JP6428028B2 - Adhesive composition, insulating film, method for producing insulating film, and flat cable - Google Patents

Description

  The present invention relates to an adhesive composition, an insulating film, a method for producing an insulating film, and a flat cable.

  A multi-core flat cable is used as an electric wire for internal wiring of electronic equipment. A flat cable is manufactured by sandwiching a plurality of conductors in parallel between two insulating films and fusing the insulating films together to integrate them. Generally, this insulating film has an adhesive layer in contact with a conductor and a resin film on the outside thereof. As this resin film, a biaxially stretched polyethylene terephthalate (PET) film having excellent mechanical properties and electrical properties is widely used. Moreover, polyester etc. which were excellent in the electrical property are used as a resin component of the adhesive composition which forms an adhesive bond layer. In particular, polyester having a high melt viscosity is excellent in heat resistance, and is therefore suitable as a resin component of an adhesive layer of a flat cable that places importance on heat resistance.

  By the way, high flame retardancy may be required for the flat cable. For example, in order to conform to the United States UL (Underwriters Laboratories Inc.) standard, it is necessary to pass the vertical flame retardant test (VW-1 test). . In order to satisfy such flame retardant standards, it is necessary to include a flame retardant in the adhesive layer. As a flame retardant, a halogen flame retardant such as a brominated flame retardant or a chlorine flame retardant, or a phosphorus flame retardant. Non-halogen flame retardants such as flame retardants, nitrogen flame retardants, magnesium hydroxide and aluminum hydroxide are used.

  Flat cables using halogenated flame retardants are undesirable in terms of environment because they generate combustion gases harmful to the human body such as hydrogen halide gas during incineration. In recent years, materials using non-halogenated flame retardants are mainly used. Yes. Among non-halogen flame retardants, phosphorus flame retardants have improved flame retardancy in a small amount compared to other non-halogen flame retardants such as nitrogen flame retardant, magnesium hydroxide, aluminum hydroxide, etc. Since it has little influence on the rate, it is preferably used as a flame retardant for an adhesive layer of a flat cable (see JP 2001-076550 A).

  Here, in the method for producing an adhesive composition, melt kneading is generally performed in order to disperse a phosphorus-based flame retardant in polyester. However, it is difficult to satisfactorily disperse the phosphorus-based flame retardant in polyester having a high melt viscosity in a general melt kneader. In particular, the insulating film used for the flat cable is generally as thin as 100 μm or less, and the thickness of the adhesive layer is about 10 μm to 90 μm. For this reason, when an adhesive layer is formed with an adhesive composition in which the phosphorus-based flame retardant is not well dispersed, the appearance of the adhesive layer may be deteriorated and the flame retardancy and electrical characteristics may be insufficient. is there. Thus, as a method for satisfactorily dispersing the phosphorus-based flame retardant in the polyester, a method of melt-kneading crystalline polyester, polyolefin, and a phosphorus-based flame retardant has been proposed (see JP 2013-175341 A).

JP 2001-076550 A JP 2013-175341 A

  However, when a resin component other than polyester is contained in the adhesive composition, the phosphorus-based flame retardant can be dispersed well, but the polyester has the best electrical characteristics and heat resistance. I can't.

  This invention is made | formed based on the above situations, and it aims at provision of the adhesive composition excellent in the heat resistance after hardening, an external appearance, a flame retardance, and an electrical property.

  The adhesive composition according to one embodiment of the present invention, which has been made to solve the above problems, includes one or more first polyesters having a melt viscosity at 200 ° C. of less than 350 Pa · s, and a melt viscosity at 200 ° C. of 350 Pa · s. 1 type or more 2nd polyester which is the above, and a phosphorus flame retardant, The content of the said phosphorus flame retardant with respect to 100 mass parts of total amounts of said 1st polyester and said 2nd polyester is 20 mass parts or more and 100 masses Or less.

  Moreover, the manufacturing method of the insulating film which concerns on another aspect of this invention made | formed in order to solve the said subject is manufacturing an insulating film provided with the resin film and the adhesive bond layer laminated | stacked on one surface of this resin film. It is a method, Comprising: It is a manufacturing method of an insulating film provided with the process of laminating | stacking the said adhesive composition on one side of the said resin film.

  The adhesive composition according to one embodiment of the present invention is excellent in heat resistance after solidification, appearance, flame retardancy, and electrical characteristics. Therefore, the adhesive composition can be suitably used for insulating films and flat cables. Moreover, the manufacturing method of the insulating film which concerns on another aspect of this invention can manufacture the insulating film which is excellent in heat resistance, an external appearance, a flame retardance, and an electrical property.

It is typical sectional drawing which shows the insulating film which concerns on 1 aspect of this invention. It is typical sectional drawing which shows the flat cable which concerns on 1 aspect of this invention.

[Description of Embodiment of the Present Invention]
The adhesive composition according to one embodiment of the present invention includes at least one first polyester having a melt viscosity at 200 ° C. of less than 350 Pa · s, and at least one second polyester having a melt viscosity at 200 ° C. of at least 350 Pa · s. And the content of the said phosphorus flame retardant with respect to the total amount of 100 mass parts of said 1st polyester and said 2nd polyester is 20 mass parts or more and 100 mass parts or less.

