TWI748014B - High molecular compound containing carboxylic acid group and adhesive composition containing the high molecular compound - Google Patents

Abstract

The subject of the present invention is to provide an adhesive composition that maintains good adhesive properties while having excellent moisture and heat resistance. Among them, the good adhesive properties are suitable for various plastic films, or metals such as copper, aluminum, and stainless steel, and glass rings. In terms of oxygen resin; the damp and heat resistance refers to the high degree of damp and heat resistance that can also correspond to lead-free solder under high humidity. The solution to this problem is a polymer compound containing a carboxylic acid group, which at least includes a polymer polyol (A) with a number average molecular weight (Mn1) of 7,000 or more, which is different from the polymer polyol (A) and has a number average molecular weight ( Mn2) is 1,000 or more polymer polyol (B), and tetracarboxylic dianhydride as the copolymerization component, and meet the following (1) ~ (2): (1) In the copolymerization component, the polymer polyol ( A) has the largest number average molecular weight (Mn1); (2) the number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is less than 1.7 times the number average molecular weight (Mn1) of the polymer polyol (A).

Description

High molecular compound containing carboxylic acid group and adhesive composition containing the high molecular compound

The present invention relates to a carboxylic acid group-containing polymer compound with excellent adhesion to various plastic films, copper, aluminum, stainless steel and other metals, glass epoxy resin, and moisture and heat resistance, and the adhesion containing the polymer compound A composition, an adhesive sheet, and a printed wiring board including this sheet as a constituent element.

In recent years, adhesives have been used in various fields. However, due to the diversification of the purpose of use, it is required to compare The adhesives that have been used in the past have improved performance. For example, an adhesive for a circuit board, such as a flexible printed wiring board (hereinafter sometimes referred to as FPC), requires adhesiveness, processability, electrical properties, and storage properties. In the past, in this application, epoxy/acrylic butadiene-based adhesives, epoxy/polyvinyl butyral-based adhesives, etc. have been used.

In particular, in recent years, considering the use environment corresponding to lead-free solder or FPC, an adhesive with a higher degree of heat resistance is required. In addition, considering the high density of wiring, the multilayering of FPC wiring boards, and the workability, there is a strong demand for solder resistance under high humidity. In response to these problems, existing documents have disclosed resin compositions for adhesives containing specific polyesters or polyester-polyurethane and epoxy resins as main components (for example, Patent Documents 1 to 2). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 11-116930 [Patent Document 2] Japanese Patent Application Publication No. 2008-205370

[The problem to be solved by the invention]

However, the composition described in Patent Document 1 does not necessarily provide satisfactory results from the viewpoint of solder heat resistance under lead-free conditions. In addition, the composition shown in Patent Document 2 is not sufficiently satisfactory regarding the solder heat resistance under lead-free conditions depending on the type of substrate.

The subject of the present invention is to improve the various problems of these conventional adhesives, and to provide a carboxylic acid group-containing polymer compound and an adhesive composition containing the carboxylic acid group-containing polymer compound that maintain good The adhesiveness is also excellent in heat and humidity resistance. Among them, the good adhesiveness is for various plastic films, or metals such as copper, aluminum, stainless steel, and glass epoxy resin; the heat and humidity resistance means that it can also correspond to high High degree of heat and humidity resistance of lead-free solder under humidity. [Means to solve the problem]

After in-depth discussion, the inventors found that the above-mentioned problems can be solved by the following methods, and the present invention has even been completed. That is, the present invention is constituted by the following.

A polymer compound containing a carboxylic acid group, which includes at least the following components as copolymerization components, and satisfies the following (1) to (2); A polymer polyol (A) with a number average molecular weight (Mn1) of 7,000 or more; and The polymer polyols (A) are different and the number average molecular weight (Mn2) is 1,000 or more. The number average molecular weight (Mn1) is the largest; (2) The number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is less than 1.7 times the number average molecular weight (Mn1) of the polymer polyol (A).

The polymer polyol (A) and/or the polymer polyol (B) are preferably polyester polyol or polycarbonate polyol.

An adhesive composition containing the aforementioned polymer compound containing carboxylic acid groups. An adhesive sheet containing the hardened substance of the adhesive composition. A printed wiring board containing the adhesive sheet as a constituent element. [Effects of the invention]

The carboxylic acid group-containing polymer compound and the adhesive composition containing the carboxylic acid group-containing polymer compound of the present invention maintain good adhesiveness and have excellent moisture and heat resistance (solder resistance). Among them, the good The adhesiveness is for various plastic films, or metals such as copper, aluminum, stainless steel, and glass epoxy resin; the heat and humidity resistance refers to the high degree of heat and humidity resistance that can also correspond to lead-free solder under high humidity.

<Polymer polyol (A)> The number average molecular weight (Mn1) of the polymer polyol (A) must be 7,000 or more. It is preferably 7,000 or more, more preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 12,000 or more. If Mn1 is less than 7,000, the crosslinking density will increase, and the coating film obtained from the adhesive composition will become harder, and the adhesive force will tend to decrease. In addition, the stress of water vapor generated during humidification resistance soldering becomes difficult to relieve, and the resistance to humidification solder tends to deteriorate. In addition, Mn1 is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. If it is too large, crosslinking may become insufficient and heat resistance may decrease.

The acid value (mgKOH/g) of the polymer polyol (A) is not particularly limited, and is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. If it is low, there is no problem, but if it is too large, the acid addition chain extension due to tetracarboxylic dianhydride may become impossible. Therefore, because the polymer polyols (B) react with each other, the cross-linking density becomes high, the coating film derived from the adhesive composition becomes hard, and the adhesive force tends to decrease.

The hydroxyl value (mgKOH/g) of the polymer polyol (A) is not particularly limited. As far as the maximum value is concerned, it is preferably 24 mgKOH/g or less, more preferably 21 mgKOH/g or less, and even more preferably 16 mgKOH/g or less, It is particularly preferably below 14mgKOH/g. If it is too large, the reaction may become insufficient and heat resistance may not be exhibited. In terms of the minimum value, it is preferably 2 mgKOH/g or more, more preferably 3 mgKOH/g or more, and even more preferably 3.5 mgKOH/g or more. If it is too small, the cross-linking density may decrease and heat resistance may not be exhibited.

The glass transition temperature of the polymer polyol (A) is not particularly limited, but it is preferably 0°C or higher, and more preferably 5°C or higher. If the glass transition temperature is too low, the adhesive composition will become more viscous, and bubbles will tend to be trapped during bonding and become defective. Furthermore, it is preferably 60°C or lower, more preferably 50°C or lower, even more preferably 40°C or lower, and particularly preferably 30°C or lower. If the glass transition temperature is too high, the coating film will become brittle, and embrittlement will become a problem.

<Polymer polyol (B)> The polymer polyol (B) is a polyol different from the polymer polyol (A), and the number average molecular weight (Mn2) must be 1,000 or more. Being different from the polymer polyol (A) means that it is different in at least one of composition and physical properties. The number average molecular weight (Mn2) is preferably 1,200 or more, more preferably 1,500 or more. If it is less than 1,000, the polymer polyols (B) tend to form bonds with each other, so they tend to have low molecular weights and high acid values, and the coating film after crosslinking tends to produce gels. Moreover, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 6,000 or less. If it is too large, the amount of carboxylic acid groups that can be imparted decreases, and the crosslink density of the resulting coating film may be insufficient, resulting in insufficient heat resistance.

The acid value (mgKOH/g) of the polymer polyol (B) is not particularly limited, and is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. If it is too high, the acid addition chain extension caused by tetracarboxylic dianhydride may become impossible.

