WO2018105543A1 - High-molecular-weight compound containing carboxylic acid group, and adhesive agent composition containing same - Google Patents
High-molecular-weight compound containing carboxylic acid group, and adhesive agent composition containing same Download PDFInfo
- Publication number
- WO2018105543A1 WO2018105543A1 PCT/JP2017/043420 JP2017043420W WO2018105543A1 WO 2018105543 A1 WO2018105543 A1 WO 2018105543A1 JP 2017043420 W JP2017043420 W JP 2017043420W WO 2018105543 A1 WO2018105543 A1 WO 2018105543A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carboxylic acid
- polyol
- number average
- acid group
- molecular weight
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Definitions
- the present invention relates to various plastic films, metals such as copper, aluminum, and stainless steel, a carboxylic acid group-containing polymer compound excellent in adhesiveness to glass epoxy and wet heat resistance, and an adhesive composition and adhesive containing the same.
- the present invention relates to a sheet and a printed wiring board including the sheet as a component.
- adhesives have been used in various fields, but due to diversification of purposes of use, various plastic films, adhesiveness to metal, glass epoxy, etc., moisture and heat resistance, etc., compared to conventionally used adhesives, There is a need for higher performance.
- adhesives for circuit boards including flexible printed wiring boards (hereinafter sometimes abbreviated as FPC) are required to have adhesiveness, workability, electrical characteristics, and storage stability.
- FPC flexible printed wiring boards
- epoxy / acryl butadiene adhesives, epoxy / polyvinyl butyral adhesives, and the like are used for this application.
- the problem of the present invention is to improve each of the problems of these conventional adhesives, and to maintain good adhesion to various plastic films, metals such as copper, aluminum and stainless steel, and glass epoxy.
- Another object of the present invention is to provide a carboxylic acid group-containing polymer compound that is capable of dealing with lead-free solder under high humidity and has a high degree of moisture and heat resistance, and an adhesive composition containing the carboxylic acid group-containing polymer compound. .
- the present invention has the following configuration.
- the polymer polyol (A) and / or polymer polyol (B) is preferably a polyester polyol or a polycarbonate polyol.
- An adhesive composition containing the carboxylic acid group-containing polymer compound An adhesive sheet containing a cured product of the adhesive composition.
- a printed wiring board comprising the adhesive sheet as a constituent element.
- the carboxylic acid group-containing polymer compound of the present invention and the adhesive composition containing the carboxylic acid group-containing polymer compound are excellent in adhesion to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy. Highly moist and heat-resistant (solder resistance) that can be used for lead-free soldering under high humidity while maintaining its properties.
- the polymer polyol (A) needs to have a number average molecular weight (Mn1) of 7,000 or more. Preferably it is 7,000 or more, More preferably, it is 8,000 or more, More preferably, it is 10,000 or more, Especially preferably, it is 12,000 or more.
- Mn1 is less than 7,000, the crosslinking density increases, and the coating film obtained from the adhesive composition becomes hard, so the adhesion tends to decrease.
- Mn1 is preferably 50,000 or less, more preferably 40,000 or less, and further preferably 30,000 or less. If it is too large, crosslinking may be insufficient and heat resistance may be reduced.
- the acid value (mgKOH / g) of the polymer polyol (A) is not particularly limited, but is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. If it is low, there is no problem, but if it is too large, acid addition chain extension by tetracarboxylic dianhydride may not be possible. Therefore, since the reaction between the polymer polyols (B) proceeds, the crosslink density increases, and the coating film obtained from the adhesive composition becomes hard, so that the adhesion tends to decrease.
- the hydroxyl value (mgKOH / g) of the polymer polyol (A) is not particularly limited, but the maximum value is preferably 24 mgKOH / g or less, more preferably 21 mgKOH / g or less, and further preferably 16 mgKOH / g or less. Especially preferably, it is 14 mgKOH / g or less. If it is too large, the reaction becomes insufficient and heat resistance may not be exhibited.
- the minimum value is preferably 2 mgKOH / g or more, more preferably 3 mgKOH / g or more, and still more preferably 3.5 mgKOH / g or more. If it is too small, the crosslinking density is lowered, and heat resistance may not be exhibited.
