided. In the reaction apparatus, 60 parts by mass of the Mixed Liquid 5, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were placed, and the resulting mixture was heated to 60 C., to prepare Mixed Liquid 6. The Mixed Liquid 6 was maintained under the condition with heating at 60 C. for 20 minutes. A mixture of 40 parts by mass of Mixed Liquid 5, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate was prepared, to prepare Mixed Liquid 7. Subsequently, Mixed Liquid 7 was added dropwise to Mixed Liquid 2 using the dropping funnel for 2 hours, to prepare Mixed Liquid 8. Thereafter, the Mixed Liquid 8 was maintained under the condition with heating at 60 C. for 2 hours, and then cooled to not more than 50 C. The liquid was then transferred to a container equipped with a stirrer and decompression equipment. To the liquid, 60 parts by mass of 25% aqueous ammonia and 900 parts by mass of pure water were added. While the resulting mixture was heated to 60 C., isopropyl alcohol and unreacted monomers were recovered under reduced pressure, to obtain an acrylic resin dispersed in pure water.

Reference Example 14

[0201] A polyester resin having the following copolymerization composition was prepared as an aqueous dispersion.

<Copolymerization Components>

(Dicarboxylic Acid Components)

[0202] Dimethyl 2,6-naphthalenedicarboxylate: 88 mol % [0203] Dimethyl 5-sulfoisophthalate sodium: 12 mol %

(Diol Components)

[0204] A compound prepared by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mol % [0205] 1,3-Propanediol: 14 mol %

Reference Example 15

[0206] As a silicone resin, a mixture of KM-3951, manufactured by Shin-Etsu Chemical Co., Ltd., X-52-6015, manufactured by Shin-Etsu Chemical Co., Ltd., and CAT-PM-10A, manufactured by Shin-Etsu Chemical Co., Ltd., at a mass ratio of 85:15:5 was prepared.

Reference Example 16

[0207] Synthesis was carried out by the same method as in Reference Example 1 except that 2-perfluorohexyl ethyl acrylate (synthesized by a known method using 2-perfluorohexyl ethanol as a raw material followed by purification by simple distillation) was used instead of docosyl acrylate, to obtain a fluorocarbon resin f1.

Reference Example 17

[0208] Synthesis was carried out by the same method as in Reference Example 1 except that 2-perfluorodecyl ethyl acrylate (synthesized by a known method using 2-perfluorodecyl ethanol as a raw material followed by purification by simple distillation) was used instead of docosyl acrylate, to obtain a fluorocarbon resin f2.

Example 1

[0209] Coating Agent Composition:

[0210] A coating agent composition was obtained by adding 0.1 part by mass of a fluorocarbon surfactant (PLAS COAT RY-2, manufactured by Goo Chemical Co., Ltd.) to 100 parts by mass of long-chain alkyl group-containing resin a1, to obtain a coating agent composition. For improvement of applicability to a polyester film, a fluorocarbon surfactant was added.

[0211] Polyester Film:

[0212] PET pellets (limiting viscosity, 0.64 dl/g) comprising 4 mass % of silica particles (primary particle size, 0.3 m) and 2 mass % of calcium carbonate particles (primary particle size, 0.8 m) were sufficiently dried under vacuum. Subsequently, the PET pellets were fed into an extruder, and melted at 280 C., followed by extrusion from a T-shaped die into a sheet shape. The sheet was then wound around a mirror-finished casting drum with a surface temperature of 25 C. by using the electrostatic voltage application casting method, to allow cooling and solidification of the sheet. The resulting undrawn film was heated to 90 C., and drawn in the longitudinal direction at a ratio of 3.1, to obtain a uniaxially drawn film (Film B).

