CN106675003A - Thermoplastic resin composition and adhesive prepared from composition, insulation adhesive film for laminated bus bars, and preparation method of insulation adhesive film - Google Patents

Abstract

The invention provides a thermoplastic resin composition, which comprises 40-80 parts of copolyamide resin, 5-35 parts of saturated polyester resin, 1-10 parts of compatibilizer and 20 parts of flame retardant in terms of parts by mass. ～100 parts and 0.1～1 part of antioxidant. Copolyamide resin has strong polarity, strong intermolecular force, can form a partial crystal structure, has a high melting point, and has good adhesion to metals, but poor adhesion to polymer films; while saturated polyester resin has a melting point of It has low polarity and relatively weak polarity, and has good adhesion to polymer films; the compatibilizer can improve the compatibility between the copolyamide resin and the saturated polyester resin, and improve the cohesive strength of the thermoplastic resin composition. The thermoplastic resin composition does not contain curing agent, has good fluidity at high temperature and can be pressed at low temperature. The present invention also provides an adhesive made of the above thermoplastic resin composition, an insulating adhesive film for laminated busbars, and a preparation method for the insulating adhesive film for laminated busbars.

Description

A thermoplastic resin composition and the adhesive prepared therefrom, and insulation for laminated busbars Adhesive film, the preparation method of the insulating adhesive film

technical field

The invention relates to the field of insulating adhesive films for laminated busbars, in particular to a thermoplastic resin composition and an adhesive prepared therefrom, an insulating adhesive film for laminated busbars, and a method for preparing the insulating adhesive film.

Background technique

Laminated busbars are also called composite busbars, laminated busbars, composite copper bars, composite busbars, etc., and the English name is Laminated Busbar. It is mainly based on the electromagnetic theory, and the wide and thin copper bar is hot-pressed with a very thin insulating material. The opposite current passes through the adjacent wires, and the magnetic fields cancel each other, which can reduce the parasitic inductance. As the bonding between the conductors in the laminated busbar and the insulating film of the insulating material, its performance has a crucial impact on the safety and reliability of the laminated busbar. The insulating film is mainly composed of an insulating film and an adhesive coated on its surface. At present, the adhesives used for laminated busbar insulation films are mainly epoxy adhesives and polyester adhesives. Epoxy adhesive is a kind of thermosetting adhesive, which has the advantages of good bonding performance, excellent heat resistance, good electrical insulation performance, excellent dielectric performance, etc., but there are also disadvantages such as short storage period, long pressing time, and high pressing temperature. , so that its application in the insulating adhesive film for laminated busbars is limited. Saturated polyester adhesive is a kind of thermoplastic adhesive. Although it has the advantages of long storage time and short pressing time, the high-temperature bonding performance of saturated polyester adhesive is generally poor, and it is difficult to meet the requirements of insulating adhesive for laminated busbars. Membrane application requirements.

In order to improve the high-temperature bonding performance of saturated polyester adhesives, blending with epoxy resin or adding a small amount of curing agent is usually used to form an interpenetrating polymer network structure or produce partial crosslinking to improve the performance of saturated polyester adhesives. Adhesive high temperature performance. For example, Chinese patent CN104178044A discloses an epoxy-modified saturated polyester resin adhesive, which is prepared from the following components in mass percentage: saturated polyester resin A20-50%, saturated polyester resin B5-30%, epoxy 2-20% resin, 1-10% isocyanate, 20-70% flame retardant, 0.05-5% dispersant, dispersed in organic solvent according to the above ratio, to obtain epoxy-modified saturated polyester for laminated busbar adhesive. However, the reaction temperature of epoxy resin ring-opening and isocyanate is usually higher than 200 °C, and it is difficult to form an interpenetrating polymer network structure with saturated polyester resin at lower temperatures to improve the high-temperature performance of saturated polyester adhesive systems; and saturated polyester Adding epoxy resin modification to the resin may cause the modified adhesive to become brittle and reduce storage performance. Another example is Chinese patents CN105176468A and CN105199649A which disclose a method of adding an acid anhydride curing agent to partially crosslink the saturated polyester resin, but still maintain thermoplasticity overall, which can significantly improve the high-temperature bonding performance of the saturated polyester adhesive. Adding a curing agent makes the saturated polyester resin form a partially cross-linked network structure, which can certainly improve the high-temperature bonding performance of the saturated polyester adhesive, but the saturated polyester adhesive forms a partially cross-linked network structure before pressing, although the overall retention Thermoplastic, but it has formed a certain three-dimensional network structure, has no obvious melting point, and its fluidity and wettability are greatly reduced at high temperatures. Generally, it needs to be pressed above 150°C to achieve effective bonding. The increase of pressing temperature will not only bring about an increase in energy consumption, but also long-term pressing at high temperature will lead to a decrease in the performance of the polymer film. In addition, as the structure of laminated busbars becomes more and more complex, in many cases multiple high-temperature pressing is required to form, and excessively high pressing temperatures will lead to a decrease in the yield of finished products.