- the glass transition temperature of the polymer polyol (A) is not particularly limited, but is preferably 0 ° C. or higher, more preferably 5 ° C. or higher. If the glass transition temperature is too low, the tackiness of the adhesive composition becomes strong, and bubbles are likely to be caught and poorly bonded. Moreover, it is preferable that it is 60 degrees C or less, More preferably, it is 50 degrees C or less, More preferably, it is 40 degrees C or less, Most preferably, it is 30 degrees C or less. If the glass transition temperature is too high, the coating film becomes brittle and there is a concern that embrittlement becomes a problem.
- the polymer polyol (B) is a polyol different from the polymer polyol (A), and the number average molecular weight (Mn2) needs to be 1,000 or more.
- the difference from the polymer polyol (A) means that at least either the composition or the physical properties are different.
- 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 polyol (B) can easily form a bond, so that it tends to have a low molecular weight and a high acid value, and a gel-like substance is likely to be generated in the crosslinked coating film.
- the resulting coating film may have insufficient crosslinking density, resulting in insufficient heat resistance.
- the acid value (mgKOH / g) of the polymer polyol (B) is not particularly limited, but is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. If it is too high, it may become impossible to extend the acid addition chain with tetracarboxylic dianhydride.
- the hydroxyl value (mgKOH / g) of the polymer polyol (B) is not particularly limited, but the maximum value is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and still more preferably 80 mgKOH / g or less. is there. If the hydroxyl value is too high, the polymer polyols (B) are likely to be bonded to each other, so that a low molecular weight and a high acid value are obtained, and a gel-like product is likely to be generated in the coating film after crosslinking.
- the minimum value is preferably 11 mgKOH / g or more, more preferably 14 mgKOH / g or more, and still more preferably 18 mgKOH / g or more. If it is too low, acid addition chain extension by tetracarboxylic dianhydride may not be possible.
- the glass transition temperature of the polymer polyol (B) is not particularly limited, but in the case of the polyester polyol, it is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and further preferably 0 ° C. or higher. Yes, more preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, and most preferably 30 ° C. or higher.
- 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.
- the temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower.
- the temperature is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and further preferably ⁇ 20 ° C. or lower. If the glass transition temperature is too high, the coating film becomes brittle and there is a concern that embrittlement becomes a problem.
- the number average molecular weight (Mn1) of the polymer polyol (A) needs to be larger than the number average molecular weight (Mn2) of the polymer polyol (B), and the difference in molecular weight is not particularly limited, but is 6,000 or more. It is preferable that there is, more preferably 8,000 or more, and still more preferably 10,000 or more.
- the difference in molecular weight it is possible to achieve improvement in the compatibility, heat resistance and humidification solder resistance of the carboxylic acid group-containing polymer compound. That is, the polymer polyol (A) can relieve the stress caused by water vapor generated during the evaluation of the humidification solder resistance by introducing a long chain block to increase the molecular weight.
- the upper limit of the difference in molecular weight is not particularly limited, but is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less.
- the polymer polyol (A) and / or polymer polyol (B) is not particularly limited, but is preferably a polyester polyol or a polycarbonate polyol. These can be used alone or in combination of two or more. When the same kind of polyol is used for both the polymer polyol (A) and the polymer polyol (B), phase separation is relatively difficult to occur, which is advantageous in that the reaction proceeds efficiently. On the other hand, by using a plurality of different types of polyols in combination, it becomes possible to impart characteristics that cannot be obtained when used alone. For example, improvement of hydrolysis resistance can be expected by using a polyester polyol for the polymer polyol (A) and a polycarbonate polyol for the polymer polyol (B). Preferably, both the polymer polyol (A) and the polymer polyol (B) are polyester polyols.
- the polyester polyol is preferably composed of a polycarboxylic acid component and a polyol component.
- the polycarboxylic acid component constituting the polyester polyol when the total polycarboxylic acid is 100 mol%, the aromatic dicarboxylic acid is preferably contained in an amount of 60 mol% or more. More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, and it may be 100 mol%. If the amount is too small, the cohesive force of the coating film is weak, and the adhesive strength to various substrates may be reduced.
- the aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and diphenic acid.
- Aromatic dicarboxylic acids having a sulfonic acid group such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid,
- aromatic dicarboxylic acids having a sulfonate group such as metal salts and ammonium salts thereof.
- terephthalic acid, isophthalic acid, and a mixture thereof are particularly preferable from the viewpoint of increasing the cohesive strength of the coating film.