  The adhesive composition contains the first polyester having a low melt viscosity and the second polyester having a high melt viscosity, so that the dispersibility of the phosphorus-based flame retardant is enhanced. The reason for this is not clear, but it is presumed that the dispersibility of the adhesive composition is enhanced because an appropriate shear stress is applied to the phosphorus-based flame retardant due to the presence of polyesters having different melt viscosities during melt kneading. Since the phosphorus-based flame retardant is well dispersed, the adhesive composition is excellent in appearance after solidification, flame retardancy, and electrical characteristics. Moreover, since the said adhesive composition contains the 2nd polyester which is high in melt viscosity and excellent in heat resistance, it is excellent in heat resistance after solidification. Therefore, the said adhesive composition can be used suitably for the insulating film for flat cables, etc.

  A nitrogen-based flame retardant may be further contained, and the content of the nitrogen-based flame retardant with respect to 100 parts by mass of the total amount of the first polyester and the second polyester is preferably 10 parts by mass or more and 75 parts by mass or less. Thus, by further containing a nitrogen-based flame retardant and setting the content of the nitrogen-based flame retardant within the above range, the flame retardancy after solidification can be further increased.

  As content of the said 1st polyester with respect to the total amount of said 1st polyester and said 2nd polyester, 10 mass% or more and 80 mass% or less of said 2nd polyester with respect to the total amount of said 1st polyester and said 2nd polyester As content, 20 mass% or more and 90 mass% or less are preferable. Thus, the heat resistance after a solidification, an external appearance, a flame retardance, and an electrical property can be improved more by making content ratio of 1st polyester and 2nd polyester into the said range.

  The difference between the melt viscosity of the first polyester at 200 ° C. and the melt viscosity of the second polyester at 200 ° C. is preferably 100 Pa · s or more. Thus, by setting the difference between the melt viscosity of the first polyester and the melt viscosity of the second polyester within the above range, the heat resistance after solidification, appearance, flame retardancy, and electrical characteristics can be further improved. it can.

  At least one of the first polyester and the second polyester may be a crystalline polyester, and the melting point of the crystalline polyester is preferably 100 ° C. or higher. Since crystalline polyester is difficult to soften up to near the melting point, the heat resistance after solidification can be further improved by using at least one of the first polyester and the second polyester as a crystalline polyester having a melting point of 100 ° C. or higher. Can do.

  The phosphorus flame retardant and the nitrogen flame retardant may be solid at the melting point of the crystalline polyester. Thus, the flame retardancy after solidification can be further enhanced by containing a solid flame retardant at the temperature at the time of melt-kneading that is equal to or higher than the melting point of the crystalline polyester.

  The phosphorus flame retardant may include a phosphinic acid metal salt, polyphosphazene, phosphaphenanthrene, or a combination thereof. Thus, the flame retardance after solidification can be improved more by containing the said compound as a phosphorus flame retardant.

  Moreover, the insulating film which concerns on another aspect of this invention is an insulating film provided with the resin film and the adhesive bond layer laminated | stacked on one surface of this resin film, Comprising: The said adhesive bond layer is the said adhesive composition. It is formed by.

  Since the adhesive layer is formed of the adhesive composition, the insulating film has excellent heat resistance, appearance, flame retardancy, and electrical characteristics. Therefore, the said insulating film can be used conveniently for a flat cable etc.

  A method for producing an insulating film according to still another aspect of the present invention is a method for producing an insulating film comprising a resin film and an adhesive layer laminated on one surface of the resin film, wherein one of the resin films is provided. A step of laminating the adhesive composition on the surface.

  According to the manufacturing method of the said insulating film, the insulating film excellent in heat resistance, an external appearance, a flame retardance, and an electrical property can be provided.

  The flat cable according to still another aspect of the present invention is a flat cable including a pair of covering materials and a conductor sandwiched between these covering materials, and at least one of the pair of covering materials is This is the insulating film.

  The flat cable is excellent in heat resistance, appearance, flame retardancy, and electrical characteristics because at least one of the pair of covering materials is the insulating film.

Here, “melt viscosity at 200 ° C.” was measured using a capillary rheometer in accordance with JIS-K7199: 1999 “Plastic-capillary rheometer and plastic flow property test method using slit die rheometer”. It is a melt viscosity at 200 ° C. and a shear rate of 100 sec ⁻¹ . “Crystalline polyester” refers to a polyester in which a melting peak derived from crystals is observed by differential scanning calorimetry (DSC) based on JIS-K7121: 1987 “Method for measuring transition temperature of plastic”. The “melting point of crystalline polyester” is the melting peak temperature obtained by the differential scanning calorimetry.

[Details of the embodiment of the present invention]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[Adhesive composition]
The adhesive composition includes one or more first polyesters having a melt viscosity at 200 ° C. of less than 350 Pa · s, one or more second polyesters having a melt viscosity at 200 ° C. of 350 Pa · s or more, and a phosphorus-based flame retardant. contains. The said adhesive composition may contain 1 type of 1st polyester or 2nd polyester, and may contain 2 or more types of 1st polyester or 2nd polyester. The adhesive composition preferably further contains a nitrogen-based flame retardant. The said adhesive composition may contain another flame retardant or another arbitrary component in the range which does not impair the effect of this invention. However, it is preferable that the said adhesive composition does not contain other resin substantially.

