KR101153132B1 - Adhesive agent and coating film for electric material using the same - Google Patents

Abstract

This invention provides the adhesive agent which has the outstanding adhesive performance in the wide temperature range from low temperature to high temperature, an adhesive layer is formed using this adhesive agent, and provides the coating film for electrical materials with high durability and handleability.

The present invention has crystallinity, and the loss tangent (tanδ) in the temperature dispersion curve by dynamic viscoelasticity measurement is 4.9 × 10 ⁻² or more at −40 ° C. to 40 ° C., and the maximum peak value of the loss tangent (tanδ). It is in the range of -15 degreeC-40 degreeC, and melting | fusing point (Tm) is related with the adhesive agent which consists of a polyester type hot melt resin or a hot melt type resin composition containing the said resin.

Description

Adhesive and coating material for electrical materials using same {ADHESIVE AGENT AND COATING FILM FOR ELECTRIC MATERIAL USING THE SAME}

The present invention relates to an adhesive and a coating film for an electrical material using the same. More specifically, an adhesive layer having an adhesive property in a wide temperature range from a low temperature to a high temperature, an adhesive layer is formed using this adhesive, and can be heat-bonded by a method such as thermal lamination or hot pressing. It is related with the coating film for electrical materials suitable for the use (for example, reinforcement board (protect tape) for flexible flat cables), such as coating of the core wire of wiring wires, such as an electronic device.

The laminated | multilayer film which has the adhesive bond layer adhered by heat melting generally consists of a base material and an adhesive bond layer, and a biaxially stretched polyester film is used as a base material in consideration of mechanical strength and electrical insulation. For example, when it is necessary to provide flame retardancy to a laminated film, a flame retardant is added to an adhesive bond layer, and when it is necessary to provide concealability, a pigment, dye, etc. are added to an adhesive bond layer.

The said laminated | multilayer film is useful as structural members, such as a flat electric wire used for wiring of an electrical device, an electronic device, etc., and is used in order to coat | cover a core wire and insulate and protect. A flat electric wire is normally obtained by unifying by heat-compressing the coating body and laminated | multilayer film which are coat | covered using a heating roll or a hot press. For this reason, the laminated | multilayer film needs the adhesive bond layer which can melt and integrate by heating. As a material which comprises this adhesive bond layer, the hot melt resin which has a vinyl chloride resin, polyester resin, polyolefin resin, etc. as a main component is used.

The polyester resin generally used for forming the adhesive layer has a glass transition temperature (Tg) of 0 ° C or higher, and most of Tg near room temperature has been used. By the way, it was confirmed that the adhesive performance was remarkably lowered at the boundary of Tg, and the adhesive might peel off from the adherend when used in the same winter or low temperature range. In particular, in recent years, the adhesiveness at low temperature has been required from the viewpoint of quality. Therefore, the low-temperature characteristic was able to be improved by using what Tg is -22 degreeC or more and 0 degrees C or less as polyester type hot melt system resin composition (for example, refer patent document 1).

In addition, at the time when such an improvement was being carried out, there was no limit on improving low temperature characteristics because no commercially available polyester-based hot melt resin had a lower Tg. However, the required performance is increased year by year, and even if the conventional low Tg polyester-based hot melt resin is used, the demand for maintaining stable good adhesion properties is not satisfied, so that a polyester-based hot melt resin with high adhesion performance is required. It is becoming.

Moreover, the laminated | multilayer film which has such an adhesive bond layer was strong in self-locking (blocking) property, and when it was set as the winding object, it peeled off and was inferior to the handling characteristic in many cases. For this reason, there have been devises such as attaching a masking film to the adhesive surface.

In recent years, further demands have emerged, and only polyester-based hot melt resins cannot fully cope with the problems. For example, durability in high temperature, high humidity is also important, and the use in the field | area where more reliability is requested | required is increasing. For example, when the adhesive strength should be maintained to a certain extent for 169 hours in an environment of a high temperature and high humidity of a temperature of 80 ° C. and a humidity of 85% RH, interlayer peeling occurs because the hydrolysis of the adhesive proceeds and the cohesive force decreases as a conventional laminated film. Moreover, when this laminated | multilayer film was used for coating | covering a signal line, there existed a problem that the defects, such as a short circuit of a signal line, generate | occur | produce.