- polycarboxylic acid components include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its anhydride, alicyclic dicarboxylic acids, succinic acid, adipic acid And aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, dodecanedioic acid and dimer acid.
- An oxycarboxylic acid compound having a hydroxyl group and a carboxyl group in the molecular structure such as -hydroxyphenyl) valeric acid can also be used.
- the glycol component constituting the polyester polyol
- the glycol component when the total polyol is 100 mol%, the glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, and 100 mol%. There is no problem.
- the glycol component is preferably an aliphatic glycol, an alicyclic glycol, an aromatic-containing glycol, or an ether bond-containing glycol.
- aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 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), hydroxypivalic acid neopentyl glycol ester, dimethylol heptane, 2,2,4-trimethyl-1,3-pentanediol and the like.
- Examples of alicyclic glycols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol A, and hydrogenated bisphenol A. Examples thereof include an ethylene oxide adduct and a propylene oxide adduct.
- Examples of ether bond-containing glycols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, and neopentyl glycol propylene oxide adduct. Can be mentioned.
- aromatic-containing glycols include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adducts of 1,4-phenylene glycol, bisphenol A, ethylene oxide addition of bisphenol A
- examples thereof include glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as products and propylene oxide adducts. These can be used alone or in combination of two or more.
- aliphatic glycols are preferable, and 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.
- a tri- or higher functional component may be copolymerized with the polycarboxylic acid component and / or the polyol component for the purpose of introducing a branched skeleton if necessary.
- the total polycarboxylic acid component and the total polyol component are each 100 mol%, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and preferably 5 mol% or less. The mol% or less is more preferable.
- a branched skeleton By making it within the above-mentioned range, particularly when a cured coating film is produced by reacting with a curing agent, a branched skeleton can be introduced, the terminal group concentration (reaction point) of the resin is increased, the crosslinking density is high, and the strength Can be obtained. On the other hand, if it exceeds 5 mol%, mechanical properties such as elongation at break of the coating film may be lowered, and gelation may occur during polymerization.
- tri- or higher functional polycarboxylic acid components include trimellitic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride Product (BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2 Examples thereof include compounds such as' -bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA).
- An acid value may be introduced into the polyester polyol.
- the acid value of the polyester polyol is preferably 10 mgKOH / g or less, and more preferably 8 mgKOH / g or less. If it is low, there is no particular problem, but if it is too high, it may not be possible to extend the acid addition chain with tetracarboxylic dianhydride.
- Examples of the method for introducing an acid value include a method of introducing a carboxylic acid into a polyester polyol by acid addition after polymerization. If a monocarboxylic acid, dicarboxylic acid, or trifunctional or higher polycarboxylic acid compound is used for acid addition, the molecular weight may be reduced by transesterification. Therefore, a compound having at least one carboxylic anhydride group should be used. preferable.
- Carboxylic anhydrides include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride Product (ODPA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2'-bis [(dicarboxyphenoxy ) Phenyl] propane dianhydride (BSAA) and the like.
- ODPA oxydiphthalic
- the polycarbonate polyol is a polyol having a carbonate bond, and is preferably a polycarbonate diol.
- a commercially available product can be used as the polycarbonate diol.
- Examples of commercially available polycarbonate diol include trade names Duranol (registered trademark) T-4692 (number average molecular weight 2000), T-5562 (number average molecular weight 2000), T-5651 (number average molecular weight 1000) manufactured by Asahi Kasei Chemicals Corporation.
- 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 manufactured by Kuraray Co., Ltd. -2050 (number average molecular weight 2000), C-2090 (number average molecular weight 2000), C-3090 (number average molecular weight 3000), trade name ETERNACOLL (registered trademark) UH-100 (number average molecular weight 1000) manufactured by Ube Industries, Ltd.
- the polycarbonate polyol is preferably a liquid from the viewpoint of workability, and the DURANOL (registered trademark) series is particularly preferable.
- tetracarboxylic dianhydride examples include an aromatic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, and an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride is preferable.