The hydroxyl value (mgKOH/g) of the polymer polyol (B) is not particularly limited. As far as the maximum value is concerned, it is preferably 120 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 80 mgKOH/g or less. If the hydroxyl value is too high, the polymer polyol (B) becomes easy to bond to each other, so it has a low molecular weight and a high acid value, and the coating film after crosslinking becomes easy to produce a gel. In terms of the minimum value, it is preferably 11 mgKOH/g or more, more preferably 14 mgKOH/ or more, and even more preferably 18 mgKOH/g or more. If it is too low, the acid addition chain extension due to tetracarboxylic dianhydride may become impossible.

The glass transition temperature of the polymer polyol (B) is not particularly limited. In the case of polyester polyols, it is preferably -20°C or higher, more preferably -10°C or higher, more preferably 0°C or higher, and 10°C or higher More preferably, it is particularly preferably above 20°C, and most preferably above 30°C. In the case of polycarbonate polyols, the temperature is preferably -100°C or higher, more preferably -90°C or higher, still more preferably -80°C or higher, and particularly preferably -70°C or higher. If the glass transition temperature is too low, the adhesive composition tends to become more viscous, and bubbles tend to be trapped during bonding and become defective. In the case of polyester polyols, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. In the case of polycarbonate polyol, it is preferably below 0°C, more preferably below -10°C, and even more preferably below -20°C. If the glass transition temperature is too high, the coating film will become brittle, and embrittlement will become a problem.

The number average molecular weight (Mn1) of the polymer polyol (A) must be greater than the number average molecular weight (Mn2) of the polymer polyol (B), and the difference in molecular weight is not particularly limited. It is preferably 6,000 or more, more preferably 8,000 or more. Best, more preferably 10,000 or more. By setting the aforementioned difference in molecular weight, the compatibility, heat resistance, and resistance to humidified solder of the carboxylic acid group-containing polymer compound can be improved. That is, the high molecular weight of the high molecular polyol (A) by introducing long-chain blocks can relieve stress caused by water vapor generated during the evaluation of the resistance to humidified solder. In addition, the amount of carboxylic acid groups can be adjusted by the short-chain block of the polymer polyol (B), so heat resistance can be imparted. In this way, the heat resistance and the resistance to humidified solder can be improved. The upper limit of the difference in molecular weight is not particularly limited, but it is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less.

The polymer polyol (A) and/or the polymer polyol (B) are not particularly limited, and are preferably polyester polyol or polycarbonate polyol. These can be used alone or in combination of two or more kinds. When both the polymer polyol (A) and the polymer polyol (B) are used independently of the same type, phase separation is less likely to occur, and the viewpoint that the reaction can proceed efficiently is advantageous. On the other hand, by using multiple different types of polyols in combination, it is possible to impart characteristics that cannot be obtained when used alone. For example, by using a polyester polyol for the polymer polyol (A) and a polycarbonate polyol for the polymer polyol (B), improvement in hydrolysis resistance can be expected. Ideally, both the polymer polyol (A) and the polymer polyol (B) are polyester polyols.

<Polyester polyol> The polyester polyol is preferably composed of a polyvalent carboxylic acid component and a polyol component. With regard to the polycarboxylic acid components constituting the polyester polyol, when the total polycarboxylic acid is 100 mol%, it is preferable to contain 60 mol% or more of the aromatic dicarboxylic acid. It is more preferably 70 mol% or more, more preferably 80 mol% or more, and 100 mol% is not a problem. If it is too small, the cohesive force of the coating film will be weak, and the bonding strength to various substrates will decrease.

There are no particular restrictions on aromatic dicarboxylic acids, and examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and 2,2'-biphenyl dicarboxylic acid. Formic acid. In addition, examples include: sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfo Aromatic dicarboxylic acids having sulfonic acid groups such as phenoxy) isophthalic acid, and aromatic dicarboxylic acids having sulfonic acid salt groups such as their metal salts and ammonium salts. These can be used alone or in combination of two or more kinds. Among them, terephthalic acid, isophthalic acid, and mixtures thereof are particularly preferable from the viewpoint of enhancing the cohesive force of the coating film.

As for other polycarboxylic acid components, alicyclic rings such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and anhydrides thereof, etc. Aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid. In addition, 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenyl alcohol, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis(p-hydroxyphenyl) (Hydroxyphenyl) valeric acid and other hydroxycarboxylic acid compounds having a hydroxyl group and a carboxyl group in the molecular structure.

Regarding the polyol components constituting the polyester polyol, when the total polyol is 100 mol%, the glycol component is preferably 90 mol% or more, preferably 95 mol% or more, which is 100 mol% It's okay.

The glycol components are preferably aliphatic glycols, alicyclic glycols, aromatic glycols, or ether bond-containing glycols. Examples of aliphatic glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1 ,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-Ethyl-2-butylpropanediol (DMH), neopentyl glycol hydroxytrimethyl acetate, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol, etc. . Examples of alicyclic diols include: 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, and dimethyloltricyclodecane , Spirodiol, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adducts and propylene oxide adducts, etc. Examples of glycols containing ether bonds include: diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ring Ethylene oxide adduct, neopentyl glycol propylene oxide adduct. Examples of aromatic-containing glycols include: p-xylene glycol, meta-xylene glycol, o-xylene glycol, 1,4-phenylene glycol, and 1,4-phenylene glycol Ethylene oxide adducts of base diols; bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts are separately added to the two phenolic hydroxyl groups of bisphenols Diols derived from 1 to several moles of ethylene oxide or propylene oxide, etc. These can be used alone or in combination of two or more kinds. Among them, it is preferably aliphatic glycols, such as ethylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl- 1,3-propanediol or 1,6-hexanediol is more preferable.

In polyester polyols, for the purpose of introducing branch skeletons according to needs, components with trifunctional or higher functions can also be copolymerized with polycarboxylic acid components and/or polyol components. During copolymerization, when the total polycarboxylic acid component and the total polyol component are each 100 mol%, the trifunctional or higher component is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and more preferably 5 mol% or less, preferably 3 mol% or less. By setting it within the above range, especially when a hardened coating film is prepared by reacting trifunctional or higher components with a hardener, the branch skeleton can be introduced, and the terminal group concentration (reaction site) of the resin can be increased, and Obtain a coating film with high crosslinking density and strength. In addition, if it exceeds 5 mol%, mechanical properties such as elongation at the breaking point of the coating film may decrease, which may cause gelation during polymerization.

Examples of polycarboxylic acid components with more than three functions include: trimellitic acid, trimellitic acid, ethylene glycol bis(dehydrated trimellitic acid), and glycerol ginseng (dehydrated trimellitic acid). , Trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3 ,3',4,4'-Diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-Diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-( Compounds such as hexafluoroisopropylene)diphthalic dianhydride (6FDA), 2,2'-bis((dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), etc. On the other hand, examples of trifunctional or higher polyols include glycerin, trimethylolethane, trimethylolpropane, neopentylerythritol, and the like.

The acid value can also be introduced into the polyester polyol. The acid value of the polyester polyol is preferably 10 mgKOH/g or less, more preferably 8 mgKOH/g or less. If it is low, there is no particular problem, but if it is too high, the acid addition chain extension due to tetracarboxylic dianhydride may become impossible.

As for the method of introducing the acid value, a method of introducing carboxylic acid into the polyester polyol by acid addition after polymerization can be exemplified. If monocarboxylic acid, dicarboxylic acid, or trifunctional or higher polycarboxylic acid compound is used for acid addition, since the molecular weight may decrease due to transesterification, it is preferable to use a compound having at least one carboxylic anhydride group. For carboxylic anhydrides, succinic anhydride, maleic anhydride, phthalic anhydride, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride can be listed (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyl Tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) diphthalic acid Dianhydride (6FDA), 2,2'-bis((dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), etc.