In particular, when the laminated film is used for a reinforcement plate (protect tape) used for an end portion of a flexible flat cable or the like, when the end portion is inserted into a connector, the reinforcement plate is likely to be bent due to the bending of the reinforcement plate in the winter season where the temperature decreases. The improvement of the adhesive strength at low temperature was calculated | required.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-279226

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

This invention is made | formed in view of the said situation, The adhesive agent which has the outstanding adhesive performance in the wide temperature range from low temperature to high temperature, The adhesive film is formed using this adhesive agent, The coating film for electrical materials with high durability and handleability, It aims at providing the film useful for the reinforcement board (protect tape) used especially at the edge part of flexible flat cables.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the crystalline polyester type hot melt resin or hot melt containing this resin is characterized by the loss tangent (tan-delta) in the temperature dispersion curve by dynamic viscoelasticity measurement, and having a predetermined melting point. It discovered that the said subject could be solved by the resin composition, and came to complete this invention based on this knowledge.

That is, this invention provides the following adhesives and the coating film for electrical materials.

1. With crystallinity, the loss tangent (tanδ) in the temperature dispersion curve by dynamic viscoelasticity measurement is 4.9 × 10 ⁻² or more at −40 ° C. to 40 ° C., and the maximum peak value of the loss tangent (tanδ) is The adhesive agent which consists of a polyester type hot melt resin in the range of -15 degreeC-40 degreeC, and melting | fusing point (Tm) is 95 degreeC-130 degreeC, or the said hot melt type resin composition containing this resin.

2. The adhesive according to the above 1, wherein the hot melt resin composition contains 0.05 to 2 parts by mass of the oxazoline-based additive with respect to 100 parts by mass of the polyester-based hot melt resin.

3. The adhesive according to the above 1, wherein the hot melt resin composition contains 0.05 to 2 parts by mass of a carbodiimide-based additive with respect to 100 parts by mass of the polyester-based hot melt resin.

4. Coating film for electrical materials formed by forming an adhesive bond layer on the at least one surface of a plastic base film using the adhesive agent in any one of said 1-3.

5. Coating film for electrical materials of said 4 whose surface roughness of an adhesive bond layer is 10-point average roughness (Rz) 1 micrometer or more.

6. Cover film for electrical materials of said 5 whose surface roughness of an adhesive bond layer is 10 micrometers of 10-point average roughness (Rz) or more.

7. Coating film for electrical materials in any one of said 4-6 used by bonding for reinforcement of electrical materials.

8. The covering film for electrical materials according to item 7, wherein the electrical material is a flexible flat cable.

Effects of the Invention

ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent which has adhesiveness can be obtained in a wide temperature range from low temperature to high temperature, and the coating film for electrical materials formed by laminating | stacking this adhesive agent is high in durability and handleability.
Best Mode for Carrying Out the Invention

The adhesive agent of this invention consists of crystalline polyester-type hot melt resin or the polyester-type hot melt resin composition containing this resin. The polyester-based hot melt resin may be a mixture of two or more kinds. In addition, the polyester type hot melt resin composition adds the additive mentioned later to the polyester type hot melt resin. Polyester-based hot melt resins are polycondensation polymers of dibasic acids and glycols. Specific examples of the dibasic acid include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid and the like. Examples of the glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.

As the crystalline polyester hot melt resin used in the present invention, two or more polyester hot melts are used in processing steps such as an adhesive coating step rather than producing a polyester hot melt resin having predetermined viscoelastic properties by polymerization. Obtaining a polyester-based hot melt resin having predetermined viscoelastic properties by mixing the resin has a high effect in improving the self-adhesiveness described later.

In this case, as a crystalline polyester type hot melt resin to mix, an incompatible thing is preferable. When mixing an incompatible polyester hot melt resin, for example, a polyester hot melt resin having a glass transition temperature (hereinafter abbreviated as Tg), which is crystalline and has a range of -5 ° C to 40 ° C as a main component, And the method of polymer-mixing the low Tg polyester-type hot melt resin below -5 degreeC is mentioned. In this case, a resin having a Tg of -5 ° C to 40 ° C exists in the domain portion, and a resin of less than -5 ° C that raises the low temperature property exists as a matrix, so that self-adhesiveness is improved while maintaining the low temperature property. .

On the other hand, in the case of mixing a compatible polyester-based hot melt resin, even when using two or more resins, the kneading machine used at the time of extrusion film formation is mutually related to each other's Tg and melting point (hereinafter abbreviated as Tm). Because it causes the action, it causes an increase in Tg or a drop in Tm. For this reason, finally, it will be in the same state as when using a primary resin, and there exists a possibility that a sufficient effect may not be acquired.

