CN115279858A - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
CN115279858A
CN115279858A CN202180020026.0A CN202180020026A CN115279858A CN 115279858 A CN115279858 A CN 115279858A CN 202180020026 A CN202180020026 A CN 202180020026A CN 115279858 A CN115279858 A CN 115279858A
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polyester
adhesive composition
acid
parts
mass
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坂本晃一
川楠哲生
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Dongyang Textile Mc Co ltd
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Toyobo Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/06Polyurethanes from polyesters
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The adhesive composition of the present invention provides an adhesive composition which has excellent flexibility of an uncured coating film, and is excellent in heat resistance of a wet solder and peel strength at high temperatures as an adhesive for a flexible printed wiring board. The adhesive composition of the invention comprises a polyester having a glass transition temperature or melting point of greater than 80 ℃ and a polyisocyanate.

Description

Adhesive composition
Technical Field
The present invention relates to an adhesive composition. More specifically, the present invention relates to an adhesive composition which has excellent flexibility of an uncured coating film and is excellent in heat resistance of a solder in a humidified state and peel strength at high temperatures as an adhesive for a flexible printed wiring board.
Background
A flexible printed circuit board (FPC) is a substrate in which a circuit is formed on a base material obtained by bonding a thin and flexible film having insulation properties such as polyimide to a conductive metal such as copper foil with an adhesive. Unlike a rigid substrate, since it is very thin and flexible, it can be used in a small space or a curved movable portion of an electronic device, and is therefore used in many everyday electronic devices such as personal computers and smart phones. In recent years, many FPCs are mounted on automobiles, and thus, the adhesive is required to have adhesiveness at high temperature.
Polyesters are widely used as raw materials for resin compositions used in coating agents, inks, adhesives, and the like, and are generally composed of polycarboxylic acids and polyhydric alcohols. Since flexibility and molecular weight due to selection and combination of a polycarboxylic acid and a polyhydric alcohol can be freely controlled, the resin composition is widely used for various applications including coating agent applications and adhesive applications.
The polyester is excellent in adhesion (peel strength) to a metal containing copper, and is used in an adhesive for FPC by being blended with a curing agent.
(for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-125043
Disclosure of Invention
Problems to be solved by the invention
However, the polyester resin described in patent document 1 is only composed of a polyester resin having a glass transition temperature (Tg) as low as 80 ℃ or lower, and therefore the peel strength at high temperatures is insufficient.
The present invention has been made in view of the above-mentioned problems of the prior art. That is, an object of the present invention is to provide an adhesive composition which has excellent flexibility of an uncured coating film (B-stage) and is excellent in heat resistance of a solder in a humidified state and peel strength at high temperatures as an adhesive for a flexible printed wiring board.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by the means shown below, and have completed the present invention.
That is, the present invention has the following configuration.
An adhesive composition comprising a polyester (A1) having a glass transition temperature or melting point of more than 80 ℃ and a polyisocyanate (B).
The adhesive composition preferably further contains a polyester (A2) having a glass transition temperature of 0 ℃ or lower and a melting point of 80 ℃ or lower or being amorphous.
The content of the polyester (A2) in the adhesive composition is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyester (A1).
The content of the polyisocyanate (B) in the adhesive composition is preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the polyester (A1) and the polyester (A2).
The adhesive composition is suitable for use in flexible printed wiring boards.
ADVANTAGEOUS EFFECTS OF INVENTION
The uncured coating film of the adhesive composition of the present invention has excellent flexibility, and the adhesive composition for FPC has excellent heat resistance to a humidified solder and excellent peel strength at high temperatures.
Detailed Description
Hereinafter, one embodiment of the present invention will be described in detail. However, the present invention is not limited to this, and can be implemented by adding various modifications within the range described above.
< polyester (A1) >
The adhesive composition of the present invention contains a polyester (A1) having a glass transition temperature or melting point of more than 80 ℃. By using the polyester (A1) having a glass transition temperature (Tg) or a melting point (Tm) higher than 80 ℃, the heat resistance of a humidified solder and the peel strength at high temperatures can be improved.
The polyester (A1) is composed of a chemical structure obtainable by a polycondensate of a polycarboxylic acid component or a polycarboxylic acid ester component and a polyol component, wherein the polycarboxylic acid component or the polycarboxylic acid ester component and the polyol component are each composed of 1 or 2 or more selected components.