[0213] Laminated Film:

[0214] The obtained uniaxially drawn film was subjected to corona discharge treatment in air, and the coating agent composition shown in Table 1 was applied thereto to a coating thickness of about 6 m using a bar coater. Subsequently, both end portions in the width direction of the uniaxially drawn film to which the coating agent composition was applied were held with clips, and the film was introduced to a preheating zone. In the preheating zone, the ambient temperature was set to 90 to 100 C., and the solvent in the coating agent composition was dried. Subsequently, the film was continuously drawn in the width direction at a ratio of 3.6 in a drawing zone at 100 C., and then subjected to heat treatment for 20 seconds in a heat treatment zone at 230 to 240 C., followed by allowing formation of a resin layer. Further, while relaxation treatment was carried out at a ratio of 5% in the width direction at the same temperature, the film was cooled at 55 C. for 30 seconds, to obtain a laminated film in which the crystal orientation of the polyester film was completed. In the obtained laminated film, the thickness of the polyester film was 50 m, and the thickness of the resin layer was 30 nm. Properties and the like of the laminated films obtained in Examples are shown in Tables 3 to 6.

Examples 2 to 65

[0215] Laminated films were obtained by the same method as in Example 1 except that the coating agent compositions shown in Table 1 and Table 2, and the temperature conditions shown in Table 3 and Table 4 were employed. The resins shown in Table 1 and Table 2 are as follows: as long-chain alkyl group-containing resins a1 to a12, the resins obtained in Reference Examples 1 to 12 were used; as the acrylic resin, the resin obtained in Reference Example 13 was used; and as the polyester resin, the resin obtained in Reference Example 14 was used. As the melamine resin, NIKALAC (registered trademark) MW-035 (solids concentration, 70 mass %; solvent, water), manufactured by SANWA Chemical Co., Ltd., was used. As the oxazoline compound, EPOCROS (registered trademark) WS-500 (solids concentration, 40 mass %; solvent, water), manufactured by NIPPON SHOKUBAI Co., Ltd., was used. The solid content mass ratio represents the ratio to the total mass of the resin or compound described in the table. In any of the Examples, the PVB applicability and the peeling property were favorable.

Comparative Example 1

[0216] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained an olefin resin (CHEMIPEARL (registered trademark) XEP800H, manufactured by Mitsui Chemicals, Inc.) and the acrylic resin obtained in Reference Example 13, and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Properties and the like of the obtained laminated film are shown in Table 4 and Table 6. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

Comparative Example 2

[0217] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained the silicone resin prepared in Reference Example 15 and a melamine resin NIKALAC (registered trademark) MW-035 (solids concentration, 70 mass %; solvent, water), manufactured by SANWA Chemical Co., Ltd., and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB peeling property was favorable, the PVB applicability, and the PVB adhesion at high temperature were poor.

Comparative Example 3

[0218] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained the fluorocarbon resin f1 obtained in Reference Example 16 and the acrylic resin obtained in Reference Example 13, and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

Comparative Example 4

[0219] A laminated film was obtained by the same method as in Example 1 except that long-chain alkyl group-containing resin a7 was used instead of long-chain alkyl group-containing resin a1, that the coating agent composition contained the acrylic resin obtained in Reference Example 13, and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

Comparative Example 5

[0220] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained the acrylic resin obtained in Reference Example 13 and a melamine resin NIKALAC (registered trademark) MW-035 (solids concentration, 70 mass %; solvent, water), manufactured by SANWA Chemical Co., Ltd., and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

Comparative Example 6

[0221] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained an olefin resin (CHEMIPEARL (registered trademark) XEP800H, manufactured by Mitsui Chemicals, Inc.) and the acrylic resin obtained in Reference Example 13, and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

Comparative Example 7

[0222] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained the silicone resin prepared in Reference Example 15 and a melamine resin NIKALAC (registered trademark) MW-035 (solids concentration, 70 mass %; solvent, water), manufactured by SANWA Chemical Co., Ltd., and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB peeling property was favorable, the PVB applicability, and the PVB adhesion at high temperature were poor.

Comparative Example 8

[0223] A laminated film was obtained by the same method as in Example 1 except that no long-chain alkyl group-containing resin was substantially included, that the coating agent composition contained the fluorocarbon resin f1 obtained in Reference Example 17 and the acrylic resin obtained in Reference Example 13, and that the coating agent composition shown in Table 2 and the temperature conditions shown in Table 4 were employed. Although the PVB applicability, and the PVB adhesion at high temperature were favorable, the PVB peeling property was poor.