In addition, in the case where an amorphous resin having a low Tg is used, the embossed shape collapses and the contact area gradually increases and the self-adhesion property is increased even if the adhesive layer is embossed to the adhesive layer of the present invention described later. It becomes high and a defect occurs at the time of use. The defect is improved by using a crystalline polyester-based hot melt resin.

As a polyester type hot melt resin, a commercially available thing can be used, for example, and the brand names "Byron GM900", "Byron GM920", "Byron GA6400" by Toyo Spinning Co., Ltd., and a brand name by Toyo Spinning Co., Ltd. "Byron GM990", "Byron GA5410", "Byron GM995", brand name `` Aron Melt PES111 '', `` PES111EE '', `` Alon Melt PES120E '', `` Alon Melt PES120H '', Toray Corporation made by Dong-A Synthetic Co., Ltd. The brand name "Kemi R248" etc. can be mentioned, The target polyester type hot melt resin can be obtained by mixing these as needed.

When the adhesive constituting the adhesive layer contains only one kind of polyester-based hot melt resin as an active ingredient, the loss tangent (tanδ) in the temperature dispersion curve by dynamic viscoelasticity measurement of the polyester-based hot melt resin is -40. It is necessary that it is 4.9x10 <^-2> or more in the range of -40 degreeC. When using the mixture of 2 or more types of polyester-type hot melt resins as an active ingredient, it is necessary that loss tangent (tan-delta) in this mixture is 4.9x10 <^-2> or more in -40 degreeC-40 degreeC range.

In the present invention, the polyester hot melt resin needs to have a melting point (Tm) in the range of 95 to 130 ° C, and preferably in the range of 100 to 120 ° C. If polyester type hot melt resin is crystalline and Tm is 95 degreeC or more, heat resistance will improve, and if Tm is 130 degrees C or less, the adhesiveness of the coating film for electrical materials of this invention becomes favorable. In the case of using a mixture of two or more polyester-based hot melt resins, the polyester-based hot melt having a Tm outside the range of 95 to 130 ° C in a range where the Tm of the mixture is in the range of 95 to 130 ° C and does not impair the effects of the present invention. Melt resin can be mixed. In addition, in the following description, polyester-type hot melt resin shall also include the case where it is a mixture which mixed 2 or more types.

The polyester-based hot melt resin used in the present invention needs to have a maximum peak value of the loss tangent (tanδ) in the range of -15 ° C to 40 ° C, and is -5 ° C or more from the viewpoint of handleability (antiblocking property). It is preferable.

In the polyester-based hot melt resin, the ester group in the backbone of the polymer is likely to be decomposed by water, and in particular, the decomposition is accelerated by water and heat, and the adhesive force decreases due to molecular weight decrease. In order to prevent this adhesive force fall, the polyester hot melt resin composition which added the oxazoline type additive and / or the carbodiimide type additive to the polyester type hot melt resin is preferable as an adhesive agent. Since the three-dimensional crosslinking is carried out when extrusion molding the resin composition, the heat and moisture resistance is improved, and 169 hours in an environment of a temperature of 80 ° C. and a relative humidity of 85% (hereinafter abbreviated as “80 ° C. × 85% RH”). It is possible to maintain sufficient cohesion even after leaving.

The oxazoline-based additive or the carbodiimide-based additive has an effect of capturing an acid component that promotes hydrolysis when subjected to extrusion processing or a wet heat resistance endurance test. Moreover, since it has the effect of extending | stretching chain by reacting with the terminal acids of the polyester component which generate | occur | produced by decomposition, the molecular weight fall of polyester-type hot melt resin can be prevented.

Oxazoline-based additives or carbodiimide-based additives theoretically increase durability as the amount of the additive is increased. However, care should be taken because the crosslinking reaction during processing may cause thickening or gelation. The amount of addition should be determined by considering the thermal properties.

Therefore, the addition amount of an oxazoline type additive, a carbodiimide type additive, or the additive which combined these has the preferable range of 0.05-2 mass% with respect to 100 mass parts of polyester-type hot melt resins, and makes processing characteristics favorable 0.05-0.5 mass% is more preferable at the point. As an oxazoline type additive used for this invention, a commercially available thing can be used, for example, the brand name "1-3PBO" by the Mikuni Chemical Co., Ltd., and the brand name "Epoclos RPS" by Nihon Shokubai Co., Ltd. -1005 ", and the like. Examples of carbodiimide-based additives include Nisshin Spinning Co., Ltd. product name "Carbodiilite HMV08CA", Bayer Co., Ltd. product name "Starbakzol I", "Starbakzol P", and the like.