The polycarboxylic acid component constituting the polyester (A1) is not limited, and the following polycarboxylic acids, esters thereof and polycarboxylic acid anhydrides can be used. Specific examples of the polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, adipic acid, sebacic acid, dimer acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, fumaric acid, maleic acid, dimethyl isophthalate-5-sulfonic acid sodium salt, trimellitic acid, pyromellitic acid, and esters thereof. Examples of the polyvalent carboxylic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hydrogenated naphthalenedicarboxylic acid. Particularly, aromatic polycarboxylic acid components such as naphthalenedicarboxylic acid and terephthalic acid are preferable. By using an aromatic polycarboxylic acid, the Tg becomes high, and the peel strength at high temperatures can be improved.
The polyhydric alcohol constituting the polyester (A1) is not particularly limited, and there may be used, for example, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1-methyl-1, 8-octanediol, 2-methyl-2-ethyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-ethyl-2-n-propyl-1, 3-propanediol, 2-di-n-propyl-1, 3-propanediol, 2-n-butyl-2-ethyl-1, 3-propanediol, 2-di-n-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 2-ethyl-1, 3-hexanediol, 1, 4-cyclohexanedimethanol, tricyclodimethanol, polytetramethylene ether, polyalkylene ether, etc., and glycol components such as glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, α -methylglucose, mannitol, sorbitol, and dimer diol, and 1 or 2 or more of these may be used. In particular, a polyol having no long chain alkyl group such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, etc., or an alicyclic polyol such as 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, etc., is preferable. By using these polyols, tg becomes high, and peel strength at high temperature can be improved.
The polyester (A1) may be copolymerized with a trivalent or higher polycarboxylic acid component and/or a trivalent or higher polyhydric alcohol component. Examples of the trivalent or higher polycarboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimesic acid, trimellitic anhydride (TMA) and pyromellitic anhydride (PMDA), and aliphatic carboxylic acids such as 1,2,3, 4-butane tetracarboxylic acid, and 1 or 2 or more of these can be used. Examples of the trihydric or higher polyhydric alcohol component include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, α -methylglucose, mannitol, and sorbitol, and 1 or 2 or more kinds thereof can be used.
The polyester (A1) may further contain a copolyester or a lactam. For example, epsilon-caprolactone, epsilon-caprolactam may be used.
Examples of the polycondensation reaction for producing the polyester (A1) include: 1) A method of heating a polycarboxylic acid and a polyhydric alcohol in the presence of a known catalyst to conduct a polyol removal/polycondensation reaction through a dehydration esterification step; 2) A method of heating an alcohol ester of a polycarboxylic acid and a polyhydric alcohol in the presence of a known catalyst to perform a polyol-removing/polycondensation reaction through an ester exchange reaction; 3) A method of performing depolymerization; and the like. In the method of 1) 2), a part or all of the acid component may be replaced with an acid anhydride.
In the production of the polyester (A1), conventionally known polymerization catalysts can be used, for example, titanium compounds such as tetra-n-butyl titanate, tetra-isopropyl titanate and titanium oxide acetylacetonate, antimony compounds such as antimony trioxide and antimony tributoxide, germanium compounds such as germanium oxide and germanium tetra-n-butoxide, and other acetates of magnesium, iron, zinc, manganese, cobalt, aluminum and the like can be used. These catalysts may be used in combination of 1 or 2 or more.
Examples of the method for increasing the acid value of the polyester (A1) include: (1) A method in which a trivalent or higher polycarboxylic acid and/or a trivalent or higher polycarboxylic acid anhydride is added after the completion of the polycondensation reaction to cause the reaction (acid addition); (2) During the polycondensation reaction, the resin is intentionally modified by the action of heat, oxygen, water and the like; and the like, and these methods can be carried out arbitrarily. The polyvalent carboxylic acid anhydride used for acid addition in the above-mentioned acid addition method is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3', 4' -benzophenonetetracarboxylic dianhydride, 3', 4' -biphenyltetracarboxylic dianhydride, ethylene glycol dianhydrosilyltrimellitate, and 1 or 2 or more of these can be used.