<Polycarbonate polyol> The polycarbonate polyol is a polyol having a carbonate bond, preferably a polycarbonate diol. A commercially available product can be used as the polycarbonate diol. Commercially available polycarbonate diols include, for example, the trade names DURANOL (registered trademark) T-4692 (number average molecular weight 2000), T-5652 (number average molecular weight 2000), manufactured by Asahi-Kasei Chemicals, T-5651 (number average molecular weight 1000), T-6002 (number average molecular weight 2000), CD-220 (number average molecular weight 2000), CD-220PL (number average molecular weight 2000), CD-220HL (number average molecular weight 2000); Trade names KURARAY POLYOL C-2050 (number average molecular weight 2000), C-2090 (number average molecular weight 2000), C-3090 (number average molecular weight 3000) manufactured by Kuraray; trade names ETERNACOLL manufactured by Ube Industries Co., Ltd. (registered Trademark) UH-100 (number average molecular weight 1000), UH-200 (number average molecular weight 2000), PH-100 (number average molecular weight 1000), PH-200 (number average molecular weight 2000), etc. Using a polyester polyol with a low glass transition temperature as the polymer polyol (B) is disadvantageous from the viewpoint of hydrolyzability. However, it is believed that the use of polycarbonate polyol can eliminate ester bonds with poor hydrolyzability. Can improve hydrolysis. Regarding the polycarbonate polyol, considering the workability, it is preferable to be in a liquid form, and the DURANOL (registered trademark) series is particularly desirable.

<Tetracarboxylic dianhydride> Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, or alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride is preferable. Specifically, examples include: pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) , 3,3',4,4'-Diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-Diphenyl tetracarboxylic dianhydride (DSDA), 4,4' -(Hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2'-bis((dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), they can be used alone or 2 Combine the above. Among them, pyromellitic anhydride is preferable.

<Carboxylic acid group-containing polymer compound> The carboxylic acid group-containing polymer compound of the present invention includes at least the aforementioned polymer polyol (A), polymer polyol (B) and tetracarboxylic dianhydride as copolymerization components, And (1) among the copolymerization components, the number average molecular weight (Mn1) of the polymer polyol (A) is the largest; (2) the number average molecular weight (Mn3) of the polymer compound containing carboxylic acid groups is the polymer polyol (A) ) Is less than 1.7 times the number average molecular weight (Mn1).

The present invention uses polymer polyols of two or more components including a polymer polyol (A) with a number average molecular weight of 7,000 or more and a polymer polyol (B) with a number average molecular weight of 1,000 or more by copolymerizing components, and further uses Tetracarboxylic dianhydride is used for chain extension to improve heat resistance and resistance to humidified solder. That is, by using a long-chain polymer polyol (A) block to relieve the stress of water vapor generated during the evaluation of the resistance to humidified solder, the resistance to humidified solder can be improved, and at the same time, by introducing short-chain In the polymer polyol (B) block, a sufficient amount of carboxylic acid can be introduced for imparting heat resistance. If the polymer polyol (A) is chain-extended with tetracarboxylic dianhydride alone, the molecular weight will increase, and the crosslinking necessary to withstand solder may not be obtained. In addition, if a chain extender is used at this time, the reaction product of the chain extenders is likely to be produced due to the relationship of the molar balance, so that the cured coating film becomes easy to produce a gel.

The glass transition temperature of the carboxylic acid group-containing polymer compound is not particularly limited, and it is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. If the glass transition temperature is too low, the adhesive composition will become more viscous, and bubbles will tend to be trapped during bonding and become defective. Furthermore, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. If the glass transition temperature is too high, the coating film will become brittle, and embrittlement will become a problem.

<Requirement (1)> The requirement (1) is explained. Among the copolymerization components of the carboxylic acid group-containing polymer compound, the number average molecular weight (Mn1) of the polymer polyol (A) must be the largest. As for the copolymerization component, polymer polyol (A), polymer polyol (B), and tetracarboxylic dianhydride are used. In addition, any other polyol components can be used, for example, other polyol components, or the following However, the number average molecular weight (Mn1) of the polymer polyol (A) must be the largest among the number average molecular weight of all the copolymerization components including them. By maximizing the number-average molecular weight (Mn1) of the polymer polyol (A), it will become the largest long-chain polymer polyol among the polymer compounds containing carboxylic acid groups. The base polymer compound has excellent resistance to humidified solder.

<Requirement (2)> Requirement (2) is explained. The number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound must be less than 1.7 times the number average molecular weight (Mn1) of the polymer polyol (A). That is, Mn3/Mn1≦1.7. Ideally, it is 1.6 times or less. When it exceeds 1.7 times, it is considered that the difference in molecular weight is small, or the amount of tetracarboxylic dianhydride is excessive. Therefore, the carboxylic acid group content of the carboxylic acid group-containing polymer compound is insufficient and the heat resistance is reduced, or the elastic modulus of the cured coating film becomes too high and the adhesiveness tends to become low. The lower limit of Mn3/Mn1 is preferably 0.8 times or more, more preferably 0.9 times or more, and even more preferably 1.0 times or more. If it is too small, the reaction between the polymer polyol (B) and the chain extender (tetracarboxylic dianhydride) may occur more often, so it is possible that the block of the polymer polyol (A) may not sufficiently interact with the carboxylic acid dihydric alcohol (B). Anhydride reacts, and the resistance to humidified solder becomes insufficient. In addition, if the carboxylic acid group-containing polymer compound is within the range of the number average molecular weight (Mn3/Mn1), it contains only the polymer polyol (A) and the carboxylic dianhydride resin, or only the polymer polyol ( B) Resins with carboxylic dianhydride are also okay.

The acid value of the carboxylic acid group-containing polymer compound of the present invention is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and even more preferably 15 mgKOH/g or more. Furthermore, it is preferably 100 mgKOH/g or less, more preferably 60 mgKOH/g or less, and even more preferably 40 mgKOH/g or less. If the acid value is too low, sufficient heat resistance may not be obtained due to insufficient cross-linking. If the acid value is too high, the cross-linking density may become too high and the cured coating film may become hard and the adhesiveness may decrease. condition. In addition, the storage stability of a varnish prepared by dissolving a carboxylic acid group-containing polymer compound in a solvent may decrease, and the crosslinking reaction may proceed easily at room temperature, and a stable sheet life may not be obtained.

The carboxylic acid group-containing polymer compound of the present invention does not need to be limited to the three components of the aforementioned polymer polyol (A), polymer polyol (B) and tetracarboxylic dianhydride, and other high molecular weight components can be used as The fourth copolymerization component. Examples of the fourth copolymer component include polymer polyols that are different from the polymer polyol (A) and the polymer polyol (B). When the fourth copolymerization component is used, the number average molecular weight of the fourth copolymerization component is preferably less than Mn1 of the polymer polyol (A) and more than Mn2 of the polymer polyol (B).

In terms of the copolymerization ratio of the polymer polyol (A) and the polymer polyol (B) in the carboxylic acid group-containing polymer compound, relative to 100 parts by mass of the polymer polyol (A), the polymer polyol (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. In addition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. A case where the number of terminals that react with tetracarboxylic anhydride is reduced, resulting in insufficient heat resistance.

In terms of the copolymerization ratio of the polymer polyol (A) and the tetracarboxylic dianhydride in the carboxylic acid group-containing polymer compound, relative to 100 parts by mass of the polymer polyol (A), the tetracarboxylic dianhydride is suitable It is 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. In addition, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. The coating film may become hard and sufficient adhesion may not be obtained.