TABLE-US-00001 TABLE 1 Coating Agent Composition HSP Distance from Components Other Than Carbon Tc Release Agent Mass Ratio of Type Numbers ( C.) (MPa.sup.1/2) Solid Content Example 1 Resin a1 having Long Chain Alkyl Groups 22 53 100 Example 2 Resin a1 having Long Chain Alkyl Groups 22 53 17 20 Example 3 Resin a1 having Long Chain Alkyl Groups 22 53 16 20 Example 4 Resin a1 having Long Chain Alkyl Groups 22 53 16 20 Example 5 Resin a1 having Long Chain Alkyl Groups 22 53 17 20 Example 6 Resin a1 having Long Chain Alkyl Groups 22 53 16 20 Example 7 Resin a1 having Long Chain Alkyl Groups 22 53 16 50 Example 8 Resin a1 having Long Chain Alkyl Groups 22 53 16 20 Example 9 Resin a1 having Long Chain Alkyl Groups 22 53 15 20 Example 10 Resin a1 having Long Chain Alkyl Groups 22 53 15 20 Example 11 Resin a1 having Long Chain Alkyl Groups 22 53 15 20 Example 12 Resin a2 having Long Chain Alkyl Groups 18 51 100 Example 13 Resin a2 having Long Chain Alkyl Groups 18 51 10 20 Example 14 Resin a2 having Long Chain Alkyl Groups 18 51 9 20 Example 15 Resin a2 having Long Chain Alkyl Groups 18 51 9 20 Example 16 Resin a2 having Long Chain Alkyl Groups 18 51 9 20 Example 17 Resin a2 having Long Chain Alkyl Groups 18 51 9 20 Example 18 Resin a2 having Long Chain Alkyl Groups 18 51 9 20 Example 19 Resin a3 having Long Chain Alkyl Groups 18 19 100 Example 20 Resin a3 having Long Chain Alkyl Groups 18 19 9 20 Example 21 Resin a3 having Long Chain Alkyl Groups 18 19 8 20 Example 22 Resin a3 having Long Chain Alkyl Groups 18 19 8 20 Example 23 Resin a4 having Long Chain Alkyl Groups 18 45 100 Example 24 Resin a4 having Long Chain Alkyl Groups 18 45 16 20 Example 25 Resin a4 having Long Chain Alkyl Groups 18 45 15 20 Example 26 Resin a4 having Long Chain Alkyl Groups 18 45 15 20 Example 27 Resin a5 having Long Chain Alkyl Groups 20 37 100 Example 28 Resin a5 having Long Chain Alkyl Groups 20 37 12 20 Example 29 Resin a5 having Long Chain Alkyl Groups 20 37 11 20 Example 30 Resin a5 having Long Chain Alkyl Groups 20 37 11 20 Example 31 Resin a6 having Long Chain Alkyl Groups 12 18 100 Example 32 Resin a6 having Long Chain Alkyl Groups 12 18 8 20 Example 33 Resin a6 having Long Chain Alkyl Groups 12 18 7 20 Example 34 Resin a6 having Long Chain Alkyl Groups 12 18 7 20 Example 35 Resin a8 having Long Chain Alkyl Groups 22 55 100 Coating Agent Composition Mass Ratio of Mass Ratio of Type Solid Content Type Solid Content Example 1 Example 2 Acrylic Resin 80 Example 3 Acrylic Resin 40 Melamine Resin 40 Example 4 Acrylic Resin 15 Melamine Resin 65 Example 5 Polyester Resin 80 Example 6 Polyester Resin 40 Oxazoline Compound 40 Example 7 Polyester Resin 25 Oxazoline Compound 25 Example 8 Polyester Resin 40 Melamine Resin 40 Example 9 Polyester Resin 40 Oxazoline Compound 40 Example 10 Polyester Resin 40 Oxazoline Compound 40 Example 11 Polyester Resin 40 Oxazoline Compound 40 Example 12 Example 13 Acrylic Resin 80 Example 14 Acrylic Resin 40 Melamine Resin 40 Example 15 Acrylic Resin 15 Melamine Resin 65 Example 16 Polyester Resin 80 Example 17 Polyester Resin 40 Oxazoline Compound 40 Example 18 Polyester Resin 40 Melamine Resin 40 Example 19 Example 20 Polyester Resin 80 Example 21 Acrylic Resin 40 Melamine Resin 40 Example 22 Polyester Resin 40 Oxazoline Compound 40 Example 23 Example 24 Polyester Resin 80 Example 25 Acrylic Resin 40 Melamine Resin 40 Example 26 Polyester Resin 40 Oxazoline Compound 40 Example 27 Example 28 Polyester Resin 80 Example 29 Acrylic Resin 40 Melamine Resin 40 Example 30 Polyester Resin 40 Oxazoline Compound 40 Example 31 Example 32 Polyester Resin 80 Example 33 Acrylic Resin 40 Melamine Resin 40 Example 34 Polyester Resin 40 Oxazoline Compound 40 Example 35 .sup.Notes) Melamine Resin: Manufactered by SANWA Chemical Co., Ltd. NIKALAC (Registered Trademark) MW-035 (Solid content concentration: 70 mass %, Solvent: water); Oxazoline Compound: Manufactered by NIPPON SHOKUBAI Co., Ltd. EPOCROS (Registered Trademark) WS-500 (Solid content concentration: 40 mass %, Solvent: water)