Therefore, how to reduce the pressing temperature and the pressing time without reducing the high-temperature performance of the thermoplastic resin composition and the insulating adhesive film for laminated busbars is one of the key problems to be solved in the industry.

Contents of the invention

One of the purposes of the present invention is to provide a thermoplastic resin composition; the second purpose of the present invention is to provide an adhesive made of the above-mentioned thermoplastic resin composition; the third purpose of the present invention is to provide a The insulating adhesive film for laminated busbars made of objects; the fourth object of the present invention is to provide a preparation method for the insulating adhesive film for laminated busbars. The insulating adhesive film for laminated busbars adopts the above-mentioned thermoplastic resin composition, which has a low pressing temperature and a short pressing time, and has excellent high-temperature peel strength, processability and thermal shock performance, and can meet the requirements of low-temperature pressing and lamination. Application requirements for layer busbars.

To achieve this purpose, the present invention provides a thermoplastic resin composition, which comprises 40 to 80 parts of copolyamide resin, such as 45 parts, 50 parts, 55 parts, 58 parts, 60 parts in parts by mass. Parts, 65 parts, 70 parts, 75 parts or 79 parts; 5 to 35 parts of saturated polyester resin, such as 6 parts, 8 parts, 10 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts or 34 parts 1-10 parts of compatibilizer, such as 2 parts, 3 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts; and 20-100 parts of flame retardant, such as 21 parts, 30 parts, 40, 50, 60, 70, 80, 90 or 99 servings.

The thermoplastic resin composition of the present invention is composed of copolyamide as the main resin, combined with saturated polyester resin, compatibilizer and flame retardant, wherein the copolyamide resin has strong polarity, strong intermolecular force, and can form a partial crystal structure , has a high melting point, good adhesion to metals, but poor adhesion to polymer films; while saturated polyester resin has a low melting point, relatively weak polarity, and good adhesion to polymer films ; The compatibilizer can improve the compatibility between the copolyamide resin and the saturated polyester resin, and improve the cohesive strength of the thermoplastic resin composition. The thermoplastic resin composition obtained by using saturated polyester resin and copolyamide resin as the main resin does not contain curing agent, has good high-temperature fluidity, can be pressed at low temperature, and can be used as an adhesive for laminated busbars. It has excellent high-temperature peel strength, Thermal shock performance and processing performance.

Preferably, the number average molecular weight Mn of the copolyamide resin is 10000-30000, and the melting point Tm is 110°C-130°C, such as 115°C, 120°C, 125 or 129°C. The glass transition temperature Tg is -30°C to 40°C, such as -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C or 39°C, and the acid value is 2 to 15mgKOH/g, For example, 3mgKOH/g, 5mgKOH/g, 10mgKOH/g, 12mgKOH/g or 14mgKOH/g; the amine value is 3~10mgKOH/g, such as 3mgKOH/g, 5mgKOH/g, 10mgKOH/g.

Preferably, the number-average molecular weight Mn of the saturated polyester resin is 8000-30000, and the glass transition temperature Tg is between -30°C and 110°C, such as -30°C, -20°C, -10°C, 0°C , 10°C, 20°C, 30°C, 50°C, 65°C, 70°C, 80°C, 90°C or 109°C; the hydroxyl value is 2-10mgKOH/g, such as 2.5mgKOH/g, 3mgKOH/g, 5mgKOH/g , 10mgKOH/g. The saturated polyester resin can be preferably ES450, ES850, ES750, ES901, ES600, ES120, etc. manufactured by SK Chemicals in Korea, and S1611, S1426, S1313, L952, L912, etc. manufactured by Evonik Company in Germany.

Preferably, the compatibilizer is selected from one or both of reactive compatibilizers and non-reactive compatibilizers. The reactive compatibilizer is any one or at least two of low molecular weight carboxyl-terminated copolyamide resins, low molecular weight carboxyl-terminated polyester resins, isocyanate grafted copolyamide resins, and isocyanate grafted saturated polyester resins. Mixture; the non-reactive compatibilizer is a block copolymer obtained by the copolymerization reaction of dibasic acid, dibasic alcohol and dibasic amine.