<First polyester>
The first polyester is a polyester having a melt viscosity at 200 ° C. of less than 350 Pa · s. By containing the first polyester having the melt viscosity less than the upper limit, the dispersibility of the phosphorus-based flame retardant can be enhanced. The upper limit of the melt viscosity is preferably 300 Pa · s, more preferably 250 Pa · s, and even more preferably 200 Pa · s. On the other hand, the lower limit of the melt viscosity is preferably 10 Pa · s, more preferably 60 Pa · s, and further preferably 120 Pa · s from the viewpoint of moldability. If the melt viscosity exceeds the above upper limit, the dispersibility of the phosphorus-based flame retardant of the adhesive composition cannot be sufficiently increased, and the appearance after solidification of the adhesive composition may be deteriorated or flame retardant In addition, electrical characteristics may be insufficient. On the other hand, when the melt viscosity is less than the lower limit, it may be difficult to form the adhesive composition by heating.

(polyester)
Polyester is a resin having an ester bond in the main chain. Examples thereof include polymers used as structural units, and copolymers thereof. Known polyesters can be used, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, etc. Examples include polyester. Examples of the polyester copolymer include polyethylene terephthalate / sebacate copolymer, polybutylene terephthalate / sebacate copolymer, polybutylene terephthalate / adipate copolymer, polyethylene terephthalate / succinate copolymer, polyethylene terephthalate / adipate copolymer. -Copolymer, polyethylene terephthalate / dodecadionate copolymer, polybutylene terephthalate / succinate copolymer, polybutylene terephthalate / dodecadionate copolymer, polyhexylene terephthalate / succinate copolymer, polyhexylene terephthalate -Adipate copolymer, polyhexylene terephthalate-sebacate copolymer, polyhexylene terephthalate-dodecadionate copolymer and the like. The polyester may be an unsaturated polyester having a structural unit derived from an unsaturated polycarboxylic acid such as fumaric acid or itaconic acid. The polyester may have a structure derived from another monomer that can be copolymerized as long as the effects of the present invention are not impaired.

<Second polyester>
The second polyester is a polyester having a melt viscosity at 200 ° C. of 350 Pa · s or more. By containing the second polyester having the melt viscosity equal to or higher than the lower limit, the dispersibility of the phosphorus-based flame retardant and the heat resistance after solidification can be improved. The lower limit of the melt viscosity is preferably 400 Pa · s, more preferably 450 Pa · s, and even more preferably 500 Pa · s. On the other hand, the upper limit of the melt viscosity is preferably 1200 Pa · s, more preferably 1000 Pa · s, and still more preferably 900 Pa · s. When the said melt viscosity is less than the said minimum, there exists a possibility that the heat resistance after the solidification of the said adhesive composition may become inadequate. On the other hand, when the melt viscosity exceeds the upper limit, it may be difficult to form the adhesive composition by heating.

  The lower limit of the difference between the melt viscosity of the first polyester at 200 ° C. and the melt viscosity of the second polyester at 200 ° C. is preferably 100 Pa · s, more preferably 200 Pa · s, and even more preferably 300 Pa · s. On the other hand, the upper limit of the difference in melt viscosity is preferably 1000 Pa · s, more preferably 800 Pa · s, and still more preferably 700 Pa · s. When the difference in the melt viscosity is less than the lower limit, the dispersibility of the phosphorus-based flame retardant of the adhesive composition cannot be sufficiently increased, and the appearance after solidification may be deteriorated or the flame retardancy and electrical characteristics May become insufficient. Conversely, when the difference in melt viscosity exceeds the upper limit, it may be difficult to mix the first polyester and the second polyester by melt kneading.

  As a minimum of content of the 1st polyester to the total amount of the 1st polyester and the 2nd polyester, 10 mass% is preferred, 15 mass% is more preferred, and 25 mass% is still more preferred. On the other hand, the upper limit of the content is preferably 80% by mass, and more preferably 65% by mass. When the content is less than the lower limit, the dispersibility of the phosphorus-based flame retardant in the adhesive composition cannot be sufficiently increased, and the appearance after solidification may be deteriorated, and the flame retardancy and electrical characteristics are poor. May be sufficient. On the contrary, when the content exceeds the upper limit, the heat resistance after the adhesive composition is solidified may be insufficient.

  As a minimum of content of the 2nd polyester to the total amount of the 1st polyester and the 2nd polyester, 20 mass% is preferred and 35 mass% is more preferred. On the other hand, the upper limit of the content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 75% by mass. When the said content is less than the said minimum, there exists a possibility that the heat resistance after the solidification of the said adhesive composition may become inadequate. On the other hand, when the content exceeds the upper limit, the dispersibility of the phosphorus-based flame retardant of the adhesive composition cannot be sufficiently increased, and the appearance after solidification may be deteriorated, flame retardancy, and electrical characteristics. May become insufficient.

  Preferably, at least one of the first polyester and the second polyester is a crystalline polyester, more preferably at least one of the first polyester and at least one of the second polyester is a crystalline polyester, More preferably, all of the polyester is a crystalline polyester. By containing crystalline polyester that is difficult to soften up to near the melting point, the heat resistance after solidification of the adhesive composition can be further increased.