In order to improve processability and functionality, the adhesive of the present invention may contain polyolefin resin, epoxy or the like as an active ingredient as necessary. These also have the effect of stress relaxation and crystallization promotion. Examples of the polyolefin resin include high density polyethylene, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate-maleic anhydride terpolymer, Ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-methacrylate glycidyl copolymer, ethylene-vinyl acetate-methacrylate glycidyl terpolymer, ethylene-ethyl acrylate-methacrylate And dill terpolymers. These can be used individually by 1 type or in combination of 2 or more type. Moreover, what provided adhesive functions, such as acid denaturation, can also be used as needed. However, when the acid-modified adhesive resin is used, hydrolysis may occur during extrusion processing or when performing a heat and humidity resistance test, which may lead to deterioration in performance.

In addition, although both bisphenol-A type and novolak-type can be used as an epoxy resin, it is preferable that a softening point is 100 degreeC around 100 degreeC from a viewpoint of compatibility and adhesiveness. Moreover, since epoxy resin is very effective for metal adhesion, when it is added in trace amount according to a use, adhesive strength with respect to a metal improves. However, if it is added more than necessary, it will bleed at the time of film forming processing, and therefore, it may adversely affect and be careful.

The addition amount of polyolefin resin is about 1-40 mass parts normally with respect to 100 mass parts of polyester-type hot melt resins, Preferably it is 5-10 mass parts. The addition amount of an epoxy resin is about 1-10 mass parts normally with respect to 100 mass parts of polyester type hot melt resins, Preferably it is 2-5 mass parts.

The product which coat | covered the coating film for electrical materials of this invention often requires a flame retardance. Therefore, it is preferable that the adhesive bond layer of a coating film, ie, the adhesive agent of this invention, contains a flame retardant so that this coating film itself may be self-extinguishing. As the flame retardant, a flame retardant mainly composed of halogen-based compounds such as fluorine and chlorine is particularly preferable, but a mixture mainly composed of known additive flame retardants such as phosphorus, nitrogen, and metal hydroxide may be used. These flame retardants can be used in the addition amount within the range which does not adversely affect the physical property of an adhesive agent.

It is preferable from the viewpoint of workability that the adhesive of the present invention has appropriate fluidity. As a melt viscosity value which is an index of a suitable fluidity | liquidity, it is preferable that the measured value by the high-priced flow meter at the measurement temperature of 160 degreeC and the shear rate of 10 sec <^-1> is 300-5,000 Pa.s. If the melt viscosity of the adhesive is 300 Pa · s or more, the adhesive does not bleed out of the plastic film serving as the substrate when it is heated and pressurized, so that there is no risk of problems during manufacturing. Moreover, when melt viscosity is 5,000 Pa * s or less, since fluidity | liquidity is enough, defects, such as a space generate | occur | produced between a coating body and a coating film, will not generate | occur | produce.

The coating film for electrical materials of this invention is a coating film in which the adhesive bond layer was formed in at least one surface of the plastic base film using the said adhesive agent. In addition, generally, the boundary between a film and a sheet is not defined, and it is difficult to distinguish clearly, and "film" in this invention shall include both a film and a sheet. In the present invention, the thickness of the adhesive layer is preferably in the range of 0.1 to 2.0 times the thickness of the plastic base film in consideration of the thickness of the object to which the coating film is applied.

In this invention, an adhesive bond layer has a function which exhibits adhesiveness at low temperature. In the case where an adhesive having a low Tg is used, processing is often performed at a temperature of Tg or more, so that blocking is likely to occur in the coated film at the time of use of the coating film for electrical materials. In particular, blocking is likely to occur when the coating film is wound on a roll before the crystallization of the crystalline polyester-based hot melt resin as the main component is completed.

Therefore, it is preferable to take the following means as a means for preventing blocking. That is, if the crystalline polyester-based hot melt resin, which is the main component of the adhesive, is sufficiently crystallized, the self-adhesion becomes low and does not interfere with the handleability. However, it is difficult to secure the time to complete the crystallization in-line. For this reason, it is necessary to reduce the contact area on the surface of the adhesive force. Therefore, in order to reduce self-adhesion until it fully crystallizes, it is suitable to provide a fine unevenness | corrugation on the adhesive bond layer surface.