Preferably, the flame retardant includes any one or a mixture of at least two of halogenated flame retardants, halogenated flame retardant synergists, and metal hydroxides; the halogenated flame retardant is decabromo Any one or at least two of diphenylethane, brominated styrene, brominated epoxy resin, tetrabromobisphenol A, hexabromocyclododecane, and ethylene bistetrabromophthalimide mixture; the halogenated flame retardant synergist is any one or a mixture of at least two of antimony trioxide and antimony pentoxide; the metal hydroxide is magnesium hydroxide, aluminum hydroxide Either or a mixture of both.

Preferably, the thermoplastic resin composition further includes an antioxidant, and the addition amount of the antioxidant is 0.1 to 1 part by mass, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part parts, 0.7 parts, 0.8 parts, 0.9 parts. . It can prolong the service life of the insulating adhesive film for laminated busbars, slow down or inhibit the aging process of the adhesive during hot pressing, and the hindered phenolic antioxidants 1010, 1076, 1098, 2246 and phosphite antioxidants are preferably used in the present invention Agents 168, 618.

The present invention also provides an adhesive, comprising the above-mentioned thermoplastic resin composition and an organic solvent, the solid content of the adhesive is 30wt% to 60wt%, preferably 35wt% to 60wt%, which can obtain a suitable viscosity and provide a good Processability, to ensure that there will be no apparent defects during use (such as coating).

Preferably, the organic solvent is ethanol, propanol, isopropanol, butanol, n-pentanol, cyclohexanol, isoamyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanol Any one or a mixture of at least two of ketone, acetone, cyclohexanone, toluene, xylene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl acetate.

The present invention also provides an insulating adhesive film for laminated busbars, comprising an insulating film and an adhesive layer formed by the above-mentioned adhesive coated on one or both sides of the insulating film.

Preferably, the insulating film is polyethylene terephthalate film (PET), polybutylene terephthalate film (PBT), polyethylene naphthalate film (PEN), Polyimide film (PI) or polym-phenylene isophthalamide film (NOMEX).

Preferably, the thickness of the insulating film is 100-250 μm, for example: 105 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm or 249 μm; The thickness of the adhesive layer is 10-50 μm, for example: 10 μm, 20 μm, 30 μm, 40 μm or 50 μm.

The present invention also provides a method for preparing the above-mentioned insulating adhesive film for laminated busbars, which is characterized in that it includes the steps of:

(1) Weigh the copolyamide resin, saturated polyester resin, compatibilizer, antioxidant and flame retardant according to the stated parts by mass, and use a ball mill, pot mill or sand mill to simultaneously use high-shear stirring to disperse Equipment mixes it with organic solvents to make adhesives; and

(2) Coat the adhesive on one or both sides of the insulating substrate, put it into an online drying oven, and heat it at 80-160° C. for 2-10 minutes to remove the organic solvent, form a solid adhesive layer, and collect roll to obtain the insulating adhesive film for the laminated busbar.

Preferably, the organic solvent is ethanol, propanol, isopropanol, butanol, n-pentanol, cyclohexanol, isoamyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanol Any one or a mixture of at least two of ketone, acetone, cyclohexanone, toluene, xylene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl acetate.

Compared with the prior art, the present invention has the following beneficial effects:

The thermoplastic resin composition of the present invention contains a copolyamide resin and a saturated polyester resin, the copolyamide resin has strong polarity, strong intermolecular force, can form a partial crystal structure, has a relatively high melting point, and has good adhesion properties with metals Excellent, but poor adhesion to insulating film; blending a small amount of saturated polyester resin with it, and adding a small amount of compatibilizer, can get a thermoplastic resin composition with good compatibility, the thermoplastic resin composition is on metal and Insulating films all have excellent adhesive properties. In addition, the resin composition does not contain a curing agent and is a pure thermoplastic resin composition. The flame retardancy of the insulating adhesive film prepared by using the thermoplastic resin composition can reach UL94VTM-0 level, and the pressing temperature is low and the bonding performance is good. , At the same time, it has excellent high-temperature peel strength, dimensional stability and processability, which can meet the needs of low-temperature pressure-bonded laminated busbars.

Instructions attached

FIG. 1 is a schematic diagram of a first embodiment of an insulating adhesive film for laminated busbars according to the present invention.