  As a minimum of melting point of crystalline polyester, 100 ° C is preferred, 110 ° C is more preferred, and 120 ° C is still more preferred. On the other hand, the upper limit of the melting point of the crystalline polyester is preferably 180 ° C, more preferably 170 ° C, and further preferably 160 ° C. When the melting point of the crystalline polyester is less than the above lower limit, the heat resistance after solidification may be insufficient. On the other hand, when the melting point of the crystalline polyester exceeds the above upper limit, it may be difficult to form the adhesive composition by heating.

  The lower limit of the content of the crystalline polyester is preferably 50% by mass, more preferably 80% by mass, and still more preferably 95% by mass with respect to the total amount of the first polyester and the second polyester. When content of crystalline polyester is less than the said minimum, there exists a possibility that the heat resistance after the said adhesive composition solidifies may become inadequate.

<Phosphorus flame retardant>
The phosphorus-based flame retardant imparts flame retardancy after solidification to the adhesive composition. Examples of the phosphorus flame retardant include phosphinic acid metal salts, polyphosphazenes, phosphaphenanthrenes, melamine phosphate, ammonium phosphate, and phosphate esters. As the phosphorus-based flame retardant, phosphinic acid metal salts, polyphosphazenes or phosphaphenanthrenes are preferable. A phosphorus flame retardant may be used independently and may use 2 or more types together.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素数１以上６以下のアルキル基又は炭素数１２以下のアリール基である。Ｍは、カルシウム、アルミニウム又は亜鉛である。ａは２又は３の整数で、Ｍがアルミニウムの場合はａ＝３、Ｍがカルシウム又は亜鉛の場合はａ＝２である。） As a phosphinic acid metal salt, the compound etc. which are represented, for example by following formula (1) are mentioned.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms. M is calcium, aluminum, or zinc. a is an integer of 2 or 3, a = 3 when M is aluminum, and a = 2 when M is calcium or zinc.)

  The phosphinic acid metal salt is preferably an aluminum phosphinate. Examples of commercially available aluminum phosphinic acid salts include “EXOLIT OP1230”, “EXOLIT OP1240”, “EXOLIT OP930”, “EXOLIT OP935”, and the like, which are organic phosphinic acid aluminum salts. Examples thereof include “EXOLIT OP1312” manufactured by Clariant, which is a mixture of a salt and melamine polyphosphate.

Polyphosphazene is a polymer having a main chain in which phosphorus atoms and nitrogen atoms are alternately bonded, and is represented by a structural formula (—PX ₂ ═N—) n. In the above structural formula, P represents a phosphorus atom, N represents a nitrogen atom, X represents a hydrogen atom or a substituent, and n represents an integer of 10 to 10,000. Polyphosphazene is obtained, for example, by ring-opening polymerization of cyclophosphazene. Examples of commercially available polyphosphazenes obtained by ring-opening polymerization of cyclophosphazene include, for example, “SPR-100”, “SA-100”, “SR-100”, “SRS-100”, “SPB” of Otsuka Chemical Co., Ltd. -100 "," SPB-100L "and the like.

（式（２）中、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、炭素原子数１以上６以下の炭化水素基である。ｂ及びｃは、それぞれ独立して、０以上４以下の整数である。Ａは、水素原子又は下記式（３）〜（５）で示されるいずれかの基である。） Examples of phosphaphenanthrene include a compound represented by the following formula (2).

(In Formula (2), R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. B and c are each independently 0 or more and 4 or less. A is a hydrogen atom or any group represented by the following formulas (3) to (5).)

  Examples of the phosphaphenanthrene include 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (for example, “HCA” from Sanko Co., Ltd.), 9,10-dihydro-10- (2,5-dihydroxy). Phenyl) -9-oxa-10-phosphaphenanthrene 10-oxide (for example, “HCA-HQ” manufactured by Sanko Co., Ltd.) and the like. As the phosphaphenanthrene, 9,10-dihydro-10- (2,5-dihydroxyphenyl) -9-oxa-10-phosphaphenanthrene 10-oxide is preferable.

  Examples of the melamine phosphate include melamine polyphosphate (for example, “MELAPUR200” manufactured by BASF), melamine polyphosphate, melamine phosphate, melamine orthophosphate, and melamine pyrophosphate.

  Examples of ammonium phosphate include ammonium polyphosphate, polyphosphate amide, ammonium polyphosphate amide, and polyphosphate carbamic acid.

  Examples of phosphate esters include triallyl phosphate, alkyl allyl phosphate, alkyl phosphate, dimethyl phosphate, phosphate, trimethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate , Cresylphenyl phosphate, triphenyl phosphate, polyphosphate, aromatic polyphosphate, and the like.

  Content of a phosphorus flame retardant is 20 mass parts or more and 100 mass parts or less with respect to 100 mass parts of total amounts of 1st polyester and 2nd polyester. As a minimum of content of a phosphorus system flame retardant, 30 mass parts is preferred to 40 mass parts with respect to 100 mass parts of total amounts of the 1st polyester and the 2nd polyester, and 45 mass parts is still more preferred. On the other hand, the upper limit of the content of the phosphorus-based flame retardant is preferably 80 parts by mass, more preferably 65 parts by mass, and even more preferably 55 parts by mass with respect to 100 parts by mass of the total amount of the first polyester and the second polyester. . When content of a phosphorus flame retardant is less than the said minimum, there exists a possibility that the flame retardance after the solidification of the said adhesive composition may become inadequate. Conversely, when the content of the phosphorus-based flame retardant exceeds the above upper limit, there is a possibility that the adhesiveness of the adhesive composition will deteriorate, the appearance after solidification will deteriorate, the electrical characteristics will deteriorate, and the like.