Specifically, it is preferable that surface roughness of an adhesive bond layer is 10 micrometers or more of 10-point average roughness (Rz), More preferably, it is 10 micrometers or more. In particular, the film formation rate can be increased by adhering such minute irregularities to the coated film and crystallizing the polyester-based hot melt resin after rolling up the coated film. However, the surface roughness is easily affected even when the film is rolled up, and when the winding tension is strong, the surface roughness of the adhesive layer may change, so care should be taken.

As a method of providing the minute unevenness on the surface of the adhesive, embossing transfer is performed on a cooling roll coated with frost on both sides when the coated film is wound on the roll during the production of the coated film described later and when the resin temperature is high. Embossing can be transferred to the surface of an adhesive bond layer by the method of implementing or the method of using an embossing film.

Furthermore, when the surface of the adhesive layer is flat, when bonding the coating film using a hot stamp type bonding machine, since the bottom of the processing machine itself rises considerably due to the preheating of the hot stamp, the adhesive surface melting starts with extra heat. In this case, the air sucked into the adherend becomes difficult to come out during this bonding, and air is often mixed with the adherend, so that sufficient adhesive strength cannot be obtained. Or, a coating film may exceed the predetermined thickness from mixing of air.

Such a defect can also be improved in the case of using a hot stamp type bonding machine by making a small embossing process on the surface of the adhesive layer.

In the coating film of the present invention, examples of the plastic base film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylpentene (manufactured by Mitsui Petrochemical Co., Ltd., trade name "TPX"), and stretched polypropylene (OPP). ) And a film produced from unstretched polypropylene (CPP) or the like. From the viewpoint of mechanical strength and heat resistance, polyethylene terephthalate (PET) films and polyethylene naphthalate (PEN) films are preferred, and biaxially stretched PET films and biaxially stretched PEN films are preferred.

In this invention, although the thickness of a plastic base film is not specifically limited, Usually, it can be about 12-250 micrometers.

As a method of providing an adhesive layer to the plastic substrate film by using the adhesive, in the so-called solvent coating method which is prepared by dispersing an adhesive component or the like in a solvent and applying it on a substrate, and a so-called solventless coating method without a solvent. Although any method can be adopted, it is preferable to manufacture by what is called a solventless coating method in this invention.

A conventional coating method can be applied to the solvent-free coating method, and what kind of coating method should be determined by melt viscosity, thermal stability, etc. of an adhesive agent. For example, a method of uniformly kneading each component of the adhesive using an extruder, a kneader, etc., and then cooling it once, reheating it with a hot melt applicator or the like, and uniformly kneading with a lip coater or the like and coating on a substrate, etc. Can be mentioned. Or after uniformly kneading each component of an adhesive agent and forming into a film form, this film adhesive and a base material may be bonded together and a coating film may be formed. Joining can be performed, for example by methods, such as heat press bonding.

In order to improve the adhesiveness of a plastic base film and an adhesive bond layer, the corona discharge process can be given to the adhesive bond layer side in this base film, and an anchor coat layer can be provided on a base film as needed. As an adhesive agent for anchor coats used for an anchor coat layer, adhesive agents, such as polyester type, a polyurethane type, an acryl type, and a vinyl chloride-vinyl acetate copolymerization system, are mentioned. Moreover, the coating methods, such as the roll coat method and the gravure coat method, are used suitably for application | coating of the adhesive agent for anchor coats.

In this invention, before extending | stretching a base film, an anchor coat layer can also be formed by laminating | stacking an adhesive bond layer for anchor coats, and extending | stretching a base material and an adhesive bond layer for anchors simultaneously. The thickness of the anchor coat layer can usually be about 0.1-5 micrometers.

Although an Example demonstrates this invention in detail below, this invention is not limited at all by these examples. In addition, various measurements and evaluation in the polyester-type hot melt resin used in the Example etc. were performed as follows.

(1) Measurement of glass transition temperature (Tg) and melting point (Tm)

The glass transition temperature (Tg) and melting point (Tm) of the polyester-type hot melt resin were measured on the conditions of the temperature -60 degreeC-200 degreeC, and the scanning speed of 10 degreeC / min using the differential scanning calorimeter (perkin elmer company make).

(2) Measurement of loss modulus in temperature dispersion curve by dynamic viscoelasticity measurement

The loss elastic modulus in the temperature dispersion curve by the dynamic viscoelasticity measurement of a polyester-type hot melt resin composition or a hot melt resin was measured using the dynamic-viscoelasticity measuring apparatus (product made by Haiti Japan Co., Ltd.). Measurement conditions were made into strain mode tension, temperature -100 degreeC-measurement limit temperature, and a temperature increase rate of 3 degree-C / min.