Fig. 2 is a schematic diagram of a second embodiment of the insulating adhesive film for laminated busbars of the present invention.

detailed description

The technical solutions of the present invention will be further described below through specific embodiments.

Example 1

A thermoplastic resin composition, comprising 45 parts of copolyamide resin calculated in parts by mass, 30 parts of saturated polyester resin (ES450), 2 parts of non-reactive compatibilizer, 10 parts of antimony trioxide, 5 parts of aluminum hydroxide 30 parts, 30 parts of decabromodiphenylethane, 0.1 part of antioxidant.

The thermoplastic resin composition is applied to an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first adjust the polyamide resin, saturated polyester resin, non-reactive compatibilizer, antimony trioxide and aluminum hydroxide with methyl ethyl ketone , decabromodiphenylethane, and antioxidant liquid dispersion (solid content 45%), mixed into an adhesive.

As shown in Figure 1, the adhesive is coated on one side with a coating machine on a PET insulating film 10 with a thickness of 100 μm, and the coating thickness is 20 μm;

Then treat at 100° C. for 5 minutes to volatilize methyl ethyl ketone and form a solid adhesive layer 20 on the PET insulating film;

Finally, the insulating adhesive film 1 for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 2

A thermoplastic resin composition, comprising 54 parts of copolyamide resin calculated in parts by mass, 25 parts of saturated polyester resin (L912), 3 parts of reactive compatibilizer, 15 parts of antimony pentoxide, and 5 parts of magnesium hydroxide , 35 parts of ethylene bis-tetrabromophthalimide, 0.5 part of antioxidant.

The thermoplastic resin composition is applied to the laminated busbar insulation adhesive film.

A method for preparing an insulating adhesive film for laminated busbars containing a thermoplastic resin composition: first use acetone to adjust the composition of the copolyamide resin, saturated polyester resin, reactive compatibilizer, antimony pentoxide, magnesium hydroxide, ethyl alcohol, etc. A liquid dispersion (solid content: 40%) composed of bis-tetrabromophthalimide and an antioxidant is mixed into an adhesive.

As shown in Figure 2, the double-sided coating of this adhesive with a coating machine is on the PET insulating film 10' of 188 μm in thickness, and the coating thickness is 30 μm;

Then treat at 110°C for 8 minutes to volatilize the acetone and form a solid adhesive layer 20' on the PET insulating film;

Finally, the insulating adhesive film 1' for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 3

A thermoplastic resin composition, comprising 70 parts by mass of copolyamide resin, 15 parts of saturated polyester resin (S1426), 3 parts of reactive compatibilizer, 12 parts of antimony trioxide, and 10 parts of magnesium hydroxide , 40 parts of tetrabromobisphenol A, 0.8 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first use cyclohexanone to adjust the composition of the copolyamide resin, saturated polyester resin, reactive compatibilizer, antimony trioxide, magnesium hydroxide , Tetrabromobisphenol A, and an antioxidant liquid dispersion (solid content is 50%), mixed into an adhesive.

Then use a coating machine to coat the adhesive on a PEN insulating film with a thickness of 100 μm on one side, and the coating thickness is 40 μm;

Then treat at 160°C for 10 minutes to volatilize cyclohexanone and form a solid adhesive layer on the PEN insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 4

A thermoplastic resin composition comprising 75 parts by mass of copolyamide resin, 8 parts of saturated polyester resin (ES120), 6 parts of non-reactive compatibilizer, 15 parts of antimony trioxide, and 10 parts of aluminum hydroxide 26 parts, 26 parts of brominated styrene, 0.8 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for laminated busbars containing thermoplastic resin composition: first use ethyl acetate to adjust the composition of the copolyamide resin, saturated polyester resin, non-reactive compatibilizer, antimony trioxide, hydroxide A liquid dispersion (35% solid content) composed of aluminum, brominated styrene, and an antioxidant is mixed into an adhesive.

Then apply the adhesive on a PBT insulating film with a thickness of 150 μm on one side with a coating machine, and the coating thickness is 45 μm;

Then treat at 100°C for 4 minutes to volatilize ethyl acetate and form a solid adhesive layer on the PBT insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 5

A thermoplastic resin composition, comprising 50 parts by mass of copolyamide resin, 6 parts of saturated polyester resin (ES450), 1.8 parts of reactive compatibilizer, 7 parts of antimony trioxide, 15 parts of brominated styrene 5 parts, 5 parts of aluminum hydroxide, 0.9 part of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first adjust the polyamide resin, saturated polyester resin, reactive compatibilizer, antimony trioxide and benzene bromide with ethanol and toluene A liquid dispersion (60% solid content) composed of ethylene, aluminum hydroxide and antioxidant is mixed into an adhesive.