- pyromellitic anhydride PMDA
- ODPA oxydiphthalic dianhydride
- BTDA 4,4′-benzophenonetetracarboxylic dianhydride
- BPDA 4,4′-diphenyltetracarboxylic dianhydride
- DSDA 4,4′-diphenylsulfonetetracarboxylic dianhydride
- 6FDA acid dianhydride
- BSAA 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride
- BSAA propane dianhydride
- the carboxylic acid group-containing polymer compound of the present invention contains at least the polymer polyol (A), the polymer polyol (B) and tetracarboxylic dianhydride as a copolymer component, and (1) in the copolymer component, The number average molecular weight (Mn1) of the polymer polyol (A) is the largest, and (2) the number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is the number average molecular weight (Mn1) of the polymer polyol (A). 1.7 times or less.
- a polymer polyol having two or more components including a polymer polyol (A) having a number average molecular weight of 7,000 or more and a polymer polyol (B) having a number average molecular weight of 1,000 or more is used as a copolymerization component, Furthermore, it is possible to improve heat resistance and humidification solder resistance by extending the chain using tetracarboxylic dianhydride. In other words, the short-chain polymer polyol (B) block is introduced while improving the resistance to humidification by relieving the stress of water vapor generated when evaluating the resistance to humidification soldering with the long-chain polymer polyol (A) block.
- the glass transition temperature of the carboxylic acid group-containing polymer compound is not particularly limited, and is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and further preferably 10 ° C. or higher. If the glass transition temperature is too low, the tackiness of the adhesive composition becomes strong, and bubbles are likely to be bitten and become defective during bonding. Moreover, it is preferable that it is 80 degrees C or less, More preferably, it is 70 degrees C or less, More preferably, it is 60 degrees C or less. If the glass transition temperature is too high, the coating film becomes brittle and there is a concern that embrittlement becomes a problem.
- the number average molecular weight (Mn1) of the polymer polyol (A) needs to be maximum.
- the copolymer component in addition to the polymer polyol (A), the polymer polyol (B), and the tetracarboxylic dianhydride, for example, other polyol components and a chain extender described later can be arbitrarily used.
- the number average molecular weight (Mn1) of the polymer polyol (A) is the largest among the number average molecular weights of all copolymerization components including these.
- the carboxylic acid group-containing polymer is copolymerized with the carboxylic acid group-containing polymer compound.
- the compound can exhibit excellent humidification soldering resistance.
- the lower limit of Mn3 / Mn1 is preferably 0.8 times or more, more preferably 0.9 times or more, and further preferably 1.0 times or more. If it is too small, there is a possibility that a large amount of reaction between the polymer polyol (B) and the chain extender (tetracarboxylic dianhydride) has occurred. There is a possibility that it will not react with the product, resulting in insufficient resistance to humidification soldering.
- the carboxylic acid group-containing polymer compound is within the range of the number average molecular weight (Mn3 / Mn1), the polymer polyol (A) and the resin containing only the carboxylic dianhydride, or the polymer polyol (B) And a resin containing only carboxylic acid dianhydride.
- 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 further preferably 15 mgKOH / g or more. Moreover, it is preferable that it is 100 mgKOH / g or less, More preferably, it is 60 mgKOH / g or less, More preferably, it is 40 mgKOH / g or less. If the acid value is too small, sufficient heat resistance may not be obtained due to insufficient crosslinking, and if the acid value is too high, the crosslinking density becomes too high, the cured coating film becomes hard, and adhesiveness may decrease. Moreover, the storage stability of the varnish which melt
- the carboxylic acid group-containing polymer compound of the present invention is not necessarily limited to the three components of the polymer polyol (A), the polymer polyol (B) and the tetracarboxylic dianhydride, and the fourth copolymer component.
- Other high molecular weight components can be used.
- the fourth copolymer component include a polymer polyol different from the polymer polyol (A) and the polymer polyol (B).
- the number average molecular weight of the fourth copolymer component is preferably Mn1 or less of the polymer polyol (A) and Mn2 or more of the polymer polyol (B).
- the copolymerization ratio of the polymer polyol (A) and the polymer polyol (B) in the carboxylic acid group-containing polymer compound is 5 masses for 100 mass parts of the polymer polyol (A). It is preferably at least 10 parts by mass, more preferably at least 10 parts by mass, and even more preferably at least 20 parts by mass. Further, 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. If the amount is too large, the moisture resistance solder resistance may be insufficient. The terminal which can react with a thing decreases, and heat resistance may become insufficient.
- the copolymerization ratio of the polymer polyol (A) and tetracarboxylic dianhydride is 0.5% of tetracarboxylic dianhydride with respect to 100 parts by mass of the polymer polyol (A).