  When at least one of the first polyester and the second polyester is a crystalline polyester, the phosphorus flame retardant is preferably a phosphorus flame retardant that is solid at the melting point of the crystalline polyester. Examples of such phosphorus flame retardants include phosphorus flame retardants that are solid at 180 ° C. It is considered that a phosphorus-based flame retardant that is solid at the temperature during melt kneading imparts higher flame retardancy. Therefore, the flame retardancy after solidification of the adhesive composition can be further enhanced by containing a phosphorus-based flame retardant that is solid at the melting point of the crystalline polyester.

(Nitrogen flame retardant)
The nitrogen-based flame retardant enhances the flame retardancy after solidification of the adhesive composition by a synergistic effect with the phosphorus-based flame retardant. Examples of the nitrogen-based flame retardant include melamine cyanurate, triazine, isocyanurate, urea, guanidine and the like. As the nitrogen-based flame retardant, melamine cyanurate is preferable. Examples of commercially available melamine cyanurate include “MC600”, “MC860”, “MC4000”, “MC6000”, etc., manufactured by Nissan Chemical Industries, Ltd. Nitrogen-based flame retardants may be used alone or in combination of two or more.

  As a minimum of content of a nitrogen system flame retardant, 10 mass parts are preferred to 15 mass parts with respect to 100 mass parts of total amounts of the 1st polyester and the 2nd polyester, and 20 mass parts are still more preferred. On the other hand, as an upper limit of content of a nitrogen-type flame retardant, 75 mass parts is preferable with respect to 100 mass parts of total amounts of 1st polyester and 2nd polyester, 60 mass parts is more preferable, and 40 mass parts is further more preferable. . When content of a nitrogen-type flame retardant is less than the said minimum, there exists a possibility that the flame retardance after the solidification of the said adhesive composition may become inadequate. On the other hand, when the content of the nitrogen-based flame retardant exceeds the above upper limit, there is a possibility that the adhesiveness of the adhesive composition is deteriorated, the appearance after solidification is deteriorated, and the electrical characteristics are deteriorated.

  When at least one of the first polyester and the second polyester is a crystalline polyester, the nitrogen-based flame retardant is preferably a nitrogen-based flame retardant that is solid at the melting point of the crystalline polyester. Examples of such a nitrogen-based flame retardant include a nitrogen-based flame retardant that is solid at 180 ° C., for example. A nitrogen-based flame retardant that is solid at the temperature during melt-kneading is considered to impart higher flame retardancy. Therefore, the flame retardancy after solidification of the adhesive composition can be further increased by containing a nitrogen-based flame retardant that is solid at the melting point of the crystalline polyester.

(Other flame retardants)
Other flame retardants include, for example,
Chlorinated flame retardants such as chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, perchlorpentacyclodecane;
Ethylenebispentabromobenzene, ethylenebispentabromodiphenyl, tetrabromoethane, tetrabromobisphenol A, hexabromobenzene, decabromobiphenyl ether, tetrabromophthalic anhydride, polydibromophenylene oxide, hexabromocyclodecane, ammonium bromide, etc. Brominated flame retardants;
Polyols such as phosphonate-type polyols and phosphate-type polyols;
Aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zinc borate, antimony borate, boric acid, antimony molybdate, molybdenum oxide, calcium aluminum silicate, zirconium compound, tin compound, dosonite, calcium aluminate hydrate, oxidation Inorganic compounds such as copper, metal copper powder, calcium carbonate, metal powder such as barium metaborate;
Other compounds such as silicone polymers, ferrocene, fumaric acid, maleic acid and the like can be mentioned. As another flame retardant, a flame retardant containing no halogen atom is preferable from the viewpoint of the environment. Another flame retardant may be used independently and may use 2 or more types together.

(Other optional ingredients)
Examples of other optional components include flame retardant aids, pigments, antioxidants, reflection-imparting agents, masking agents, lubricants, processing stabilizers, plasticizers, and foaming agents.

  The flame retardant aid further enhances the flame retardancy after solidification of the adhesive composition by a synergistic effect with the flame retardant. Examples of the flame retardant aid include antimony trioxide. As a minimum of content of a flame retardant adjuvant, 5 mass parts is preferred to 30 mass parts with respect to 100 mass parts of total amounts of the first polyester and the second polyester. As an upper limit of content of a flame retardant adjuvant, 90 mass parts is preferable and 60 mass parts is more preferable. When content of a flame retardant adjuvant is less than the said minimum, there exists a possibility that the flame retardance after the said adhesive composition solidifies may become inadequate. On the other hand, when the content of the flame retardant auxiliary exceeds the above upper limit, the adhesive property of the adhesive composition may be insufficient.

  The pigment colors the adhesive composition. Various known pigments can be used as the pigment, and examples thereof include titanium oxide. As an upper limit of content of a pigment, 10 mass parts is preferable with respect to 100 mass parts of total amounts of 1st polyester and 2nd polyester, and 7 mass parts is more preferable. When content of a pigment exceeds the said upper limit, there exists a possibility that the adhesiveness of the said adhesive composition may become inadequate.