The copolymerization amount of the polymer polyol (A) in the carboxylic acid group-containing polymer compound is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. By increasing the copolymerization amount of the polymer polyol (A), the improvement of the resistance to humidified solder can be expected. Furthermore, it is preferably 90% by weight or less, more preferably 85% by weight or less, and even more preferably 80% by weight or less. If it is too large, the copolymerization amount of the polymer polyol (B) or tetracarboxylic dianhydride may decrease, and the heat resistance or adhesion may decrease.

<Chain extender> The carboxylic acid group-containing polymer compound contains polymer polyol (A), polymer polyol (B), and tetracarboxylic dianhydride as long as the effect of the present invention is not impaired. In addition to the copolymerization component, a chain extender can be used arbitrarily. By using a chain extender, the acid value can be efficiently imparted. The amount of copolymerization when using a chain extender is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more with respect to 100 parts by mass of the polymer polyol (A). Furthermore, it is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. If the amount of copolymerization is too large, it may become difficult to increase the molecular weight, and the chain extenders may react with each other to cause the varnish to become cloudy.

The chain extender is preferably a low-molecular diol with a molecular weight of 1000 or less, and examples thereof include 2,2-dimethyl-1,3-propanediol, or dimethylolbutyric acid. These can be used alone or in combination of two or more kinds. Among them, from the viewpoint of solubility or compatibility, 2,2-dimethyl-1,3-propanediol is preferable.

、N,N-二異丙基乙胺、N,N-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、或6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一烯-7等三級胺類、及將這些三級胺類以苯酚、辛酸、或四級化四苯基硼酸鹽等製成胺鹽之化合物；溴化四甲基銨、溴化四乙基銨、溴化四正丁基銨、氯化四甲基銨、氯化三甲基苄銨、氯化三乙基苄銨、氫氧化四甲基銨、氫氧化三甲基苄銨、氫氧化四正丁基銨等4級銨鹽。The carboxylic acid group-containing polymer compound may also use a quaternary ammonium salt or a tertiary amine as a reaction catalyst within the range that does not impair the effect of the present invention. Examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2- Ethyl-4-methylimidazole and other imidazole compounds; triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piper

, N,N-diisopropylethylamine, N,N-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-di Azabicyclo(4,3,0)-nonene-5, or 6-dibutylamino-1,8-diazabicyclo(5,4,0)-undecene-7 and other tertiary amines Class, and these tertiary amines are made of phenol, caprylic acid, or quaternary tetraphenyl borate, etc. into amine salts; tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butyl bromide Base ammonium, tetramethyl ammonium chloride, trimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, tetramethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, etc. 4 Grade ammonium salt.

<Adhesive composition> The adhesive composition of the present invention contains at least the aforementioned carboxylic acid group-containing polymer compound, and preferably contains an organic solvent or an epoxy resin (D).

The adhesive composition preferably contains 20% by mass or more of the carboxylic acid group-containing polymer compound, more preferably 30% by mass or more, and even more preferably 40% by mass or more. Furthermore, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. If the amount is too small, the adhesiveness or moisture and heat resistance may decrease. If the amount is too large, the storage stability of the adhesive composition may decrease.

<Organic solvent> The organic solvent is not particularly limited as long as it dissolves the carboxylic acid group-containing polymer compound, but it is more preferable to also dissolve the epoxy resin (D). As for organic solvents, you can use: aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; methanol, ethanol, Alcohol solvents such as isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, etc. Ketone solvents; celluloid such as methyl cellulose and ethyl cellulose; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; trichloroethylene, Halogenated hydrocarbons such as dichloroethylene, chlorobenzene, and chloroform can be used singly or in combination of two or more. Among them, a mixed solvent of aromatic hydrocarbons and ketone solvents is preferable, and a mixed solvent of toluene and methyl ethyl ketone is more preferable.

The amount of the organic solvent relative to 100 parts by mass of the carboxylic acid group-containing polymer compound is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 100 parts by mass or more. Furthermore, it is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. If the amount is too small, the storage stability of the adhesive composition may decrease. If the amount is too large, it may become industrially disadvantageous.

<Epoxy resin (D)> If the epoxy resin (D) is crosslinked by curing reaction with the carboxyl group of the carboxylic acid group-containing polymer compound, it is not particularly limited, and it is preferable to have multiple epoxy resins in one molecule. Multifunctional epoxy resin based. By using a multifunctional epoxy resin, the hardened coating film derived from the adhesive composition can easily form three-dimensional crosslinks, which can improve heat resistance. The polyfunctional epoxy resin includes, for example, a cresol novolak resin type epoxy resin, or an epoxy resin having a dicyclopentadiene skeleton, and a phenol novolak resin type epoxy resin. If it is a cresol novolac resin type epoxy resin or a phenol novolac resin type epoxy resin, the crosslink density of the hardened coating film can be reduced, and the stress at the time of peeling can be relieved, thereby improving the resistance to humidified solder. As for the commercial products of the cresol novolak resin type epoxy resin, YDCN-700 manufactured by DIC Corporation can be mentioned. On the other hand, if it is an epoxy resin with a dicyclopentadiene skeleton, since the dicyclopentadiene skeleton is rigid, the moisture absorption of the hardened coating film can be extremely small, and the crosslinking density of the hardened coating film can be increased Decrease, and relieve the stress during peeling. Therefore, the resistance to humidified solder will be improved. As for the commercially available product of the epoxy resin having a dicyclopentadiene skeleton, the HP7200 series manufactured by DIC Corporation can be mentioned. These can be used alone or in combination of two or more kinds.

Furthermore, in addition to the above-mentioned polyfunctional epoxy resins, nitrogen atom-containing epoxy resins may also be used. If the epoxy resin containing nitrogen atoms is used in combination, the coating film of the adhesive composition can be heated at a relatively low temperature into a semi-cured state (hereinafter sometimes referred to as B-stage), and the B-stage can be suppressed The fluidity of the film has a tendency to improve the workability in the bonding operation. In addition, since the effect of suppressing the blistering of the B-stage film can be expected, it is preferable. For epoxy resins containing nitrogen atoms, for example, tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, tetraglycidyl bisaminomethyl cyclohexanone, Glyoxypropyl amines such as N,N,N',N'-tetraglycidyl m-xylene diamine, etc. The blending amount of these nitrogen atom-containing epoxy resins is preferably 20% by mass or less of the entire epoxy resin (D). If the blending amount is more than 20% by mass, the rigidity becomes too high and the adhesiveness tends to decrease. In addition, the crosslinking reaction tends to proceed easily during storage of the adhesive sheet, and the life of the sheet tends to decrease. . A more preferable upper limit of the blending amount is 10% by mass, and even more preferably 5% by mass.

It is also possible to use other epoxy resins in combination as the epoxy resin (D) used in the present invention. Examples include: glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether; glycidyl hexahydrophthalate, two Glycidyl ester type such as polyglycidyl ester; triglycidyl isocyanurate, 3,4-epoxycyclohexyl methyl carboxylic acid, epoxidized polybutadiene, epoxidized soybean oil, etc. As for the cyclic or aliphatic epoxides, one kind may be used alone, or two or more kinds may be used in combination.

The epoxy resin (D) is preferably 2 parts by mass or more with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound, and more preferably 5 parts by mass or more. Moreover, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. If the amount is too small, the curing may be insufficient, and the adhesiveness and heat resistance may decrease. If the amount is too large, the uncrosslinked epoxy resin may increase and the heat resistance may decrease.