(3) Measurement of 10-point average roughness (Rz)

The surface roughness of the adhesive bond layer was measured using the three-dimensional roughness measuring instrument (made by Kosaka Research Institute).

Examples 1-5 and Comparative Examples 1-4

As the adhesive, polyester-based hot melt resins shown in Tables 1-1 and 1-2 were used. In the case of mixing two kinds of resins, the polyester-based hot melt resins of the amounts shown in Tables 1-1 and 1-2 are sufficiently premixed with a Henschel mixer, and the temperature is set so that the resin temperature from the detention is 180 ° C. It injected into the extruder, extruded in the sheet form, and cooled with the cast roll, and formed the 50-micrometer-thick film for adhesive bond layers. In the case of one type of polyester-based hot melt resin, it was charged into the extruder without premixing.

Laminating a base film [100 μm-thick biaxially stretched polyethylene terephthalate (PET) film) subjected to a polyurethane anchor coat and the adhesive layer film by using a lamination roll set at a temperature higher than the melting point of the adhesive using a lamination roll. The film was produced.

In order to apply frost on the surface, the adhesive layer of the obtained laminated | multilayer film transferred the surface frost to the adhesive surface by the frosted cooling roll before resin solidified after heat lamination, and produced the coating film.

In the obtained coating film, evaluation shown below was performed. The results are shown in Tables 1-1 and 1-2. In addition, the evaluation results of the obtained adhesiveness, handleability, heat resistance, and bonding properties are also subjected to comprehensive judgment, and "◎" is extremely good, "○" is good, "△" is slightly good, and "×". It was impossible to use.

(1) Preparation of Sample 1 for Evaluation

Two obtained coating films were overlapped so that adhesive layers faced each other, sandwiched between a set of rolls (metal rolls / rubber rolls), one of which consists of a heated metal roll and the other unheated rubber roll, and the roll nip pressure is Sample 1 for evaluation was produced under the conditions of 98 N / cm (linear pressure) and the joining speed of 0.5 m / min. However, when an adhesive agent included 2 types of polyester type hot melt resin, the joining temperature was bonded on 20 degreeC higher temperature conditions than the higher Tm in these resin.

(2) Evaluation of low temperature adhesiveness (measurement of peeling strength)

The prepared sample 1 for evaluation was cut into a width of 10 mm, and a tensile tester (incubator attached material tester "201X", manufactured by Intesco Co., Ltd.) was used under each atmosphere at a temperature of -10 ° C to 0 ° C for each 10 ° C. Peel strength of 180 degrees was measured at a peel rate of 10 mm / min. About the measurement result, it evaluated based on the evaluation criteria shown below, and represented by symbol. In this invention, when a measured value is 500 g / cm or more, it is a level which is satisfactory practically.

<Evaluation Criteria>

1500g / cm or more or cohesive failure, substrate failure: A

1000 g / cm or more and less than 1500 g / cm: B

500 g / cm or more and less than 1000 g / cm: C

Less than 500g / cm: D

(3) evaluation of heat resistance

The produced sample 1 for evaluation was cut out to the size of 60 mm x 90 mm, leaned in the oven of 100 degreeC at the angle of inclination of 45 degree | times, and it investigated whether the flow of an adhesive agent and the sample were bent. In this case, when neither the flow of an adhesive agent nor the curvature of a sample was confirmed, it evaluated as "defect" when either of "good", the flow of an adhesive agent, or the curvature of a sample was confirmed.

(4) handleability evaluation

Antiblocking property (blocking resistance) a and b were evaluated. The obtained coating film was cut | disconnected to width 5cm and length 20cm. Two cut coating films were superposed so that the adhesive layer surfaces faced each other, a load of 4.9 N was maintained in an oven at a temperature of 40 ° C. for 24 hours, and taken out to prepare a sample a for evaluation. Moreover, what superimposed the adhesive bond layer surface of the cut | discovered coating film on the unprocessed PET film (thickness 100 micrometers) was carried out after carrying out the load of 4.9N for 24 hours in 40 degreeC oven, and took out, and produced the sample b for evaluation.

With respect to the obtained two types of evaluation samples a and b, a 180 ° peel strength at a peel rate of 10 mm / min using a tensile tester (a constant temperature layer material tester "201X", manufactured by Intesco) under a 23 ° C atmosphere. Was measured and the anti blocking properties of samples a and b were evaluated based on the following criteria. If the measured value is less than 300 g / cm, the level is practically no problem.