- the amount is preferably at least 1 part by mass, more preferably at least 1 part by mass, and even more preferably at least 2 parts by mass.
- 10 mass parts or less are preferable, More preferably, it is 8 mass parts or less, More preferably, it is 5 mass parts or less.
- crosslinking may be insufficient and heat resistance may become insufficient, and when too large, it is a 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 further preferably 70% by mass or more.
- the copolymerization amount of the polymer polyol (A) it is possible to expect improvement in humidification solder resistance.
- the carboxylic acid group-containing polymer compound has a chain in addition to the polymer polyol (A), polymer polyol (B), and tetracarboxylic dianhydride as a copolymerization component as long as the effects of the present invention are not impaired.
- An extender can optionally be used.
- An acid value can be efficiently provided by using a chain extender.
- the amount of copolymerization is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the polymer polyol (A). Preferably it is 1 part by mass or more.
- the chain extender is preferably a low molecular diol having a molecular weight of 1000 or less, and examples thereof include 2,2-dimethyl-1,3-propanediol and dimethylolbutanoic acid. These can be used alone or in combination of two or more. Of these, 2,2-dimethyl-1,3-propanediol is preferred from the viewpoint of solubility and compatibility.
- the carboxylic acid group-containing polymer compound may use a quaternary ammonium salt or a tertiary amine as a reaction catalyst as long as the effects of the present invention are not impaired.
- imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2-ethyl-4-methylimidazole; Triethylamine, triethylenediamine, N′-methyl-N- (2-dimethylaminoethyl) piperazine, N, N-diisopropylethylamine, N, N-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) -undecene Tertiary amines such as -7,1,5-diazabicyclo (4,3,0) -nonene-5, or 6-dibutylamino
- the adhesive composition of the present invention contains at least the carboxylic acid group-containing polymer compound, and preferably contains an organic solvent or an epoxy resin (D).
- the carboxylic acid group-containing polymer compound is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. Moreover, it is preferable that it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. If the amount is too small, the adhesiveness and heat-and-moisture resistance may decrease. If the amount is too large, the storage stability of the adhesive composition may decrease.
- the organic solvent is not particularly limited as long as it dissolves the carboxylic acid group-containing polymer compound, and more preferably dissolves the epoxy resin (D).
- the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, Alcohol solvents such as propanediol and phenol, acetone solvents such as methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone , Ester solvents such as butyl acetate, methyl propionate and butyl formate, and
- the amount of the organic solvent is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound. Moreover, it is preferable that it is 500 mass parts or less, More preferably, it is 400 mass parts or less, More preferably, it is 300 mass parts or less. If the amount is too small, the storage stability of the adhesive composition may be lowered. If the amount is too large, it may be industrially disadvantageous.
- the epoxy resin (D) is not particularly limited as long as it cures and crosslinks with the carboxyl group of the carboxylic acid group-containing polymer compound, but is a polyfunctional epoxy resin having a plurality of epoxy groups in one molecule. Is preferred. By using a polyfunctional epoxy resin, a cured coating film obtained from the adhesive composition can easily form a three-dimensional cross-link and improve heat resistance.
- the polyfunctional epoxy resin include a cresol novolac type epoxy resin, an epoxy resin having a dicyclopentadiene skeleton, and a phenol novolac type epoxy resin.
- cresol novolac type epoxy resin When it is a cresol novolac type epoxy resin or a phenol novolac type epoxy resin, the crosslink density of the cured coating film can be lowered to relieve the stress at the time of peeling, so that the moisture resistance soldering property is improved.
- cresol novolac epoxy resins include YDCN-700 manufactured by DIC Corporation.
- an epoxy resin having a dicyclopentadiene skeleton has a rigid dicyclopentadiene skeleton, so the hygroscopic property of the cured coating becomes extremely small, the crosslinking density of the cured coating is lowered, and the stress at the time of peeling is reduced. Can be relaxed. Therefore, humidification solder resistance improves.
- HP7200 series manufactured by DIC can be mentioned. These can be used alone or in combination of two or more.
- an epoxy resin containing a nitrogen atom can also be used.
- the coating film of the adhesive composition can be brought into a semi-cured state (hereinafter sometimes referred to as B stage) by heating at a relatively low temperature, and the B stage.
- B stage a semi-cured state
- the workability in the bonding operation can be improved by suppressing the fluidity of the film.