TABLE-US-00002 TABLE 2 Coating Agent Composition HSP Distance from Carbon Tc Components Other Than Type Numbers ( C.) Release Agent (MPa.sup.1/2) Example 36 Resin a8 having Long Chain Alkyl Groups 22 55 11 Example 37 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 38 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 39 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 40 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 41 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 42 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 43 Resin a8 having Long Chain Alkyl Groups 22 55 10 Example 44 Resin a9 having Long Chain Alkyl Groups 22 57 11 Example 45 Resin a9 having Long Chain Alkyl Groups 22 57 11 Example 46 Resin a9 having Long Chain Alkyl Groups 22 57 11 Example 47 Resin a9 having Long Chain Alkyl Groups 22 57 11 Example 48 Resin a9 having Long Chain Alkyl Groups 22 57 10 Example 49 Resin a9 having Long Chain Alkyl Groups 22 57 10 Example 50 Resin a9 having Long Chain Alkyl Groups 22 57 11 Example 51 Resin a10 having Long Chain Alkyl Groups 22 48 9 Example 52 Resin a10 having Long Chain Alkyl Groups 22 48 9 Example 53 Resin a10 having Long Chain Alkyl Groups 22 48 8 Example 54 Resin a10 having Long Chain Alkyl Groups 22 48 8 Example 55 Resin a10 having Long Chain Alkyl Groups 22 48 9 Example 56 Resin a11 having Long Chain Alkyl Groups 18 43 10 Example 57 Resin a11 having Long Chain Alkyl Groups 18 43 10 Example 58 Resin a11 having Long Chain Alkyl Groups 18 43 10 Example 59 Resin a11 having Long Chain Alkyl Groups 18 43 10 Example 60 Resin a11 having Long Chain Alkyl Groups 18 43 10 Example 61 Resin a12 having Long Chain Alkyl Groups 22 58 12 Example 62 Resin a12 having Long Chain Alkyl Groups 22 58 12 Example 63 Resin a12 having Long Chain Alkyl Groups 22 58 12 Example 64 Resin a12 having Long Chain Alkyl Groups 22 58 12 Example 65 Resin a12 having Long Chain Alkyl Groups 22 58 11 Coating Agent Composition Mass Ratio of Mass ratio of Mass ratio of Solid Content Type solid content Type solid content Example 36 50 Acrylic Resin 50 Example 37 30 Acrylic Resin 35 Melamine Resin 35 Example 38 30 Acrylic Resin 10 Melamine Resin 60 Example 39 30 Acrylic Resin 10 Melamine Resin 60 Example 40 30 Acrylic Resin 10 Melamine Resin 60 Example 41 50 Polyester Resin 25 Melamine Resin 25 Example 42 50 Polyester Resin 25 Oxazoline Compound 25 Example 43 50 Polyester Resin 10 Oxazoline Compound 40 Example 44 50 Acrylic Resin 50 Example 45 30 Acrylic Resin 35 Melamine Resin 35 Example 46 30 Acrylic Resin 10 Melamine Resin 60 Example 47 30 Acrylic Resin 10 Melamine Resin 60 Example 48 50 Polyester Resin 25 Melamine Resin 25 Example 49 50 Polyester Resin 25 Oxazoline Compound 25 Example 50 50 Polyester Resin 10 Oxazoline Compound 40 Example 51 50 Acrylic Resin 50 Example 52 30 Acrylic Resin 10 Melamine Resin 60 Example 53 50 Polyester Resin 25 Melamine Resin 25 Example 54 50 Polyester Resin 25 Oxazoline Compound 25 Example 55 50 Polyester Resin 10 Oxazoline Compound 40 Example 56 50 Acrylic Resin 50 Example 57 30 Acrylic Resin 10 Melamine Resin 60 Example 58 50 Polyester Resin 25 Melamine Resin 25 Example 59 50 Polyester Resin 25 Oxazoline Compound 25 Example 60 50 Polyester Resin 10 Oxazoline Compound 40 Example 61 50 Acrylic Resin 50 Example 62 30 Acrylic Resin 10 Melamine Resin 60 Example 63 50 Polyester Resin 25 Melamine Resin 25 Example 64 50 Polyester Resin 25 Oxazoline Compound 25 Example 65 50 Polyester Resin 10 Oxazoline Compound 40 Coating Agent Composition HSP Distance from Carbon Tc Components Other Than Mass Ratio of Type Numbers ( C.) Release Agent(MPa.sup.1/2) Solid Content Comparative Olefin Resin x 12 20 Example 1 Comparative Silicone Resin x 15 20 Example 2 Comparative Fluoro Resin f1 x 14 20 Example 3 Comparative Resin a7 having Long 8 15 6 20 Example 4 Chain Alkyl Groups Comparative x Example 5 Comparative Olefin Resin 12 30 Example 6 Comparative Silicone Resin 15 30 Example 7 Comparative Fluoro Resin f2 x 16 70 Example 8 Coating Agent Composition Mass ratio of Mass ratio of Type solid content Type solid content Comparative Acrylic Resin 80 Example 1 Comparative Melamine Resin 80 Example 2 Comparative Acrylic Resin 80 Example 3 Comparative Acrylic Resin 80 Example 4 Comparative Acrylic Resin 50 Melamine Resin 50 Example 5 Comparative Acrylic Resin 70 Example 6 Comparative Melamine Resin 70 Example 7 Comparative Acrylic Resin 30 Example 8 .sup.Notes) Melamine Resin: Manufactered by SANWA Chemical Co., Ltd. NIKALAC (Registered Trademark) MW-035 (Solid content concentration: 70 mass %, Solvent: water); Oxazoline Compound: Manufactered by NIPPON SHOKUBAI Co., Ltd. EPOCROS (Registered Trademark) WS-500 (Solid content concentration: 40 mass %, Solvent: water)