  The antioxidant prevents oxidation of the adhesive composition. Various known antioxidants can be used, and examples thereof include phenolic antioxidants. As an upper limit of content of antioxidant, 5 mass parts is preferable with respect to 100 mass parts of total amounts of 1st polyester and 2nd polyester, and 3 mass parts is more preferable. When content of antioxidant exceeds the said upper limit, there exists a possibility that the adhesiveness of the said adhesive composition may become inadequate.

<Method for producing adhesive composition>
The adhesive composition is prepared by kneading a composition containing a first polyester, a second polyester, a phosphorus-based flame retardant, and, if necessary, a nitrogen-based flame retardant, another flame retardant, or other optional components, with a kneader. Can be prepared. Examples of the kneading machine include an open roll, a kneader, and a twin-screw mixing extruder.

[Insulating film]
FIG. 1 is a schematic cross-sectional view showing a main part of an insulating film according to an embodiment of the present invention. An insulating film 1 in FIG. 1 includes a resin film 2 and an adhesive layer 3 laminated on one surface of the resin film 2.

<Resin film>
The resin film 2 functions as a protective film such as a flat cable and a flexible printed wiring board (FPC) described later. This resin film 2 is used to improve wear resistance, voltage resistance, etc., and has an insulating resin material as a main component. Here, the “main component” is a component having the highest content, for example, a component having a content of 50% by mass or more.

  Examples of the insulating resin material include polyester, polyphenylene sulfide, and polyimide. As the insulating resin material, a versatile polyester for a flat cable is preferable.

  Examples of the polyester include those described in the adhesive composition. As the polyester, polyethylene terephthalate is preferable from the viewpoint of electrical characteristics, mechanical characteristics, cost, and the like.

  The resin film 2 may have a surface treated on one surface in order to enhance adhesion. Examples of the surface treatment include corona treatment. By performing such corona treatment, a polar functional group such as a hydroxyl group or a carbonyl group is introduced on the surface of the resin film 2 to impart hydrophilicity. The corona treatment is effective when polyphenylene sulfide is used as the insulating resin material, but may be arbitrarily performed when other insulating resin materials are used. Further, the surface treatment can be performed by other methods such as chemical treatment.

  What is necessary is just to set the length dimension and width dimension of the resin film 2 suitably according to a use etc. As a minimum of average thickness of resin film 2, 6 micrometers is preferred, 9 micrometers is more preferred, and 12 micrometers is still more preferred. On the other hand, the upper limit of the average thickness of the resin film 2 is preferably 75 μm, more preferably 50 μm, and still more preferably 40 μm. If the average thickness of the resin film 2 is less than the above lower limit, the rigidity may be insufficient. Conversely, if the average thickness of the resin film 2 exceeds the above upper limit, the flexibility may be insufficient.

<Adhesive layer>
The adhesive layer 3 is formed by the above-described adhesive composition. The adhesive layer 3 has a role of bonding the insulating film 1 to another member. The adhesive layer 3 is adhered to an adhesive layer of a conductor or other insulating film when, for example, a flat cable described later is manufactured, and a conductive pattern is formed on the base film when manufacturing a flexible printed wiring board (FPC). Is bonded to the substrate on which is formed.

  The lower limit of the average thickness of the adhesive layer 3 is preferably 10 μm, and more preferably 30 μm. On the other hand, the upper limit of the average thickness of the adhesive layer 3 is preferably 100 μm, and more preferably 80 μm. If the average thickness of the adhesive layer 3 is less than the above lower limit, the adhesion may not be sufficiently secured. On the other hand, when the average thickness of the adhesive layer 3 exceeds the upper limit, the adhesiveness between the conductor and other adhesive layers may be reduced.

[Insulating film manufacturing method]
The method for manufacturing the insulating film includes a step of laminating the adhesive composition on one surface of the resin film 2.

<Lamination process>
A lamination process can be performed by aligning the film formed with the said adhesive composition, for example, and the resin film 2, and heat-pressing these. By this step, the insulating film 1 in which the film (adhesive layer 3) formed from the adhesive composition and the resin film 2 are integrated is obtained. The pressure heating can be performed using, for example, a heating laminator provided with a heating roller, a heating press machine, or the like. The heating temperature is, for example, 50 ° C. or higher and 200 ° C. or lower.

  A film formed from the adhesive composition can be obtained by extruding the adhesive composition into a film. Extrusion molding can be performed, for example, by a melt extrusion method such as a T-die method or an inflation method.

[Flat cable]
The flat cable 4 in FIG. 2 is obtained by sandwiching a plurality of conductors 5 arranged in a stripe pattern between a pair of insulating films 1A and 1B.

  The pair of insulating films 1A and 1B is the same as the insulating film 1 shown in FIG. The resin films 2A and 2B and the adhesive layers 3A and 3B have the same composition, average thickness and characteristics as the resin film 2 and the adhesive layer 3 of the insulating film 1 in FIG. Description is omitted.