The acid value of the polyester (A1) is preferably 200eq/106g or less, more preferably 100eq/106g or less, more preferably 50eq/106g or less, particularly preferably 30eq/106g or less, most preferably 20eq/106g is less than or equal to. By setting the resin acid value within the above range, the effects of improving the pot life, the adhesion to the substrate, and the crosslinkability can be expected. Further, as the acid value is lower, the moisture absorption can be suppressed and the heat resistance of the humidified solder can be improved.
The number average molecular weight of the polyester (A1) is preferably 5000 to 100000. More preferably 10000 or more. Further, 50000 or less is more preferable. When the number average molecular weight is within the above range, handling during dissolution in a solvent is easy, and high cohesive force is exhibited after curing, so that excellent peel strength can be exhibited.
In order to increase the Tg or Tm of the polyester to more than 80 ℃, for example, a rigid structure such as an aromatic compound or an alicyclic compound is introduced or the ester bond concentration is increased.
< polyester (A2) >
The adhesive composition of the present invention preferably further contains a polyester (A2) having a Tg of 0 ℃ or lower and a melting point of 80 ℃ or lower or being amorphous. By containing the polyester (A2) having a Tg of 0 ℃ or lower and a melting point of 80 ℃ or lower or being amorphous, flexibility can be imparted to the uncured coating film and heat resistance can be imparted to a wet solder. The Tg of the polyester (A2) is preferably-10 ℃ or lower.
The term "amorphous" means that no melting peak is shown in the melting point measurement described later.
The content of the polyester (A2) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyester (A1) having a Tg or Tm of more than 80 ℃. More preferably 25 parts by mass or more. Further, it is more preferably 70 parts by mass or less. When the content of the polyester (A2) is within the above range, the uncured coating film has excellent flexibility, peel strength at high temperature, and heat resistance to a wet solder.
The acid value of the polyester (A2) is preferably 200eq/106g or less, more preferably 100eq/106g or less, more preferably 50eq/106g or less, particularly preferably 30eq/106g or less, most preferably 20eq/106g is below. By setting the resin acid value within the above range, the effects of improving the pot life, the adhesion to the substrate, and the crosslinking property can be expected. Further, as the acid value is lower, the moisture absorption can be suppressed and the heat resistance of the humidified solder can be improved.
The number average molecular weight of the polyester (A2) is preferably 5000 to 100000. More preferably 10000 or more, still more preferably 20000 or more, and particularly preferably 25000 or more. When the number average molecular weight is equal to or more than the above value, the concentration of the relatively polar group is decreased, and therefore, the moisture absorption can be suppressed and the heat resistance of the humidified solder can be improved. Further, the number average molecular weight is more preferably 50000 or less. When the number average molecular weight is not more than the above value, the handling in dissolving in a solvent is easy, and the flexibility of the uncured coating film can be exhibited by maintaining the cohesive force even before curing.
In order to set the glass transition temperature of the polyester to 0 ℃ or lower and the melting point to 80 ℃ or lower or to be amorphous, it can be achieved by, for example, copolymerizing a monomer component having a long chain alkyl group or copolymerizing a monomer component having an asymmetric structure to destroy crystallinity.
< polyisocyanate (B) >
The adhesive composition of the present invention contains a polyisocyanate (B). The polyisocyanate (B) used in the present invention is not particularly limited as long as it is an isocyanate compound which reacts with the polyester resin and is cured.
Examples of the polyisocyanate (B) include aromatic or aliphatic diisocyanate compounds, and ternary or higher polyisocyanate compounds. These isocyanate compounds may be any of low molecular weight compounds and high molecular weight compounds. Examples thereof include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate and xylylene isocyanate, alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene isocyanate, dimer acid diisocyanate and isophorone diisocyanate, and trimers of these isocyanate compounds. Further, there may be mentioned compounds having a terminal isocyanate group obtained by reacting an excessive amount of the above isocyanate compound with a low molecular weight active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or the like. Further, there may be mentioned compounds containing a terminal isocyanate group obtained by reacting an excessive amount of the above isocyanate compound with various polyester polyols, polyether polyols, polyamide-based polymer active hydrogen compounds, and the like. These isocyanate compounds may be used alone or in combination of 2 or more. Among them, a trimer of the hexamethylene diisocyanate compound is particularly preferable.
The content of the polyisocyanate (B) in the adhesive composition of the present invention is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of the polyester (A1) and the polyester (A2). More preferably 5 parts by mass or less. Further, more preferably 1 part by mass or more. When the content of the polyisocyanate (B) is within the above range, excellent peel strength at high temperatures can be exhibited.