TABLE-US-00003 TABLE 3 Coating - Drawing Steps Properties of Coating Film Drying Temperature of Cooling Tape Peel Temperature of Heat Treatment Temperature Strength Solvent ( C.) ( C.) ( C.) I(15) I(90) (N/19 mm) Example 1 90 235 55 0.70 0.8 Example 2 90 235 55 0.54 2.0 Example 3 90 235 55 0.40 2.2 Example 4 90 235 55 0.30 2.2 Example 5 90 235 55 0.60 1.7 Example 6 90 235 55 0.90 1.7 Example 7 90 235 55 0.90 1.5 Example 8 90 235 55 0.50 1.8 Example 9 90 235 65 0.30 2.0 Example 10 90 235 60 0.40 2.2 Example 11 90 235 55 0.74 1.5 Example 12 80 230 50 0.20 2.0 Example 13 80 230 50 0.20 2.4 Example 14 80 230 50 0.20 2.2 Example 15 80 230 50 0.20 2.6 Example 16 80 230 50 0.30 2.2 Example 17 80 230 50 0.30 2.3 Example 18 80 230 50 0.30 2.3 Example 19 80 230 40 0.10 3.8 Example 20 80 230 40 0.10 3.7 Example 21 80 230 40 0.10 3.9 Example 22 80 230 40 0.10 3.7 Example 23 90 235 55 0.20 0.9 Example 24 90 235 55 0.20 1.6 Example 25 90 235 55 0.20 1.8 Example 26 90 235 55 0.20 2.0 Example 27 90 235 55 0.20 1.0 Example 28 90 235 55 0.20 1.8 Example 29 90 235 50 0.20 2.0 Example 30 90 235 55 0.20 2.2 Example 31 80 230 40 0.10 3.4 Example 32 80 230 40 0.10 3.2 Example 33 80 230 40 0.10 3.0 Example 34 80 230 40 0.10 3.0 Example 35 90 230 55 0.70 1.6 Properties of Coating Film Surface Peak Domain Water Elastic Intensity Film Size Contact [I(15) Modulus Ratio Thickness (nm) Angle () 0.1]/I(90) (Gpa) P/K (nm) Example 1 100 108 1.10 0.3 less than 0.01 30 Example 2 670 103 1.15 0.8 less than 0.01 30 Example 3 620 104 1.25 1.8 less than 0.01 30 Example 4 680 96 1.25 2.2 less than 0.01 30 Example 5 620 108 1.45 0.6 less than 0.01 30 Example 6 600 107 1.55 1.6 less than 0.01 30 Example 7 580 108 1.50 1.4 less than 0.01 30 Example 8 580 105 1.45 1.7 less than 0.01 30 Example 9 480 106 1.40 1.7 less than 0.01 10 Example 10 480 108 1.30 1.7 less than 0.01 80 Example 11 480 108 1.65 1.7 less than 0.01 160 Example 12 60 101 1.15 0.2 less than 0.01 30 Example 13 180 98 1.25 0.6 less than 0.01 30 Example 14 170 97 1.30 1.7 less than 0.01 30 Example 15 160 96 1.30 2.1 less than 0.01 30 Example 16 160 101 1.35 0.5 less than 0.01 30 Example 17 170 100 1.35 1.3 less than 0.01 30 Example 18 165 99 1.35 1.6 less than 0.01 30 Example 19 50 88 1.10 0.2 less than 0.01 30 Example 20 110 89 1.10 0.6 less than 0.01 30 Example 21 120 87 1.10 1.8 less than 0.01 30 Example 22 120 89 1.10 1.2 less than 0.01 30 Example 23 90 102 1.15 0.2 less than 0.01 30 Example 24 480 102 1.15 0.6 less than 0.01 30 Example 25 430 93 1.10 1.9 less than 0.01 30 Example 26 420 102 1.10 1.3 less than 0.01 30 Example 27 40 97 1.10 0.2 less than 0.01 30 Example 28 180 97 1.25 0.6 less than 0.01 30 Example 29 160 95 1.25 1.7 less than 0.01 30 Example 30 140 97 1.25 1.2 less than 0.01 30 Example 31 50 80 1.00 0.2 less than 0.01 30 Example 32 40 80 1.00 0.6 less than 0.01 30 Example 33 40 75 1.00 1.6 less than 0.01 30 Example 34 40 80 1.00 1.0 less than 0.01 30 Example 35 50 106 1.15 0.3 less than 0.01 50