、1,8-二氮雜雙環(5,4,0)-十一烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、或6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一烯-7等三級胺類、及將這些三級胺類以苯酚、辛酸、或四級化四苯基硼酸鹽等製成胺鹽之化合物；三烯丙基鋶六氟銻酸鹽或二烯丙基錪六氟銻酸鹽等陽離子觸媒；三苯基膦等。它們之中，就熱硬化性、耐熱性、對金屬之黏接性、及摻合後之保存安定性的觀點而言，1,8-二氮雜雙環(5,4,0)-十一烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、或6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一烯-7等三級胺類、及將這些三級胺類以苯酚、辛酸、或四級化四苯基硼酸鹽等製成胺鹽之化合物為較佳。硬化觸媒之摻合量相對於含羧酸基之高分子化合物100質量份，宜為0.01~1.0質量份。若為此範圍，則可進一步增加對於含羧酸基之高分子化合物與環氧樹脂(D)之反應的觸媒效果，並獲得牢固的黏接性能。In the present invention, a curing catalyst can be used for the curing reaction of the epoxy resin (D). Examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2- Ethyl-4-methylimidazole and other imidazole compounds; triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piper

, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, or 6-dibutyl Amino-1,8-diazabicyclo(5,4,0)-undecene-7 and other tertiary amines, and these tertiary amines are phenol, caprylic acid, or quaternary tetraphenylboronic acid Salt and other compounds made into amine salts; cationic catalysts such as triallyl hexafluoroantimonate or diallyl hexafluoroantimonate; triphenyl phosphine, etc. Among them, 1,8-diazabicyclo(5,4,0)-11 Ene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, or 6-dibutylamino-1,8-diazabicyclo(5,4,0)- Tertiary amines such as undecene-7, and compounds in which these tertiary amines are made into amine salts with phenol, caprylic acid, or quaternary tetraphenylborate, etc. are preferred. The blending amount of the hardening catalyst is preferably 0.01 to 1.0 parts by mass relative to 100 parts by mass of the carboxylic acid group-containing polymer compound. If it is within this range, the catalytic effect on the reaction between the carboxylic acid group-containing polymer compound and the epoxy resin (D) can be further increased, and firm adhesion performance can be obtained.

<Other additives> The adhesive composition of the present invention may further incorporate various curable resins or additives within a range that does not impair the effects of the present invention. Examples of curable resins include phenol resins, amino resins, isocyanate compounds, and silicone resins.

Examples of phenol-based resins include alkylated phenols and formaldehyde condensates of cresols. Specifically, it can include: alkylated (for example: methyl, ethyl, propyl, isopropyl, butyl) phenol, p-terpyl phenol, 4,4'-second butylene phenol, p-tertiary butyl Phenol, o-cresol, m-cresol, p-cresol, p-cyclohexanol, 4,4'-isopropylidene, p-nonanol, p-octanol, 3-pentadecylphenol, phenol, phenyl o Formaldehyde condensates of cresol, p-phenylphenol, xylenol, etc. These can be used alone or in combination of two or more kinds.

The amino resins include, for example, formaldehyde adducts such as urea, melamine, and benzoguanamine, and more include alkyl ether compounds obtained by using alcohols having 1 to 6 carbon atoms. Specific examples include: methoxylated methylolurea, methoxylated methylol N,N-ethylidene urea, methoxylated methylol dicyandiamine, methoxylated methylol Melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, etc. Preferably, they are methoxylated methylol melamine, butoxylated methylol melamine, and methylolated benzoguanamine, which can be used individually or in combination.

The isocyanate compound may be aromatic or aliphatic diisocyanate, trivalent or higher polyisocyanate, and may be either a low molecular compound or a high molecular compound. Examples include: tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, diisocyanate Xylene cyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or terpolymers of these isocyanate compounds. Further examples include compounds containing terminal isocyanate groups obtained by reacting excess of these isocyanate compounds with low molecular active hydrogen compounds or high molecular active hydrogen compounds. Among them, the low molecular active hydrogen compounds are, for example, ethylene glycol, propylene glycol, Trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, or triethanolamine, etc.; the polymer active hydrogen compound such as: various polyester polyols, polyether polyols, polyamides Amines and so on.

The isocyanate compound may also be a blocked isocyanate. The isocyanate blocking agent includes, for example, phenols such as phenol, thiophenol, methyl thiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; acetoxime, Methyl ethyl ketoxime, cyclohexanone oxime and other oximes; methanol, ethanol, propanol, butanol and other alcohols; 2-chloroethanol, 1,3-dichloro-2-propanol and other halogen-substituted alcohols; tertiary Tertiary alcohols such as butanol and tertiary amyl alcohol; internal amines such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactin. Other examples include: aromatic amines, imines, acetone, acetone acetate, ethyl malonate, and other active methylene compounds; mercaptans, imines, ureas, diaromatics Base compounds such as sodium bisulfite, etc. The blocked isocyanate can be obtained by the addition reaction of the above-mentioned isocyanate compound, the isocyanate compound, and the isocyanate blocking agent by a conventional appropriate method.

In the adhesive composition of the present invention, a silane coupling agent can also be blended as needed. By blending the silane coupling agent, it is very ideal because it will improve the adhesion to metal and the characteristics of heat resistance. The silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amine group. As for the silane coupling agent having an unsaturated group, vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, etc. can be mentioned. Regarding the silane coupling agent with glycidyl group, γ-glycidoxy propyl trimethoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) ethyl triethoxy silane, etc. Regarding the silane coupling agent having an amino group, examples include: N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ- Aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. From the viewpoint of heat resistance, among them, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or β-(3, 4-epoxycyclohexyl) ethyl triethoxy silane and other silane coupling agents with glycidyl groups. The blending amount of the silane coupling agent is preferably 0.5-20 parts by mass relative to 100 parts by mass of the carboxylic acid group-containing polymer compound. If the blending amount of the silane coupling agent is less than 0.5 parts by mass, the heat resistance of the resulting adhesive composition may become poor. If it exceeds 20 parts by mass, the heat resistance may be poor. Or poor adhesion.

In the adhesive composition of the present invention, flame retardants such as bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds; additives such as levelling agents, pigments, and dyes can be appropriately blended according to needs.

<Adhesive sheet> In the present invention, the adhesive sheet refers to a coating film (hereinafter also referred to as an adhesive layer) containing an adhesive composition obtained by curing the adhesive composition of the present invention. The adhesive sheet has the function of using an adhesive layer to bond the substrate to the material to be bonded. After bonding, the base material of the bonding sheet functions as a protective layer of the bonded material. In addition, if a release base material is used, after the release base material is released, the adhesive layer can be transferred to another material to be bonded. The adhesive sheet can be obtained by coating the adhesive composition on the base material or the release base material, and then drying and hardening. In terms of specific structures, examples include: base material/adhesive layer, release base material/adhesive layer, release base material/adhesive layer/substrate, release base material/adhesive layer /Release substrate, etc. In addition, depending on the situation, it may be the adhesive layer itself after peeling the release base material. In addition, the adhesive sheet may contain a trace or a small amount of organic solvent.

The adhesive sheet can be obtained by applying the adhesive composition of the present invention to various substrates according to a common method, and removing at least a part of the solvent to dry it. In addition, after removing at least a part of the solvent and drying it, the release substrate can be attached to the adhesive layer, and it can be wound without causing transfer to the substrate. The handling is excellent, and the adhesive layer It is also protected, so it has excellent storage properties and is easy to use. In addition, after coating on a release substrate and drying, if another release substrate is attached as necessary, the adhesive layer itself can also be transferred to another substrate.

The base material is not particularly limited, and examples thereof include film-like resins, metal plates, metal foils, papers, and the like. Examples of film-like resins include polyester resins, polyamide resins, polyimide resins, polyimide resins, and olefin resins. For the materials of metal plates and metal foils, exemplified: various metals such as SUS, copper, aluminum, iron, zinc, and various alloys, platings, etc., for papers, exemplified: high-quality paper, kraft paper , Roll paper, cellophane, etc. Moreover, as for the composite material, glass epoxy resin and the like can be exemplified. Considering the adhesion and durability of the substrate and the adhesive composition, polyester resin, polyamide resin, polyimide resin, polyimide resin, SUS steel plate, copper foil, aluminum foil, and glass are suitable Epoxy resin.