- the effect which suppresses foaming of a B stage film can be anticipated, it is preferable.
- Examples of the epoxy resin containing a nitrogen atom include glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. The system etc. are mentioned. It is preferable that the compounding quantity of the epoxy resin containing these nitrogen atoms is 20 mass% or less of the whole epoxy resin (D).
- glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like.
- the system etc. are mentioned
- the blending amount is more than 20% by mass, the rigidity becomes excessively high and the adhesiveness tends to be lowered, and the crosslinking reaction tends to proceed during storage of the adhesive sheet, and the sheet life tends to be lowered.
- the upper limit of the more preferable amount is 10 mass%, More preferably, it is 5 mass%.
- epoxy resins can be used in combination as the epoxy resin (D) used in the present invention.
- glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanurate, 3 , 4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, alicyclic or aliphatic epoxide such as epoxidized soybean oil, and the like may be used alone or in combination of two or more.
- the epoxy resin (D) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound. Moreover, it is preferable that it is 50 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 20 mass parts or less. If the amount is too small, curing may be insufficient, and adhesiveness and heat-and-moisture resistance may decrease. If the amount is too large, uncrosslinked epoxy resin may increase and heat resistance may decrease.
- a curing catalyst can be used for the curing reaction of the epoxy resin (D).
- imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2-ethyl-4-methylimidazole;
- Triethylamine triethylenediamine, N′-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo (5,4,0) -undecene-7, 1,5-diazabicyclo (4,3,0) -Tertiary amines such as nonene-5 or 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7 and these tertiary amines in phenol, octylic acid or quaternized Compounds converted to amine salts
- the blending amount of the curing catalyst is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound. If it is this range, the catalytic effect with respect to reaction of a carboxylic acid group containing high molecular compound and an epoxy resin (D) will increase further, and firm adhesive performance can be obtained.
- the adhesive composition of the present invention can further contain various curable resins and additives as long as the effects of the present invention are not impaired.
- the curable resin include phenolic resins, amino resins, isocyanate compounds, and silicone resins.
- phenolic resins include formaldehyde condensates of alkylated phenols and cresols. Specifically, alkylated (eg, methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tert-amylphenol, 4,4′-sec-butylidenephenol, p-tert-butylphenol, o-cresol, m -Cresol, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol, xylenol, etc.
- Formaldehyde condensates can be used alone or in combination of two or more.
- amino resins include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds of these alcohols having 1 to 6 carbon atoms.
- Specific examples include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine and the like.
- isocyanate compound examples include aromatic or aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
- examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds.
- an excess amount of these isocyanate compounds for example, low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, or triethanolamine, or various polyester polyols, Examples thereof include terminal isocyanate group-containing compounds obtained by reacting polyether polyols, polyamides and other polymer active hydrogen compounds.
- the isocyanate compound may be a blocked isocyanate.
- the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetoxime, methylethyl ketoxime, and cyclohexanone oxime; methanol, ethanol, propanol, Alcohols such as butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; ⁇ -caprolactam, ⁇ -valero And lactams such as lactam, ⁇ -butyrolactam, and ⁇ -propyllactam.
- the blocked isocyanate is obtained by subjecting the above isocyanate compound, isocyanate compound and isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.
- a silane coupling agent may be blended in the adhesive composition of the present invention as necessary. It is very preferable to add a silane coupling agent because adhesion to metal and heat resistance are improved. Although it does not specifically limit as a silane coupling agent, What has an unsaturated group, What has a glycidyl group, What has an amino group, etc. are mentioned. Examples of the silane coupling agent having an unsaturated group include vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane.
- silane coupling agents having a glycidyl group examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane.
- Examples of the silane coupling agent having an amino group include N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ .
- -Aminopropyltrimethoxysilane and the like.
- ⁇ -glycidoxypropyltrimethoxysilane ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc.
- a silane coupling agent having a glycidyl group is preferred.
- the blending amount of the silane coupling agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound. When the blending amount of the silane coupling agent is less than 0.5 parts by mass, the resulting adhesive composition may have poor heat resistance, and when it exceeds 20 parts by mass, heat resistance or adhesion may be poor. There is.
- flame retardants such as bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds, leveling agents, pigments, dyes, and other additives can be appropriately blended as necessary.