TABLE-US-00004 TABLE 4 Coating - Drawing Steps Properties of Coating Film Drying Temperature of Cooling Tape Peel Temperature of Heat Treatment Temperature Strength Solvent ( C.) ( C.) ( C.) I(15) I(90) (N/19 mm) Example 36 90 230 55 0.65 1.7 Example 37 90 230 55 0.60 1.8 Example 38 90 230 55 0.60 2.0 Example 39 90 230 65 0.55 2.2 Example 40 90 230 100 0.45 2.3 Example 41 90 230 55 0.60 1.8 Example 42 90 230 55 0.65 2.0 Example 43 90 230 55 0.60 1.9 Example 44 95 235 57 0.80 1.8 Example 45 95 235 57 0.70 1.8 Example 46 95 235 57 0.65 1.6 Example 47 95 235 100 0.50 2.3 Example 48 95 235 57 0.65 1.8 Example 49 95 235 57 0.60 1.6 Example 50 95 235 57 0.60 1.7 Example 51 85 230 48 0.55 1.9 Example 52 85 230 48 0.50 1.8 Example 53 85 230 48 0.55 1.9 Example 54 85 230 48 0.40 2.0 Example 55 85 230 48 0.45 1.9 Example 56 85 230 43 0.30 2.2 Example 57 85 230 43 0.30 2.3 Example 58 85 230 43 0.25 2.1 Example 59 85 230 100 0.15 2.8 Example 60 85 230 43 0.30 2.3 Example 61 90 235 58 0.60 1.8 Example 62 90 235 58 0.55 1.7 Example 63 90 235 58 0.50 1.6 Example 64 90 235 100 0.30 2.3 Example 65 90 235 58 0.45 1.9 Properties of Coating Film Surface Peak Domain Water Elastic Intensity Film Size Contact [I(15) Modulus Ratio Thickness (nm) Angle () 0.1]/I(90) (Gpa) P/K (nm) Example 36 230 105 1.15 0.6 less than 0.01 50 Example 37 185 104 1.25 1.8 less than 0.01 80 Example 38 160 103 1.45 2.0 less than 0.01 50 Example 39 160 104 1.55 2.2 less than 0.01 50 Example 40 160 103 1.35 2.3 less than 0.01 50 Example 41 90 105 1.45 1.5 less than 0.01 80 Example 42 95 108 1.35 1.2 less than 0.01 50 Example 43 180 109 1.45 1.6 less than 0.01 50 Example 44 240 107 1.15 0.4 less than 0.01 30 Example 45 220 106 1.70 1.8 less than 0.01 50 Example 46 210 107 1.80 2.0 less than 0.01 50 Example 47 210 104 1.75 2.1 less than 0.01 50 Example 48 200 110 1.75 1.6 less than 0.01 100 Example 49 180 109 1.35 1.3 less than 0.01 50 Example 50 210 110 1.45 1.7 less than 0.01 50 Example 51 90 105 1.15 0.5 less than 0.01 20 Example 52 85 106 1.55 2.1 less than 0.01 50 Example 53 86 106 1.65 1.7 less than 0.01 50 Example 54 83 107 1.30 1.3 less than 0.01 50 Example 55 84 105 1.45 1.6 less than 0.01 10 Example 56 145 104 1.15 0.4 less than 0.01 50 Example 57 130 105 1.35 2.1 less than 0.01 50 Example 58 87 105 1.25 1.6 less than 0.01 50 Example 59 98 103 1.25 1.3 less than 0.01 50 Example 60 95 106 1.25 1.6 less than 0.01 60 Example 61 236 108 1.10 0.4 less than 0.01 50 Example 62 210 109 1.45 2.3 less than 0.01 50 Example 63 350 109 1.45 1.6 less than 0.01 70 Example 64 450 110 1.20 1.2 less than 0.01 50 Example 65 250 106 1.25 1.7 less than 0.01 150 Coating - Drawing Steps Properties of Coating Film Drying Temperature of Cooling Tape Peel Temperature of Heat Treatment Temperature Strength Solvent ( C.) ( C.) ( C.) I(15) I(90) (N/19 mm) Comparative 90 230 100 0.00 3.9 Example 1 Comparative 90 230 100 0.00 1.5 Example 2 Comparative 90 230 110 0.00 3.2 Example 3 Comparative 90 230 100 0.05 3.5 Example 4 Comparative 90 230 100 0.00 5.5 Example 5 Comparative 90 230 100 0.05 3.8 Example 6 Comparative 90 230 100 0.05 1.2 Example 7 Comparative 90 230 100 0.00 3.6 Example 8 Properties of Coating Film Surface Peak Domain Water Elastic Intensity Film Size Contact [I(15) Modulus Ratio Thickness (nm) Angle () 0.1]/I(90) (Gpa) P/K (nm) Comparative 90 85 0.90 0.2 less than 0.01 30 Example 1 Comparative 550 111 0.90 0.8 0.65 30 Example 2 Comparative 490 94 0.95 0.6 less than 0.01 30 Example 3 Comparative 40 80 1.05 0.9 less than 0.01 30 Example 4 Comparative 20 75 0.90 1.6 less than 0.01 30 Example 5 Comparative 120 85 0.90 0.7 less than 0.01 50 Example 6 Comparative 510 112 0.90 0.9 0.65 100 Example 7 Comparative 530 110 0.90 0.6 less than 0.01 30 Example 8