<Evaluation Criteria>

Less than 100 g / cm: A

100 g / cm or more and less than 300 g / cm: B

300 g / cm or more: C

(5) Bondability (adhesion evaluation in 23 ° C atmosphere)

The obtained coating film was cut into width 30cm and length 40cm. Two sheets of cut | disconnected coating films were overlapped so that an adhesive bond layer might face each other, and it hold | maintained for 1 minute under the press temperature of 120 degreeC, and pressure of 0.3 MPa, and cooled to room temperature, and produced sample c for evaluation. In addition, the adhesive layer obtained by cutting the obtained coated film into a width of 30 cm and a length of 40 cm was superimposed on an untreated PET film (thickness of 100 μm) and held at the same press temperature and pressure as described above for 1 minute, and then cooled to room temperature to evaluate the sample for evaluation. d was produced.

For each of the two types of evaluation samples c and d obtained, a peel test was performed at a peel rate of 10 mm / min for 180 degrees using a tensile tester (thermostat material tester "201X", manufactured by Intesco) under a 23 ° C atmosphere. Was measured and evaluated based on the evaluation criteria shown below for joining characteristics c and d. If the measured value is 1000 g / cm or more, it is a level which is satisfactory practically.

<Evaluation Criteria>

1500g / cm or more or cohesive failure, substrate destruction: A

1000 g / cm or more and less than 1500 g / cm: B

500 g / cm or more and less than 1000 g / cm: C

Less than 500g / cm: D

(week)

1) Byron GM920: polyester hot melt resin, manufactured by Toyo Spinning Co., Ltd.

2) Byron GA6400: polyester hot melt resin, manufactured by Toyo Spinning Co., Ltd.

3) Aaron Melt PES111: Polyester-based hot melt resin, manufactured by Dong-A Synthetic Co., Ltd.

4) Aaron Melt PES120H: Polyester-based hot melt resin, Dong-A Synthetic Co., Ltd.

5) Aaron Melt PES126E: Polyester-based hot melt resin, manufactured by Dong-A Synthetic Co., Ltd.

6) Chemit R248: polyester-based hot melt resin, manufactured by Toray Co., Ltd.

As is apparent from Tables 1-1 and 1-2, the coated films of Examples 1 to 5 exhibited good adhesion in the low temperature region of 0 ° C or lower, and also described in the adhesive flow chart described in the high temperature region of 100 ° C. It is known that it is possible to provide good bonding at a temperature of 120 ° C. without deformation, and to provide a surface roughness of 1 μm or more on the surface of the adhesive layer, thereby providing a material excellent in handling and workability even at low temperature materials. It became. That is, since these coating films are the high level which can be practical in any of evaluation, it turned out that they show more than a favorable level in comprehensive judgment.

Example 6

Additives of the type and amount shown in Table 2-1 and Table 2-2 were added to the adhesive component used in Example 1 and sufficiently premixed in a Henschel mixer to set the temperature so that the resin temperature resulting from the detention was the temperature shown in Table 2. It injected into the extruder, extruded in the sheet form, and cooled with the cast roll, and formed the 50-micrometer-thick film for adhesive bond layers.

The base material (100 micrometer-thick biaxially stretched PET film) on which the polyurethane-type anchor coat was applied, and the formed adhesive layer film were bonded together using the lamination roll set to 20 degreeC higher than melting | fusing point of an adhesive, and the laminated film which has an adhesive bond layer was produced. In order to apply frost to the surface, the adhesive side of the laminated | stacked film transferred the surface frost to the adhesive surface in the frosted cooling roll after heat lamination, and before resin solidified, and produced the coating film.

In addition, for the comparison, the same operation was performed also about the thing which did not add the additive, and the coating film was produced. The following evaluation was performed about the obtained coating film. The results are shown in Table 2-1 and Table 2-2.

(1) Evaluation of heat and humidity resistance

The produced sample 1 for evaluation was cut | disconnected in 10 mm width, and it put into the high temperature high humidity tank under high temperature, high humidity of 80 degreeC * 85% RH, and peeling evaluation after 169 hours passed.

<Evaluation Criteria>

Peel strength maintained above 80% relative to initial phase: A

Peel strength maintained above 60% relative to initial phase: B

Peel strength remains 40% or less relative to initial stage: C

(2) Evaluation of Extrusion Stability

10 m <^2> (1m * 10m) of adhesive sheets after 8 hours of extrusion time were extract | collected, and evaluated about 50 micrometers or more of crosslinked gels based on the following evaluation criteria.