Then use a coating machine to coat the adhesive on a PI insulating film with a thickness of 110 μm on one side, and the coating thickness is 12 μm;

Then treat at 110°C for 9 minutes to volatilize ethanol and toluene, and form a solid adhesive layer on the PI insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 6

A thermoplastic resin composition comprising 78 parts by mass of copolyamide resin, 19 parts of saturated polyester resin (ES850), 5.9 parts of non-reactive compatibilizer, 14 parts of antimony pentoxide, brominated epoxy 30 parts of resin, 10 parts of magnesium hydroxide, 0.4 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for laminated busbars containing thermoplastic resin composition: first use propanol and toluene to adjust the polyamide resin, saturated polyester resin, non-reactive compatibilizer, antimony pentoxide, bromide A liquid dispersion (solid content of 45%) composed of epoxy resin, magnesium hydroxide, and antioxidant is mixed into an adhesive.

Then use the coating machine to coat the adhesive on the NOMEX insulating film with a thickness of 130 μm on one side, and the coating thickness is 17 μm;

Then treat at 165°C for 7 minutes to volatilize propanol and toluene and form a solid adhesive layer on the NOMEX insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 7

A thermoplastic resin composition, comprising 53 parts by mass of copolyamide resin, 10 parts of saturated polyester resin (ES750), 3.4 parts of reactive compatibilizer, 12 parts of antimony trioxide, hexabromocyclododecane 42 parts of alkane, 12 parts of aluminum hydroxide, and 1.0 part of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first use butanol and xylene to adjust the polyamide resin, saturated polyester resin, reactive compatibilizer, antimony trioxide, hexabromo A liquid dispersion (solid content of 57%) composed of cyclododecane, aluminum hydroxide and an antioxidant is mixed to form an adhesive.

Then use a coating machine to coat the adhesive on a PET insulating film with a thickness of 150 μm on one side, and the coating thickness is 20 μm;

Then treat at 170°C for 6 minutes to volatilize butanol and xylene to form a solid adhesive layer on the PET insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 8

A thermoplastic resin composition, comprising 74 parts by mass of copolyamide resin, 12 parts of saturated polyester resin (ES901), 6.2 parts of non-reactive compatibilizer, 9 parts of antimony trioxide, antimony pentoxide 10 parts, 35 parts of decabromodiphenylethane, 8 parts of aluminum hydroxide, 3 parts of magnesium hydroxide, 0.5 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for laminated busbars containing thermoplastic resin composition: first use n-amyl alcohol and methyl ethyl ketone to adjust the composition of the copolyamide resin, saturated polyester resin, non-reactive compatibilizer, antimony trioxide, Liquid dispersion (53% solid content) composed of antimony pentoxide, decabromodiphenylethane, aluminum hydroxide, magnesium hydroxide and antioxidant is mixed into an adhesive.

Then use a coating machine to coat the adhesive on a PBT insulating film with a thickness of 140 μm on one side, and the coating thickness is 31 μm;

Then treat at 140°C for 7 minutes to volatilize n-amyl alcohol and butanone, and form a solid adhesive layer on the PBT insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 9

A thermoplastic resin composition, comprising 59 parts by mass of copolyamide resin, 15 parts of saturated polyester resin (ES600), 4.9 parts of reactive compatibilizer, 11 parts of antimony trioxide, 12 parts of antimony pentoxide 50 parts, 50 parts of brominated styrene, 13 parts of aluminum hydroxide, 0.7 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for laminated busbars containing thermoplastic resin composition: first use toluene to adjust the composition of the copolyamide resin, saturated polyester resin, reactive compatibilizer, antimony trioxide, antimony pentoxide, A liquid dispersion (solid content of 41%) composed of brominated styrene, aluminum hydroxide, and an antioxidant is mixed to form an adhesive.

Then use a coating machine to coat the adhesive on a PEN insulating film with a thickness of 160 μm on one side, and the coating thickness is 38 μm;

Then treat at 130°C for 6 minutes to volatilize the toluene and form a solid adhesive layer on the PEN insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Example 10

A thermoplastic resin composition, comprising 79 parts by mass of copolyamide resin, 18 parts of saturated polyester resin (S1426), 7.1 parts of non-reactive compatibilizer, 31 parts of antimony trioxide, brominated epoxy 57 parts of resin, 8 parts of aluminum hydroxide, 1 part of magnesium hydroxide, 0.2 part of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first adjust the polyamide resin, the saturated polyester resin, the non-reactive compatibilizer, the antimony trioxide, and the brominated ring with xylene. A liquid dispersion (solid content of 37%) composed of oxygen resin, aluminum hydroxide, magnesium hydroxide, and antioxidant is mixed into an adhesive.