There are no particular restrictions on the release substrate. For example, it can be exemplified by setting up a coating layer of clay, polyethylene, polypropylene and other fillers on both sides of paper such as high-quality paper, kraft paper, roll paper, cellophane, etc., and then Each coating layer is coated with silicone-based, fluorine-based, and alkyd-based mold release agents. In addition, various olefin films themselves, such as polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and the like, and application of the above-mentioned release agent to polyethylene terephthalate, etc. Those made on the film. Considering the demolding force of the mold release substrate and the adhesive layer, and the adverse effects of polysiloxane on the electrical properties, etc., it is suitable to be used on both sides of high-quality paper with polypropylene for filling and using alcohol on it. Those with acid-based mold release agents, or those with alkyd-based mold release agents used on polyethylene terephthalate.

There are no particular restrictions on the method of applying the adhesive composition on the substrate or the release substrate, and examples thereof include douche coating, reverse roll coating, and the like. Or the adhesive layer can be directly or by a transfer method according to the need to be placed on the material of the printed wiring board, that is, the rolled copper foil or the polyimide film. The thickness of the adhesive layer after drying will be appropriately changed according to needs, and it should be within the range of 5~200μm. If the thickness of the adhesive layer is less than 5 μm, the adhesive strength may become insufficient. If the thickness exceeds 200 μm, there may be problems such as increased residual solvent due to insufficient drying and swelling during the pressing of printed wiring board manufacturing. The drying conditions are not particularly limited, and the residual solvent rate after drying is preferably 4% by mass or less, and more preferably 1% by mass or less. If it is larger than 4% by mass, the following problem may occur: during the pressing of the printed wiring board, the residual solvent may foam and swell.

<Printed wiring board> The printed wiring board in the present invention includes an adhesive sheet as a constituent element, and more specifically, includes a laminate (metal foil/adhesive Adhesive layer/resin base material) as a constituent element. The printed wiring board is manufactured by a conventional method such as a subtraction method using a metal-clad laminate, for example. According to the needs, the conductor circuit formed by the metal foil is covered with a cover film, screen printing ink, etc., partly or the entire surface, collectively referred to as the so-called flexible circuit board (FPC), flat cable, and reel type Circuit boards for automatic bonding (TAB), etc.

The printed wiring board of the present invention can be made into any laminated structure that can be used as a printed wiring board. For example, it can be made into a printed wiring board composed of four layers of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. In addition, for example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer can be produced. The printed wiring board is sometimes reinforced with reinforcing materials as needed. At this time, the reinforcing materials and the adhesive layer are placed under the base film layer.

In addition, it can also be made into a structure in which 2 or 3 or more of the above-mentioned printed wiring boards are laminated according to needs.

The adhesive composition of the present invention can be suitably used in each adhesive layer of a printed wiring board. In particular, when the adhesive composition of the present invention is used as an adhesive, it can have high adhesiveness to a substrate constituting a printed wiring board, and can impart a high degree of heat resistance that is compatible with lead-free solder. Especially in the high temperature area where the solder resistance is evaluated, the chemical cross-linking of the resin and the resin and the physical cross-linking of the resin and the inorganic filler are given a good balance, so the solder resistance test under the humidified state will not occur. In the case of swelling or deformation caused by the impact caused by the evaporation of water in the water, the stress is relieved. Therefore, it is suitable for the adhesive between the metal foil layer and the cover film layer, and the adhesion between the base film layer and the reinforcing material layer. In particular, when using metal reinforcing materials such as SUS plates or aluminum plates, when welding is carried out in a humidified state, since water cannot evaporate from the reinforcing material side, the adhesion between the base film layer and the reinforcing material layer is reached. The impact of the adhesive layer is particularly strong, and it is suitable as the adhesive composition used for bonding at this time.

The inorganic filler used in the present invention is not particularly limited. For example, aluminum oxide, silicon dioxide, titanium oxide, tantalum oxide, zirconium oxide, silicon nitride, barium titanate, barium carbonate, and lead titanate can be used. , Lead zirconate titanate, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum hydroxide, magnesium hydroxide, aluminum titanate, yttrium oxide-containing zirconium oxide, barium silicate , Boron Nitride, Calcium Carbonate, Calcium Sulfate, Zinc Oxide, Zinc Borate, Magnesium Titanate, Magnesium Borate, Barium Sulfate, Organobentonite, Carbon, etc., they can be used alone or in combination of two or more. Considering the transparency, mechanical properties, and heat resistance of the adhesive composition, silica is preferred, and aerosol silica with a three-dimensional mesh structure is particularly preferred. In addition, in terms of imparting hydrophobicity, hydrophobic silica treated with monomethyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil, etc., is preferable. When aerosol silica is used as the inorganic filler, the average particle size of the primary particles is preferably 30nm or less, more preferably 25nm or less. If the average particle size of the primary particles exceeds 30 nm, the interaction between the particles or with the resin will decrease and the heat resistance will tend to decrease. In addition, the average particle diameter of the primary particles referred to herein refers to the average value of the diameter of a circle of 100 randomly selected particles from the image of the primary particles obtained by using a scanning electron microscope.

The blending amount of the inorganic filler relative to 100 parts by mass of the carboxylic acid group-containing polymer compound is preferably 10 parts by mass or more, more preferably 13 parts by mass or more, and even more preferably 15 parts by mass or more. If it is less than 10 parts by mass, the effect of improving heat resistance may not be exhibited. Furthermore, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. If the amount exceeds 50 parts by mass, poor dispersion of the inorganic filler may occur, or the viscosity of the solution may become too high, which may cause inconvenience to workability or decrease the adhesiveness.

In the printed wiring board of the present invention, as the base film, any resin film that has been used as a base material of a printed wiring board can be used. As for the resin of the base film, either halogen-containing resin or halogen-free resin can be used. From the viewpoint of environmental issues, halogen-free resins are preferable, but from the viewpoint of flame retardancy, halogen-containing resins can also be used. The substrate film is preferably a polyimide film or a polyimide film.

As for the metal foil used in the present invention, any conventional conductive material that can be used for circuit boards can be used. In terms of materials, for example, copper foil, aluminum foil, steel foil, and nickel foil can be used, as well as composite metal foil obtained by combining them, or metal treated with other metals such as zinc or chromium compounds. Foil. It should be copper foil.

There is no particular limitation on the thickness of the metal foil, and it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 10 μm or more. Moreover, it is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. When the thickness is too thin, it may sometimes be difficult to obtain sufficient electrical performance of the circuit. On the other hand, when the thickness is too thick, sometimes the processing efficiency when making the circuit may be reduced.

Metal foil is usually provided in the form of a roll. The form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited. When the metal foil in the form of a roll is used, its length is not particularly limited. Also, the width is not particularly limited, but it is preferably about 250 to 1000 mm.

As for the cover film, any insulating film conventionally known as an insulating film for printed wiring boards can be used. It can be used, for example, from polyimide, polyester, polyphenylene sulfide, polyether ether, polyether ether ketone, aromatic polyamide, polycarbonate, polyarylate, polyimide, polyamide Films made of various polymers such as imines. It is more preferably a polyimide film or a polyimide film, and even more preferably a polyimide film.

As for the material resin of the cover film, either halogen-containing resin or halogen-free resin can be used. From the viewpoint of environmental issues, halogen-free resins are preferable, but from the viewpoint of flame retardancy, halogen-containing resins can also be used.

The printed wiring board of the present invention can be manufactured using any conventional manufacturing process in addition to the materials of the above-mentioned layers.