TABLE-US-00005 TABLE 5 PVB PVB Peal PVB Adhesiveness at Coating Strength @ high temperature Property room temperature @ 120 C. Eval- Peel Strength Eval- Peel Strength Eval- uation (mN/20 mm) uation (mN/20 mm) uation Example 1 A 31 B 55 S Example 2 S 20 A 25 C Example 3 A 25 A 31 B Example 4 S 25 A 32 B Example 5 A 15 S 20 C Example 6 A 10 S 15 C Example 7 A 10 S 15 C Example 8 A 15 S 20 C Example 9 A 20 A 35 B Example 10 A 25 A 38 B Example 11 A 10 S 31 B Example 12 A 50 B 62 S Example 13 A 30 A 45 A Example 14 A 30 A 45 A Example 15 A 35 A 48 A Example 16 A 25 A 44 A Example 17 A 25 A 43 A Example 18 A 25 A 44 A Example 19 A 60 B 70 S Example 20 A 35 B 45 A Example 21 A 40 B 48 A Example 22 A 35 B 42 A Example 23 A 55 B 58 S Example 24 A 30 B 32 B Example 25 A 35 B 39 B Example 26 A 32 B 37 B Example 27 A 50 B 60 S Example 28 A 20 A 42 A Example 29 A 25 A 48 A Example 30 A 20 A 41 A Example 31 S 40 B 64 S Example 32 S 35 B 55 S Example 33 S 38 B 60 S Example 34 S 35 B 54 S Example 35 S 55 B 60 S