  The conductor 5 is made of a conductive metal such as copper, tin-plated annealed copper, or nickel-plated annealed copper. The conductor 5 is preferably a foil-like conductive metal. What is necessary is just to determine the average thickness of the conductor 5 according to the electric current amount etc. which are used, for example, when making the conductor 5 into foil shape, they are 20 micrometers or more and 100 micrometers or less. If the average thickness of the conductor 5 is less than the above lower limit, the mechanical strength of the conductor 5 may be insufficient. On the contrary, if the average thickness of the conductor 5 exceeds the upper limit, the flat cable 4 may become unnecessarily thick or the flexibility may be insufficient.

<Flat cable manufacturing method>
Such a flat cable 4 can be manufactured by sandwiching the conductor 5 between the pair of insulating films 1A and 1B and heating and pressing.

[Other Embodiments]
The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is not limited to the configuration of the embodiment described above, but is defined by the scope of the claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims. The

  For example, in the insulating film 1, an anchor coat layer may be formed between the resin film 2 and the adhesive layer 3 in order to improve the adhesiveness between the resin film 2 and the adhesive layer 3. Any material can be used for the anchor coat layer. For example, a urethane anchor coat material in which an isocyanate curing agent is mixed with polyurethane as a main agent is preferable. The average thickness of the anchor coat layer is preferably 0.5 μm or more and 5 μm or less.

  The insulating film 1 can be suitably used for electric wires, flexible printed wiring boards (FPCs) and the like other than flat cables.

  In the manufacturing method of the insulating film 1, the laminating step makes the adhesive composition into a solution by heating or dissolving in a solvent, and then cooling or drying after applying the solution of the adhesive composition to one surface of the resin film 2. You may go by doing. Moreover, the said lamination process may adhere | attach the film and resin film 2 which are formed with the said adhesive composition with an adhesive agent. Furthermore, you may perform the said lamination process by the coextrusion molding method of resin film material and an adhesive composition.

  In the flat cable, the insulating film 1 may be bonded only to the coating material on one side of the conductor 5 and another coating material may be bonded to the other surface.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Adhesive composition No. Production of 1-10>
The first polyester, the second polyester, the phosphorus flame retardant, the nitrogen flame retardant, the pigment, and the antioxidant are mixed uniformly with a twin screw extruder to form an adhesive composition No. 1-10 were manufactured. The amount of each component was as shown in Table 1. Table 1 also shows the melt viscosity and melting point of the first polyester and the second polyester at 200 ° C.

  Adhesive composition No. The melt viscosity and melting | fusing point in 200 degreeC of the 1st polyester and 2nd polyester which were used for manufacture of 1-10, a phosphorus flame retardant, a nitrogen flame retardant, a pigment, and antioxidant are shown below. Among the first polyester and the second polyester, those having a melting point are crystalline polyesters, and those having “no melting point” are non-crystalline polyesters.

First polyester (A1): melt viscosity at 200 ° C. 100 Pa · s, melting point 107 ° C.
First polyester (A2): melt viscosity at 200 ° C. 150 Pa · s, melting point 138 ° C.
First polyester (A3): Melt viscosity at 200 ° C. 260 Pa · s, no melting point

Second polyester (B1): melt viscosity at 200 ° C. 400 Pa · s, melting point 166 ° C.
Second polyester (B2): Melt viscosity at 200 ° C. 460 Pa · s, melting point 143 ° C.
Second polyester (B3): Melt viscosity at 200 ° C. 650 Pa · s, melting point 126 ° C.
Second polyester (B4): Melt viscosity at 200 ° C. 800 Pa · s, melting point 111 ° C.

Phosphorus flame retardant (C1): Phosphinic acid aluminum salt Phosphorus flame retardant (C2): Polyphosphazene Phosphorus flame retardant (C3): 9,10-dihydro-10- (2,5-dihydroxyphenyl) -9-oxa -10-phosphaphenanthrene 10-oxide (“HCA-HQ” from Sanko Co., Ltd.)

Nitrogen-based flame retardant: Melamine cyanurate Pigment: Titanium oxide Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” of BASF Japan Ltd.) ")

<Preparation of insulation film>
Adhesive composition No. 1 was formed by melt extrusion to produce a film having an average thickness of 40 μm and a width of 1000 mm. Next, an anchor coating agent was applied to a resin film made of PET having an average thickness of 12 μm (“Lumirror P60” manufactured by Toray Industries, Inc.) so that the average thickness after drying was 3 μm. As an anchor coat agent, what mixed 10 mass parts of "Takelac A-515" of Mitsui Chemicals, Inc. and 1 mass part of "Takenate A-12" of Mitsui Chemicals, Inc. was used. And the film formed by the resin film, the anchor coat layer, and the adhesive composition is laminated in this order, and by pressurizing and heating with a heating laminator heated to 60 ° C., the average thickness is 55 mm and the width is 1000 mm. An insulating film was produced. Furthermore, this insulating film was used by slitting to a width of 50 to 200 mm.

<Flat cable production>
Forty conductors are arranged in parallel at a pitch of 0.5 mm, these conductors are sandwiched between a pair of the insulating films, and subjected to pressure heat treatment with a heating laminator heated to 160 ° C. to obtain an average thickness of 0. A long cable with a width of 14 mm and a width of 22 mm was obtained. As the conductor, tin-plated annealed copper foil having an average thickness of 0.035 mm and an average width of 0.3 mm was used. Thereafter, the flat cable No. 1 was cut by cutting the long cable into a length of 500 mm. 11 was produced.