An ideal embodiment is to manufacture a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter referred to as "cover film-side semi-finished product"). On the other hand, it manufactures a semi-finished product in which a metal foil is laminated on a base film layer and a desired circuit pattern is formed (hereinafter referred to as a "substrate film side two-layer semi-finished product") or an adhesive layer is laminated on the substrate The thin film layer is a semi-finished product made by laminating a metal foil layer on it and forming the desired circuit pattern (hereinafter referred to as "3-layer semi-finished product on the base film side"; hereinafter the 2-layer semi-finished product on the base film side and the base film side 3 Layer semi-finished products are collectively referred to as "substrate film side semi-finished products"). By bonding the semi-finished product on the cover film side and the semi-finished product on the base film side obtained in this way, a 4-layer or 5-layer printed wiring board can be obtained.

The semi-finished product on the side of the substrate film can be obtained by a manufacturing method including the following steps, for example: (A) coating the solution of the resin to be the substrate film on the aforementioned metal foil, and preliminarily drying the coating; (B) (A) The obtained laminate of the metal foil and the preliminarily dried coating film is heat-treated and dried (hereinafter referred to as "heat treatment and solvent removal step").

A conventional method can be used to form the circuit in the metal foil layer. Additive or subtractive methods can be used. It should be the subtraction method.

The obtained semi-finished product on the base film side can be used directly for bonding with the semi-finished product on the cover film side, or it can be used for bonding with the semi-finished product on the cover film side after the release film is laminated and stored.

The cover film side semi-finished product is manufactured by applying an adhesive to the cover film, for example. The cross-linking reaction in the coated adhesive can be implemented as needed. In an ideal implementation aspect, the adhesive layer is semi-hardened.

The obtained semi-finished product on the cover film side can be used directly for bonding to the semi-finished product on the side of the substrate film, or it can be used for bonding the semi-finished product on the side of the substrate film after the release film is laminated and stored.

The semi-finished product on the base film side and the semi-finished product on the cover film side are stored separately in the form of a roll, for example, and then laminated to manufacture a printed wiring board. As for the bonding method, any method can be used, and for example, pressing or a roll can be used for bonding. In addition, it is also possible to use heating and pressing, or using a heating roller device, etc., to bond the two while heating.

The semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the reinforcing material side all belong to the laminate for printed wiring boards in the present invention.

The adhesive composition of the present invention can be suitably used in each adhesive layer of a printed wiring board, and due to its excellent adhesion to various substrates and high humidity and heat resistance, it can be used in addition to printed wiring boards as well By containing conductive powder such as metal powder, it can be used for electromagnetic wave shielding applications, touch panels, circuit formation applications of electronic parts, conductive adhesives for terminals, or wires. [Example]

In order to describe the present invention in more detail, examples and comparative examples are listed below, but the present invention is not limited by the examples at all. In addition, each measurement value described in an Example and a comparative example was measured by the following method. In addition, unless specifically limited, "parts" means "parts by mass", and "%" means "% by mass".

(Physical property evaluation method) (1) Composition of carboxylic acid group-containing polymer compound The carboxylic acid group-containing polymer compound was dissolved in deuterated chloroform and analyzed by 1H-NMR to obtain the molar ratio of each component.

(2) Number average molecular weight (Mn) Dissolve the sample (polymer compound containing carboxylic acid group, polymer polyol (A), or polymer polyol (B)) in tetrahydrofuran or dilute with tetrahydrofuran to make the sample concentration Approximately 0.5% by mass, filtered with a membrane filter made of polytetrafluoroethylene with a pore size of 0.5μm as a sample for measurement. The number average molecular weight was measured by a gel permeation chromatograph with a mobile phase of tetrahydrofuran and a differential refractometer as the detector. The flow rate is set to 1 mL/min, and the column temperature is set to 30°C. Use Showa Denko KF-802, 804L, 806L for the column. The molecular weight standard uses monodisperse polystyrene. However, when the sample does not dissolve in tetrahydrofuran, use N,N-dimethylformamide instead of tetrahydrofuran. Low-molecular compounds (oligomers, etc.) whose number average molecular weight is less than 500 are not included in the count and omitted.

(3) The glass transition temperature uses a differential scanning calorimeter "DSC220" manufactured by Seiko Electronics Co., Ltd., put 5 mg of the measurement sample into an aluminum pan, press the lid and seal it, and keep it at 250°C for 5 minutes once. Cool rapidly with liquid nitrogen, and then measure from -150°C to 250°C at a temperature rise rate of 20°C/min. The inflection point of the obtained curve is defined as the glass transition temperature. In addition, when there are two or more inflection points, it is considered to be through block copolymerization, and each inflection point is read and treated as having multiple glass transition temperatures.

(4) Acid value Dissolve 0.2 g of the sample (polymer compound containing carboxylic acid group, polymer polyol (A), or polymer polyol (B)) in 20 ml of chloroform, use phenolphthalein as an indicator, and use 0.1 The potassium hydroxide ethanol solution of N is titrated. From this titration amount, the mg number of KOH consumed for neutralization was converted into the amount per 1 g of resin, and the acid value (mgKOH/g) was calculated.

(5) Solder resistance and peel strength (5)-1 Sample preparation method for evaluation. Reserve the parts needed for stretching, and apply the adhesive composition described below to a polyimide film with a thickness of 12.5 μm (Kaneka Co., Ltd. Made, APICAL (registered trademark)), the thickness after drying becomes 25μm, and it is dried at 140°C for 5 minutes to obtain an adhesive film (B-stage product). The adhesive layer of the adhesive film is bonded with the glossy surface of the 20μm rolled copper foil, and pressed at 160°C under 35kgf/cm ² pressure for 30 seconds to bond. Then, it was heat-treated at 140°C for 4 hours to harden, and a sample for evaluation of solder resistance and peel strength was obtained.

(5)-2 Evaluation method of each characteristic The evaluation of each characteristic is implemented by the following method. Resistance to drying solder: After placing the sample for evaluation in an environment of 120°C for 30 minutes, float in a heated solder bath for 1 minute, and measure the upper limit temperature at which no swelling occurs at intervals of 10°C. Specifically, the temperature is increased from 260°C to 270°C and 280°C to 360°C at 10°C intervals. In this test, the higher measured value indicates good heat resistance. In consideration of practical performance, the temperature should be 350°C or higher, and 360°C or higher is more preferable. Evaluation criteria ◎: No swelling even at 360°C or higher. ○: No swelling occurs below 340°C, but swelling occurs below 360°C above 340°C. △: No swelling occurs below 330°C, but swelling occurs below 340°C above 330°C. ×: Puffing occurred before reaching 330°C.

Solder resistance (humidification): After leaving the sample for evaluation at 40°C and 80% humidified conditions for 3 days, float in a heated solder bath for 1 minute, and measure the upper limit temperature at which swelling does not occur at intervals of 10°C . Specifically, the temperature is increased from 220°C to 230°C, 240°C and 300°C at 10°C intervals. In this test, although the higher measured value indicates good heat resistance, it is also necessary to suppress the impact caused by the evaporation of water vapor in each substrate and adhesive layer, and require stricter heat resistance than in the dry state. . In consideration of practical performance, the temperature should be 260°C or higher, more preferably 270°C or higher. Evaluation criteria ○: No swelling even at 270°C or higher. △: Puffing occurred at a temperature above 260°C and less than 270°C. ×: Puffing occurs before reaching 260°C.