Then apply the adhesive on one side of the PI insulation film with a thickness of 175 μm with a coating machine, and the coating thickness is 42 μm;

Then treat at 140°C for 4 minutes to volatilize the xylene and form a solid adhesive layer on the PI insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Comparative example 1

A thermoplastic resin composition, comprising 70 parts by mass of copolyamide resin, 10 parts of saturated polyester resin (S1426), 10 parts of antimony trioxide, 15 parts of aluminum hydroxide, 30 parts of hexabromocyclododecane part, 0.4 part of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first adjust the polyamide resin, saturated polyester resin, antimony trioxide, aluminum hydroxide, hexabromocyclododecane with methyl ethyl ketone , Antioxidant composition liquid dispersion (solid content is 40%), mixed into adhesive.

Then apply the adhesive on one side with a coating machine on a PET insulating film with a thickness of 125 μm, and the coating thickness is 35 μm;

Then treat at 110°C for 2 minutes to volatilize butanone and form a solid adhesive layer on the PET insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Comparative example 2

A thermoplastic resin composition, comprising 75 parts of copolyamide resin, 15 parts of antimony trioxide, 10 parts of magnesium hydroxide, 30 parts of brominated epoxy resin and 0.7 parts of antioxidant in parts by mass.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for laminated busbar containing thermoplastic resin composition: first use ethyl acetate to adjust the composition of the copolyamide resin, antimony trioxide, magnesium hydroxide, brominated epoxy resin, and antioxidant The liquid dispersion (solid content is 45%), mixed into adhesive.

Then apply the adhesive on a PBT insulating film with a thickness of 175 μm on one side with a coating machine, and the coating thickness is 40 μm;

Then treat at 120°C for 5 minutes to volatilize ethyl acetate and form a solid adhesive layer on the PBT insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Comparative example 3

A thermoplastic resin composition, comprising 30 parts by mass of saturated polyester resin, 5 parts of antimony pentoxide, 15 parts of decabromodiphenylethane, and 0.3 parts of antioxidant.

The thermoplastic resin composition is used for an insulating adhesive film for a laminated busbar.

The preparation method of the insulating adhesive film for the laminated busbar containing the thermoplastic resin composition: first adjust the liquid dispersion composed of the saturated polyester resin, antimony pentoxide, decabromodiphenylethane and antioxidant with methyl ethyl ketone body (40% solids content), mixed into an adhesive.

Then use a coating machine to coat the adhesive on a PET insulating film with a thickness of 125 μm on one side, and the coating thickness is 45 μm;

Then treat at 100°C for 3 minutes to volatilize butanone and form a solid adhesive layer on the PET insulating film;

Finally, the insulating adhesive film for laminated busbars of the thermoplastic resin composition is obtained by winding.

Perform performance tests on the insulating adhesive films for laminated busbars of Examples 1 to 10, Comparative Examples 1 to 3 and existing products, and the test methods for each test item are as follows:

(1) Low temperature lamination

The insulation film and the tinned copper bar are pressed together at 130°C, and if there is no blistering, delamination, or cracking, it is qualified, otherwise it is unqualified.

(2) Peel strength

Adhesion between insulating film and copper foil, 90°peel test; Among them, the A-state peel strength is the test result in air, and the high-temperature peel strength is the test result in silicone oil at the corresponding temperature.

(3) Electric strength

After the insulating film is connected to the equipment, apply a voltage with a frequency of 50 Hz, and calculate the electric strength at the time of breakdown.

(4) Elongation

According to the standard of ASTM D-882, it is tested by material tensile testing machine.

(5) Dimensional stability

The insulating film was treated at 125°C for 4 hours, and at 150°C for 2 hours, and then the dimensional changes in the MD and TD directions before and after the treatment were measured; where MD is the radial direction and TD is the weft direction.

(6) Thermal shock performance

The insulating film and the tinned copper bar are pressed together at high temperature, and then subjected to the thermal shock test. The thermal shock test conditions are: -40°C to 105°C/200 cycles, -40°C/constant temperature for 0.5 hours, -40°C to 105°C/1 minute, 105°C/constant temperature for 0.5 hours, 105°C to -40 ℃/1 minute, the above cycle is about 1 hour.