In the present invention, an inorganic flame retardant such as an organic phosphorus compound, zinc oxide, zinc sulfate, aluminum hydroxide, or barium hydroxide, a leveling agent, and a colorant such as a dye or a pigment may be appropriately added within a range not to impair the characteristics of the adhesive composition of the present invention.
Examples
The present invention will be specifically described below with reference to examples. In the present example and comparative example, "part" for short means part by mass.
(1) Determination of the composition of the polyester
Using 400MHz1An H-nuclear magnetic resonance spectrometer (hereinafter, may be abbreviated as NMR) quantifies the molar ratio of the polycarboxylic acid component and the polyol component constituting the polyester. Deuterated chloroform was used as solvent. In additionIn addition, when the acid value of the polyester is increased by acid post-addition, the molar ratio of each component is calculated assuming that the total amount of acid components other than the acid component used for acid post-addition is 100 mol%.
(2) Measurement of glass transition temperature and melting Point
The measurement was carried out using a differential scanning calorimeter (SII Co., ltd., DSC-200). 5mg of polyester was placed in an aluminum cap type container, sealed, and cooled to-50 ℃ using liquid nitrogen. Then, the temperature was raised to 150 ℃ at a temperature raising rate of 20 ℃/min, and in the endothermic curve obtained during the temperature raising, the temperature at the intersection of the extension of the base line before the onset of the endothermic peak (glass transition temperature or less) and the tangent of the endothermic peak (the tangent having the largest slope from the rising portion of the peak to the peak apex) was taken as the glass transition temperature (Tg, unit:. Degree. C.).
In addition, in the same endothermic curve, the temperature at the peak of the crystalline melting peak was taken as the melting point (Tm, unit:. Degree. C.).
(3) Determination of number average molecular weight
The polyester sample was dissolved and/or diluted in tetrahydrofuran so that the resin concentration became about 0.5 wt%, and the solution was filtered through a polytetrafluoroethylene membrane filter having a pore diameter of 0.5 μm to prepare a sample for measurement. The molecular weight was measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL/min and the column temperature was 30 ℃. The columns used were KF-802, 804L and 806L manufactured by Showa Denko K.K. The molecular weight standard used was monodisperse polystyrene.
(4) Measurement of acid value
0.2g of the polyester sample was dissolved in 40ml of chloroform, and the solution was titrated with 0.01N potassium hydroxide ethanol solution to obtain 10-point samples6g equivalent weight of polyester (eq/10)6g) In that respect Phenolphthalein was used as an indicator.
The following will show examples of production of adhesive compositions containing the polyesters of the present invention and comparative examples, and polyisocyanates.
Production example of polyester (a 1)
359 parts of terephthalic acid, 58 parts of dimethyl 2, 6-naphthalenedicarboxylate, 67 parts of ethylene glycol, 189 parts of propylene glycol, 5 parts of trimethylolpropane and tetrabutyl orthotitanate as a catalyst in an amount of 0.03mol% based on the total acid components were charged into a reaction vessel equipped with a stirrer, a condenser and a thermometer, and the temperature was raised from 160 ℃ to 220 ℃ over 4 hours, and the esterification reaction was carried out while passing through a dehydration step. Then, the pressure in the system was reduced to 5mmHg over 20 minutes, and the temperature was further raised to 250 ℃ to perform a polycondensation reaction step. Then, the pressure was reduced to 0.3mmHg or less, and after a polycondensation reaction was performed for 60 minutes, the reaction product was taken out. As a result of composition analysis by NMR of the obtained polyester (a 1), terephthalic acid/2, 6-naphthalenedicarboxylic acid/ethylene glycol/propylene glycol/trimethylolpropane =90/10/27/72/1[ molar ratio ] in terms of molar ratio. Further, the glass transition temperature was 89 ℃. The results are set forth in Table 1.
Production examples of polyesters (a 2) to (a 11)
According to the production example of the polyester (a 1), the polyesters (a 2) to (a 11) were synthesized by changing the kinds and blending ratios of the raw materials. In addition, in the polyester (a 2), after the polymerization reaction, further adding epsilon-caprolactone, at 200 degrees C reaction for 30 minutes, implementation post addition. Further, after the polymerization reaction was completed, trimellitic anhydride was further added to the polyester (a 3), and the reaction was carried out at 230 ℃ for 30 minutes to carry out acid post-addition. The compositional analysis value, melting point (Tm), and glass transition temperature (Tg) of each polyester are shown in table 1. In addition, PTMG 1000 was polytetramethylene ether glycol (average molecular weight 1000). In table 1, the case where the melting point (Tm) was not observed is represented as "-".