  Adhesive composition No. In place of adhesive composition No. 1 The flat cable No. In the same manner as in FIG. 12-20 were produced.

<Evaluation items>
About said flat cable, it evaluated by the following method.

(Dispersibility of phosphorus flame retardant)
The dispersibility of the phosphorus-based flame retardant is determined by observing the surface of the insulating film, and the number of aggregates having a diameter of 200 μm or more per 1 m ² is less than 10 “A”, 10 to less than 50 “B”, 50 The above was designated as “C”.

(Flame retardance)
The flame retardancy was evaluated by a vertical flame test (VW-1 test) defined by UL standards. A flat cable that satisfies the standard defined by the UL standard was accepted (“G”), and a flat cable that did not meet the standard was rejected (“NG”).

(Heat-resistant)
The heat resistance is whether or not peeling between insulating films, peeling between a resin film and an adhesive layer, and cracking occur after leaving a flat cable in a folded state in a 120 ° C. constant temperature bath for 7 days. Evaluated by. The case where peeling or cracking did not occur was regarded as acceptable (“G”), and the case where peeling or cracking occurred was regarded as unacceptable (“NG”). These evaluation results are shown in Table 2.

  As shown in Table 2, the flat cable No. In Nos. 11 to 18, good results were obtained with respect to the dispersibility, flame retardancy, and heat resistance of the phosphorus-based flame retardant. On the other hand, the flat cable No. In No. 19, good results were obtained with respect to heat resistance, but good results were not obtained with respect to dispersibility and flame retardancy of the phosphorus-based flame retardant. Also, the flat cable No. For No. 20, good results were obtained for the dispersibility and flame retardancy of the phosphorus flame retardant, but no good results were obtained for heat resistance.

  As described above, the adhesive composition according to one embodiment of the present invention is excellent in heat resistance, appearance, flame retardancy, and electrical characteristics after solidification, and can be suitably used for insulating films and flat cables. Moreover, the manufacturing method of the insulating film of this invention can manufacture the insulating film excellent in heat resistance, an external appearance, a flame retardance, and an electrical property.

1, 1A, 1B Insulating film 2, 2A, 2B Resin film 3, 3A, 3B Adhesive layer 4 Flat cable 5 Conductor

Claims (7)

One or more first polyesters having a melt viscosity of less than 350 Pa · s at 200 ° C.,
One or more second polyesters having a melt viscosity at 200 ° C. of 350 Pa · s or more, and a phosphorus-based flame retardant,
The content of the first polyester with respect to the total amount of the first polyester and the second polyester is 10% by mass to 80% by mass,
The content of the second polyester with respect to the total amount of the first polyester and the second polyester is 20% by mass or more and 90% by mass or less,
The content of the phosphorus flame retardant with respect to 100 parts by mass of the total amount of the first polyester and the second polyester is 20 parts by mass or more and 60 parts by mass or less,
At least one of the first polyester and the second polyester is a crystalline polyester,
The melting point of this crystalline polyester is 100 ° C. or higher,
The phosphorus flame retardant Ri solid der in melting point of the crystalline polyester,
Further containing a nitrogen-based flame retardant,
The first polyester and the adhesive composition content of Ru der than 75 parts by mass or more 10 parts by weight of the second polyester the nitrogen-based flame retardant to the total amount 100 parts by mass. One or more first polyesters having a melt viscosity of less than 350 Pa · s at 200 ° C.,
One or more second polyesters having a melt viscosity at 200 ° C. of 350 Pa · s or more, and
Contains phosphorus flame retardants,
The content of the first polyester with respect to the total amount of the first polyester and the second polyester is 10% by mass to 80% by mass,
The content of the second polyester with respect to the total amount of the first polyester and the second polyester is 20% by mass or more and 90% by mass or less,
The content of the phosphorus flame retardant with respect to 100 parts by mass of the total amount of the first polyester and the second polyester is 20 parts by mass or more and 60 parts by mass or less,
At least one of the first polyester and the second polyester is a crystalline polyester,
The melting point of this crystalline polyester is 100 ° C. or higher,
The phosphorus flame retardant is solid at the melting point of the crystalline polyester;
Further containing a nitrogen-based flame retardant,
Adhesives compositions the nitrogen-based flame retardant is Ru solid Der in melting point of the crystalline polyester. The adhesive composition according to claim 1 or 2 , wherein a difference between a melt viscosity at 200 ° C of the first polyester and a melt viscosity at 200 ° C of the second polyester is 100 Pa · s or more. The adhesive composition according to claim 1, 2 or 3 , wherein the phosphorus flame retardant comprises a phosphinic acid metal salt, polyphosphazene, phosphaphenanthrene, or a combination thereof. An insulating film comprising a resin film and an adhesive layer laminated on one surface of the resin film,
The insulating film in which the said adhesive bond layer is formed with the adhesive composition of any one of Claims 1-4 . A method for producing an insulating film comprising a resin film and an adhesive layer laminated on one surface of the resin film,
The manufacturing method of an insulating film provided with the process of laminating | stacking the adhesive composition of any one of Claims 1-5 on one surface of the said resin film. A flat cable comprising a pair of covering materials and a conductor sandwiched between these covering materials,
The flat cable in which at least one of the pair of covering materials is the insulating film according to claim 5 .

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