If there is no blistering or cracking between the adhesive film and the tinned copper bar after thermal shock, it is qualified, otherwise it is unqualified.

(7) Damp heat aging performance

The insulating film and the tinned copper bar are pressed together at high temperature, and then subjected to a damp heat aging test. The conditions of the damp heat aging test are: 85°C×85%RH/1000 hours.

If there is no blistering, delamination or cracking between the adhesive film and the tinned copper bar after damp heat aging, it is qualified, otherwise it is unqualified.

(8) Processability (bending test)

The tin-plated copper bar with a thickness of 3mm and the adhesive film were pressed together at high temperature, cooled to room temperature, and subjected to a bending test. The bending angle was 90°. After bending, if there is no blistering, delamination, or cracking between the adhesive film and the tinned copper bar, it is qualified, otherwise it is unqualified.

(9) High temperature test

Place the bent sample in an oven at 105°C and bake for 240 hours. If there is no blistering, delamination, or cracking between the film and the tinned copper bar, it is qualified, otherwise it is unqualified.

(10) Flame retardancy

Measured according to UL 94 vertical combustion method.

The specific test results are shown in Table 1 below.

As can be seen from Table 1, in Comparative Example 1, no compatibilizer is added, the compatibility of the copolyamide resin and the saturated polyester resin is poor after blending, and the cohesive strength is low, resulting in low peel strength; and In Comparative Example 2, the copolyamide resin was used alone without adding saturated polyester resin. Due to its large polarity, the bonding performance with the polymer film was not good, so its A-state peel strength was less than 1.0N/mm, but due to Copolyamide has good high temperature resistance, and its peel strength at 105°C is still greater than 1.0N/mm; in Comparative Example 3, saturated polyester resin is used alone, and its peel strength at 105°C is only 0.12N/mm due to its poor high temperature resistance . The high temperature resistance, processability, cold and heat shock performance, and damp heat aging performance of the insulating adhesive film in the comparative example are all unqualified. In the examples, copolyamide resin and saturated polyester resin are blended and modified, and a compatibilizer is added to improve the compatibility of the two, so that a thermoplastic resin composition with good compatibility can be obtained, and the prepared laminated busbar The use of insulating adhesive film can meet the requirements of low-temperature lamination, and the adhesive performance, high-temperature resistance, processability, thermal shock performance, and damp-heat aging performance are all greatly improved compared with the comparative example and existing products, and the A-state peel strength is greater than 2.0N/mm, peel strength at 105°C greater than 1.0N/mm, after 200 cycles of cold and heat shock at -40°C/30min～105°C/30min, aging at 85°C and humidity 85% for 1000 hours, high temperature baking at 105°C for 240 Hours later, there is still no cracking and foaming phenomenon. Copolyamide resin and saturated polyester are blended and modified to effectively integrate the advantages of the two. It has excellent heat resistance and high and low temperature peel strength, and can meet the requirements of low temperature lamination.

In summary, the electrical properties and environmental resistance tests of the resin composition of the present invention and the insulating adhesive film for laminated busbars prepared by it all meet the standards, and the flame retardancy reaches the UL94VTM-0 level, which is lower than the pressing temperature of existing products. Above 20°C, and has excellent high and low temperature peel strength and good processing performance.

Compared with the prior art, the present invention has the following beneficial effects:

The thermoplastic resin composition of the present invention contains a copolyamide resin and a saturated polyester resin, the copolyamide resin has strong polarity, strong intermolecular force, can form a partial crystal structure, has a relatively high melting point, and has good adhesion properties with metals Excellent, but poor adhesion to insulating film; blending a small amount of saturated polyester resin with it, and adding a small amount of compatibilizer, can get a thermoplastic resin composition with good compatibility, the thermoplastic resin composition is on metal and Insulating films all have excellent adhesive properties. In addition, the resin composition does not contain a curing agent and is a pure thermoplastic resin composition. The flame retardancy of the insulating adhesive film prepared by using the thermoplastic resin composition can reach UL94VTM-0 level, and the pressing temperature is low and the bonding performance is good. , At the same time, it has excellent high and low temperature peel strength, dimensional stability and processability, which can meet the needs of low temperature laminated busbars.

The above are only preferred embodiments of the present invention, and for those skilled in the art, various other corresponding changes and modifications can be made according to the technical scheme and technical concept of the present invention, and all these changes and modifications are Should belong to the scope of the claims of the present invention.