Peeling strength: The sample for evaluation was pulled at 25° C., and the polyimide film was pulled at a tensile speed of 50 mm/min to perform a 90° peel test to measure the peel strength. This test shows the bonding strength at room temperature. In consideration of practical performance, it is preferably 7N/cm or more, more preferably 10N/cm or more. Evaluation criteria ◎: 15N/cm or more ○: 10N/cm or more, less than 15N/cm △: 7N/cm or more, less than 10N/cm ×: less than 7N/cm

The polymerization example of polymer polyol (A1) is 189 parts of terephthalic acid, 435 parts of isophthalic acid, 7 parts of trimellitic anhydride, 110 parts of 2-methyl-1,3-propanediol, 1,6-hexane 483 parts of diol and 0.2 parts of tetrabutyl titanate are fed into a reaction tank equipped with a stirrer, a thermometer, and a cooler for distillation. The temperature is gradually raised to 250°C, and the distilled water is continuously drained out of the system. The esterification reaction is carried out in the state. After the end of the esterification reaction, the initial polymerization was carried out while gradually reducing the pressure to 10 mmHg, and the temperature was raised to 250°C, and then the latter polymerization was carried out below 1 mmHg until it reached a predetermined stirring torque. Then, the pressure was returned to normal pressure with nitrogen, 28 parts of trimellitic anhydride was put in, and reacted at 220° C. for 30 minutes, thereby obtaining a polymer polyol (A1). The composition and characteristic values of the polymer polyol (A1) obtained in this way are shown in Table 1. Each measurement evaluation item follows the aforementioned method.

Polymeric polyol (B1) polymerization example: 390 parts of terephthalic acid, 390 parts of isophthalic acid, 367 parts of ethylene glycol, 362 parts of 2,2-dimethyl-1,3-propanediol, tetra 0.2 parts of butyl ester was fed into a reaction tank equipped with a stirrer, a thermometer, and a cooler for distillation. The temperature was gradually raised to 250°C, and the esterification reaction was carried out while continuously draining the distilled water out of the system. After the end of the esterification reaction, the pressure is gradually reduced to 10mmHg while performing the initial polymerization under reduced pressure. At the same time, the temperature is increased to 250°C, and the subsequent polymerization is performed below 1mmHg until it reaches the predetermined stirring torque. Polymer polyol (B1). The composition and characteristic values of the polymer polyol (B1) obtained in this way are shown in Table 1. Each measurement evaluation item follows the aforementioned method.

The polymer polyols (A2) and (B2) were obtained by the same method as the polymer polyol (A1). In addition, the polymer polyol (A3) was obtained by the same method as the polymer polyol (B1). Their characteristic values are shown in Table 1.

For the polymer polyols (B3) to (B5), the ones shown below were used respectively. Polymer polyol (B3): Polycarbonate diol T5652 (number average molecular weight 2000) manufactured by Asahi Kasei Co., Ltd. Polymer polyol (B4): Polyester polyol P2010 (number average molecular weight 2000) manufactured by Kuraray (Stock) Polymer polyol (B5): Asahi Kasei Co., Ltd. polycarbonate diol T5651 (number average molecular weight 1000)

[Table 1]

Synthesis example of carboxylic acid group-containing polymer compound (C1) 160 parts of polymer polyol (A1), 40 parts of polymer polyol (B1), 5.2 parts of pyromellitic anhydride, and 200 parts of toluene In the reaction tank of the stirrer, the thermometer, and the reflux tube, the temperature was gradually increased to 80°C and dissolved in toluene. After the dissolution was completed, 0.1 part of triethylamine was added as a reaction catalyst, and then the temperature was gradually raised to 105°C and allowed to react for 24 hours. After confirming the completion of the reaction by IR, it was diluted with 108 parts of toluene to obtain a solution with a solid content of 40% of the carboxylic acid group-containing polymer compound (C1). The composition and characteristic values of the carboxylic acid group-containing polymer compound (C1) obtained in this way are shown in Table 2. Each measurement evaluation item follows the aforementioned method.

<Synthesis example of carboxylic acid group-containing polymer compound (C2)~(C10)> Similar to the synthesis example of carboxylic acid group-containing polymer compound (C1), obtain the carboxylic acid group-containing polymer compound (C2)~ (C10). However, for (C6), (C8), (C9), 2,2-dimethylpropanediol was added in the feed stage. Others are the same as the synthesis example (C1) of the carboxylic acid group-containing polymer compound.

<Example 1> Nine parts of YDCN-700-10 (novolac resin type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and TETRAD (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd. were used as epoxy resins. 0.1 part of X(N,N,N',N'-tetraepoxypropyl m-xylene diamine) is added to 100 parts of solid content of carboxylic acid group-containing polymer compound (C1), adjusted with methyl ethyl ketone The solid content concentration was 35%, and an adhesive composition was obtained. The obtained adhesive composition was evaluated by the method shown below. The results are shown in Table 3.

<Examples 2 to 8, Comparative Examples 1 to 6> The carboxylic acid group-containing polymer compound and epoxy resin were changed to those shown in Table 3, and the same method as in Example 1 was used to obtain the results as shown in Table 3. The method of each blending amount was changed, and Examples 2 to 8 and Comparative Examples 1 to 6 were implemented. The results are shown in Table 3.

According to the examples in Table 3, it can be seen that the resin of the present invention has a resistance to dry solder above 340°C, and also has excellent resistance to humidified solder.

As shown in Comparative Examples 1 and 6, when the number-average molecular weight of polymer polyols of 6000 and 2000 are relatively small, the distance between cross-linking points will become shorter, so the coating film will become harder, and the peel strength and resistance to application Wet solder properties will decrease.

As shown in Comparative Examples 2 and 3, when the polymer polyol (B) is not used, a gelatinous substance is generated, and the solder resistance to humidification or peeling strength is lowered.

As shown in Comparative Example 4, when the polymer polyol (A) is not used, a coating film (film formation) cannot be obtained. As shown in Comparative Example 5, if the molecular weight of the carboxylic acid group-containing polymer compound (C) is too large, the fluidity will be low, and it will not be possible to form a coating film.

As shown in Example 6, there is no problem even if a small amount of chain extender is used. [Industrial Utilization]

The carboxylic acid group-containing polymer compound and the adhesive composition containing the carboxylic acid group-containing polymer compound of the present invention maintain good adhesiveness and have excellent moisture and heat resistance. Among them, the good adhesiveness is For various plastic films, or metals such as copper, aluminum, stainless steel, and glass epoxy resin; the damp and heat resistance refers to the high degree of damp and heat resistance that can also correspond to lead-free solder under high humidity. Therefore, it is particularly effective as an adhesive for circuit boards such as FPC.

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Claims (6)

A polymer compound containing carboxylic acid groups, at least including the following components as copolymerization components, and satisfying the following (1) ~ (2); a polymer polyol with a number average molecular weight (Mn1) of 7,000 to 50,000 (A) ; Different from the polymer polyol (A) and the number average molecular weight (Mn2) of the polymer polyol (B) is 1,000 or more and 10,000 or less, and the difference between (Mn1) and (Mn2) is 6,000 or more; and two tetracarboxylic acid Anhydride; (1) among the copolymerization components, the number average molecular weight (Mn1) of the polymer polyol (A) is the largest; (2) the number average molecular weight (Mn3) of the polymer compound containing carboxylic acid groups is the polymer polyol ( A) The number average molecular weight (Mn1) is less than 1.7 times. For example, the carboxylic acid group-containing polymer compound in the first item of the patent application, wherein the polymer polyol (A) and/or the polymer polyol (B) is a polyester polyol or a polycarbonate polyol. For example, the carboxylic acid group-containing polymer compound of item 1 or 2 in the scope of patent application has an acid value of 5-100mgKOH/g. An adhesive composition containing a carboxylic acid group-containing polymer compound as in any one of items 1 to 3 in the scope of the patent application. An adhesive sheet that contains the hardened substance of the adhesive composition as described in item 4 of the scope of patent application. A printed wiring board, including the adhesive sheet as described in item 5 of the scope of patent application as a constituent element.