TABLE-US-00006 TABLE 6 PVB Peal PVB Adhesiveness PVB Strength @ room at high temperature Coating temperature @ 120 C. Property Peel Strength Eval- Peel Strength Eval- Evaluation (mN/20 mm) uation (mN/20 mm) uation Example 36 S 40 B 45 A Example 37 S 30 A 43 A Example 38 S 14 S 43 A Example 39 S 15 S 42 A Example 40 S 20 A 48 A Example 41 S 15 S 51 S Example 42 A 28 A 52 S Example 43 A 15 S 41 A Example 44 A 48 B 49 A Example 45 S 15 S 42 A Example 46 S 14 S 43 A Example 47 S 15 S 44 A Example 48 B 14 S 45 A Example 49 B 22 A 45 A Example 50 B 15 S 41 A Example 51 S 50 B 68 S Example 52 S 13 S 55 S Example 53 S 14 S 52 S Example 54 S 15 A 54 S Example 55 S 14 S 56 S Example 56 S 55 B 44 A Example 57 S 22 A 43 A Example 58 S 26 A 52 S Example 59 S 35 B 58 S Example 60 S 25 A 53 S Example 61 A 50 B 45 A Example 62 B 14 S 42 A Example 63 B 15 S 32 B Example 64 B 31 B 38 B Example 65 A 18 A 44 A Comparative S 70 C 90 S Example 1 Comparative C 10 S 12 C Example 2 Comparative S 70 C 49 A Example 3 Comparative S 65 C 70 S Example 4 Comparative S 100 C 120 S Example 5 Comparative S 65 C 80 S Example 6 Comparative C 10 S 15 C Example 7 Comparative B 61 C 29 C Example 8

[0224] The laminated film according to embodiments of the present invention provides excellent applicability and an excellent peeling property, and also provides excellent adhesion at high temperature, for a surface layer represented by a ceramic slurry. Thus, the laminated film of the present invention can be suitably used as a processing film for the production process of an electronic component.