The present invention illustrates the detailed methods of the present invention through the above examples, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (14)

1. a kind of thermoplastic resin composition, it is characterised in that according to mass fraction meter, the thermoplastic resin composition includes Following component：

2. thermoplastic resin composition as claimed in claim 1, it is characterised in that the equal molecule of number of the copolyamide resin To measure as 10000~30000, fusing point is 110 DEG C~130 DEG C, glass transition temperature is -30 DEG C~40 DEG C, acid number is 2~ 15mgKOH/g, amine number is 3~10mgKOH/g.

3. thermoplastic resin composition as claimed in claim 1, it is characterised in that the equal molecule of number of the saturated polyester resin Measure as 8000~30000, glass transition temperature is that between -30 DEG C~110 DEG C, hydroxyl value is 2~10mgKOH/g.

4. thermoplastic resin composition as claimed in claim 1, it is characterised in that the compatilizer is selected from response type compatilizer Or one or two in non-reactive compatilizer.

5. thermoplastic resin composition as claimed in claim 4, it is characterised in that the response type compatilizer is low-molecular-weight Carboxy blocking copolyamide resin, low-molecular-weight carboxy-terminated polyester resin, isocyanates graft copolymerization amide resin, Carbimide. Ester is grafted any one in saturated polyester resin or at least two mixture；The non-reactive compatilizer be binary acid, The block copolymer that dihydroxylic alcohols and diamine copolyreaction are obtained.

6. thermoplastic resin composition as claimed in claim 1, it is characterised in that the fire retardant include halogenated flame retardant, In halogen system fire retarding synergist, metal hydroxidess any one or at least two mixture；The halogenated flame retardant is ten The double tetrabromo-phthalic diformazans of bromine diphenylethane, brominated styrene, brominated epoxy resin, tetrabromobisphenol A, HBCD, ethylene In acid imide any one or at least two mixture；The halogen system fire retarding synergist is antimony oxide, five oxidations two The mixture of any one or two kinds in antimony；The metal hydroxidess are any one in magnesium hydroxide, aluminium hydroxide Or two kinds of mixture.

7. thermoplastic resin composition as claimed in claim 1, it is characterised in that also including antioxidant, according to mass fraction Meter, the addition of the antioxidant is 0.1~1 part.

8. thermoplastic resin composition as claimed in claim 7, it is characterised in that the antioxidant is Hinered phenols antioxidant And the compositionss of any one or two kinds in phosphite ester kind antioxidant；The Hinered phenols antioxidant includes model 1010th, in 1076,1098 and 2246 any one or at least two compositionss；The phosphite ester kind antioxidant includes type The compositionss of any one or two kinds in numbers 168 and 618.

9. a kind of adhesive, it is characterised in that include thermoplastic resin composition as described in any one of claim 1~8 and Organic solvent, the solid content of the adhesive is 30wt%~60wt%.

10. adhesive as claimed in claim 9, it is characterised in that the organic solvent is ethanol, propanol, isopropanol, fourth Alcohol, n-amyl alcohol, Hexalin, isoamyl alcohol, ethylene glycol, 1,2- Propylene Glycol, 1,3- Propylene Glycol, butanone, acetone, Ketohexamethylene, toluene, two In toluene, glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate any one or at least Two kinds of mixture.

11. a kind of stack bus bar insulated rubber films, it is characterised in that be coated on including insulation film and single or double described exhausted The gluing oxidant layer that the adhesive as described in any one of claim 9~10 on edge thin film is formed.

12. stack bus bar insulated rubber films as claimed in claim 11, it is characterised in that the insulation film is for poly- to benzene two Formic acid glycol ester thin film, polybutylene terephthalate (PBT) thin film, PEN thin film, Kapton Or poly(isophthaloyl metaphenylene diamine) thin film.

13. stack bus bar insulated rubber films as claimed in claim 11, it is characterised in that the thickness of the insulation film is 100~250 μm；The thickness of the gluing oxidant layer is 10~50 μm.

A kind of 14. methods of the stack bus bar insulated rubber film prepared as described in any one of claim 11~13, its feature exists In, including step：

(1) copolyamide resin, saturated polyester resin, compatilizer and fire retardant are weighed according to the mass fraction, it is molten with organic Agent is mixed to prepare adhesive；And

(2) the adhesive single or double is coated on insulating substrate, sends into baking oven to remove the organic solvent, formed The gluing oxidant layer of solid-state, winding obtains the stack bus bar insulated rubber film.