Figure BDA0003838595610000091
Example 1
An adhesive composition was prepared by mixing 80 parts (solid content) of a polyester (a 1) having a solid content concentration of 50% dissolved in toluene, 20 parts (solid content) of a polyester (a 2) having a solid content concentration of 50% dissolved in toluene, and 2 parts of SUMIDUR N3300 (125731251241251124721254012512512540125400, manufactured by Sumika Covestro urea company). The obtained adhesive composition was evaluated for peel strength, wet solder heat resistance, and flexibility of the uncured coating film. The results are shown in Table 2.
Examples 2 to 14 and comparative examples 1 to 4
Adhesive compositions were prepared according to example 1 by changing the kinds and mixing ratios of the raw materials as shown in table 2, and the respective evaluations were carried out. The results are shown in Table 2.
Peel strength (adhesiveness)
The adhesive composition prepared in each example was applied to a polyimide film (manufactured by Kaneka, apical (registered trademark)) having a thickness of 12.5 μm so that the thickness after drying became 25 μm, and dried at 140 ℃ for 3 minutes. The adhesive film (B-stage) thus obtained was bonded to a rolled copper foil (BHY series, manufactured by JX Metal Co., ltd.) having a thickness of 18 μm. The bonding was performed by pressing the glossy surface of the rolled copper foil against the adhesive layer at 160 ℃ under a pressure of 2MPa for 30 seconds. Subsequently, the film was cured by heat treatment at 170 ℃ for 3 hours to obtain a sample for peel strength evaluation. For the peel strength, the film was pulled at 125 ℃ and a 180 DEG peel test was conducted at a stretching speed of 50mm/min to measure the peel strength. This test shows the adhesive strength at 125 ℃.
< evaluation criteria >
O: 0.3N/mm or more
And (delta): 0.1N/mm or more and less than 0.3N/mm
X: 0.1N/mm or less
Heat resistance of humidified solder
A sample was produced in the same manner as in the above peel strength evaluation. The sample was cut into a size of 2.0cm × 2.0cm, allowed to absorb moisture at 40 ℃ under a temperature and humidity environment of 80% for 2 days, floated in a solder bath melted at 260 ℃, and the time until swelling occurred was measured.
< evaluation criteria >
O: no swelling for more than 60 seconds
And (delta): swelling in 30-60 seconds
X: swelling in less than 30 seconds
Flexibility of uncured coating film
The adhesive composition prepared in each example was applied to a polyimide film (manufactured by Kaneka, apical (registered trademark)) having a thickness of 12.5 μm so that the thickness after drying became 25 μm, and dried at 140 ℃ for 3 minutes. Whether or not cracks were generated in the coating film when the adhesive film (B-stage product) thus obtained was bent at 90 ° was checked and evaluated.
< evaluation criteria >
O: has no cracks
And (delta): with folds
X: has cracks
[ Table 2]
Figure BDA0003838595610000121
Industrial applicability of the invention
The uncured coating film of the adhesive composition of the present invention is excellent in flexibility, wet solder heat resistance and peel strength at high temperatures. Therefore, the adhesive composition is suitable for an FPC exposed to high temperatures, such as an FPC for an automobile.

Claims (5)

1. An adhesive composition comprising a polyester (A1) having a glass transition temperature or melting point of more than 80 ℃ and a polyisocyanate (B).
2. The adhesive composition according to claim 1, further comprising a polyester (A2) having a glass transition temperature of 0 ℃ or lower and a melting point of 80 ℃ or lower or being amorphous.
3. The adhesive composition according to claim 2, wherein the content of the polyester (A2) is 10 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the polyester (A1).
4. The adhesive composition according to any one of claims 1 to 3, wherein when the adhesive composition does not contain the polyester (A2), the polyisocyanate (B) is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the polyester (A1); when the adhesive composition contains the polyester (A2), the polyisocyanate (B) is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the polyester (A1) and the polyester (A2).
5. The adhesive composition according to any one of claims 1 to 4, which is used for a flexible printed wiring board.
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