<Evaluation Criteria>

No crosslinked gel: A

1 crosslinked gel / 1000 m ² or more 10 / less than 1000 m ² : B

10 crosslinked gels / 1000 m ² or more: C

(week)

1) Carbodiilite HMV-8 CA: Carbodiimide additive, Nisshin Spinning Co., Ltd. product name

2) Starbakzol P: Carbodiimide-based additive, Bayer Co., Ltd.

3) epochloose RPS-1005: oxazoline-based additive, Nihon Shokubai Co., Ltd.

4) It is a mass part with respect to 100 mass parts of adhesive agents.

Example 7

Add the additives of the kind and amount shown in Table 3 to the adhesive component used in Example 4, fully premixed in a Henschel mixer, and put into an extruder set to a temperature so that the resin temperature from the mold becomes the temperature shown in Table 3. After extruding, it cooled by the cast roll and formed the film for adhesive layers of 50 micrometers in thickness.

The base material (100 micrometer-thick biaxially stretched PET film) which carried the polyurethane-type anchor coat, and the formed adhesive layer film were bonded together using the lamination roll set to 20 degreeC higher than melting | fusing point of an adhesive, and the laminated film which has an adhesive bond layer was produced. .

In order to apply frost to the surface, the adhesive side of the laminated | stacked film transferred the surface frost to the adhesive surface in the frosted cooling roll after heat lamination, and before resin solidified, and produced the coating film.

In addition, for comparison, the same operation was performed also about the thing which did not add the additive, and the coating film was produced. The obtained film was evaluated in the same manner as in Example 6. The results are shown in Table 3.

(week)

1) Carbodiilite HMV-8CA: Carbodiimide-based additive, Nisshin Spinning Co., Ltd. product, brand name

2) Starbakzol P: Carbodiimide-based additive, Bayer Co., Ltd.

3) It is a mass part with respect to 100 mass parts of adhesive agents.

From Table 2-1, Table 2-2, and Table 3, it was found that the moist heat resistance is remarkably improved by adding the carbodiimide-based additive as the adhesive component. On the other hand, in the system without an additive, the performance decline was clearly confirmed by 40% drop with respect to the initial adhesive performance.

In addition, when the additive is added to the high-temperature extrusion or the addition amount of the additive, the heat-and-moisture resistance itself is improved, but since the reaction proceeds rapidly and the increase in the crosslinking point occurs and the crosslinking density is increased, It was found that the appearance defect occurred by the occurrence.

The coating film for electrical materials in which the adhesive layer was formed using the adhesive agent of this invention can be heat-bonded by methods, such as thermal lamination | stacking and a hot press, and can coat | cover the core wire of wiring wires, such as an electrical device and an electronic device, especially flexible It is useful for reinforcing plates (protect tapes) used for ends such as flat cables.

Claims (8)

A loss tangent (tanδ) in a temperature dispersion curve by a dynamic viscoelasticity measurement of the mixture, comprising a mixture of two or more crystalline polyester-based hot melt resins, is 4.9 × 10 ⁻² or more at −40 ° C. to 40 ° C. And a polyester-based hot melt resin having a maximum peak value of the loss tangent (tanδ) of the mixture in the range of -15 ° C to 40 ° C and a melting point (Tm) of the mixture at 95 ° C to 130 ° C. The adhesive which consists of a hot-melt type resin composition to make. The method of claim 1, Adhesive which hot melt type resin composition contains 0.05-2 mass parts of oxazoline type additives with respect to 100 mass parts of polyester type hot melt resins. The method of claim 1, Adhesive which a hot melt type resin composition contains 0.05-2 mass parts of carbodiimide type additives with respect to 100 mass parts of polyester type hot melt resins. The coating film for electrical materials formed by using the adhesive agent in any one of Claims 1-3 on at least one surface of a plastic base film. The method of claim 4, wherein The coating film for electrical materials whose surface roughness of an adhesive bond layer is 10 micrometers average roughness (Rz) 1 micrometer or more. 6. The method of claim 5, The coating film for electrical materials whose surface roughness of an adhesive bond layer is 10 micrometers or more of 10-point average roughness (Rz). The method of claim 4, wherein Coating film for electrical materials used by bonding for reinforcement of electrical materials. The method of claim 7, wherein Cladding film for electrical material, wherein the electrical material is a flexible flat cable.