- an adhesive sheet contains the coating film (henceforth an adhesive bond layer) of the adhesive composition obtained by hardening the adhesive composition of this invention.
- the adhesive sheet has a function of adhering a base material to an adherend by an adhesive layer.
- the base material of the adhesive sheet functions as a protective layer for the adherend after adhesion.
- the release substrate can be released and the adhesive layer can be transferred to another adherend.
- the adhesive sheet is obtained by applying the adhesive composition to a substrate or a release substrate, drying, and curing.
- Specific configurations include a base material / adhesive layer, a release base material / adhesive layer, a release base material / adhesive layer / base material, a release base material / adhesive layer / release base material, etc. Is mentioned.
- the adhesive agent layer which peeled the mold release base material independently may be sufficient.
- the adhesive sheet may contain a trace amount or a small amount of an organic solvent.
- the adhesive sheet can be obtained by applying the adhesive composition of the present invention to various substrates according to a conventional method, removing at least a part of the solvent and drying.
- pasting the release substrate to the adhesive layer makes it possible to roll up without causing the substrate to be transferred to the substrate, and is excellent in operability and adhesion. Since the agent layer is protected, it is excellent in storage stability and easy to use.
- the adhesive layer itself can be transferred to another substrate.
- the substrate is not particularly limited, and examples thereof include a film-like resin, a metal plate, a metal foil, and papers.
- the film-like resin include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, and olefin resin.
- metal plate and metal foil materials include various metals such as SUS, copper, aluminum, iron, and zinc, and alloys and plated products thereof. Glassine paper etc. can be illustrated. Moreover, glass epoxy etc. can be illustrated as a composite material. Polyester resin, polyamide resin, polyimide resin, polyamideimide resin, SUS steel plate, copper foil, aluminum foil, and glass epoxy are preferable from the viewpoint of adhesive strength between the substrate and the adhesive composition and durability.
- the release substrate is not particularly limited.
- a coating layer of a sealant such as clay, polyethylene, or polypropylene is provided on both surfaces of paper such as fine paper, kraft paper, roll paper, and glassine paper.
- a silicone-type, fluorine-type, or alkyd-type release agent is applied on each of the coating layers.
- various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, and those obtained by applying the release agent on a film such as polyethylene terephthalate can be used.
- polypropylene seal treatment is applied to both sides of the fine paper and an alkyd release agent is used on it. Or what uses an alkyd type mold release agent on polyethylene terephthalate is preferred.
- the method for coating the adhesive composition on the substrate or the release substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater.
- an adhesive layer can be provided directly or by a transfer method on a rolled copper foil, which is a printed wiring board constituent material, or a polyimide film.
- the thickness of the adhesive layer after drying is appropriately changed as necessary, but is preferably in the range of 5 to 200 ⁇ m. If the thickness of the adhesive layer is less than 5 ⁇ m, the adhesive strength may be insufficient. If it exceeds 200 ⁇ m, the drying is insufficient, the residual solvent is increased, and there is a problem that blisters are generated at the time of printing printed circuit board production.
- the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 4% by mass or less, and more preferably 1% by mass or less. If it exceeds 4% by mass, there may be a problem that the residual solvent is foamed when the printed wiring board is pressed to cause swelling.
- the printed wiring board in the present invention includes an adhesive sheet as a constituent element, and more specifically, a laminate (metal foil / adhesive layer / resin base) formed of a metal foil and a resin base material forming a conductor circuit. Material) as a component.
- a printed wiring board is manufactured by conventionally well-known methods, such as a subtractive method, using a metal-clad laminated body, for example. If necessary, a so-called flexible circuit board (FPC), flat cable, tape automated bonding (covered by using a cover film or screen printing ink, etc., partially or entirely covered with a conductor circuit formed of metal foil (tape automated bonding) TAB) circuit board and the like.
- FPC flexible circuit board
- the printed wiring board of the present invention can have any laminated structure that can be employed as a printed wiring board.
- it can be set as the printed wiring board comprised from four layers, a base film layer, a metal foil layer, an adhesive bond layer, and a cover film layer.
- it can be set as the printed wiring board comprised from five layers, a base film layer, an adhesive bond layer, a metal foil layer, an adhesive bond layer, and a cover film layer.
- the printed wiring board may be reinforced with a reinforcing material as necessary. In that case, the reinforcing material and the adhesive layer are provided under the base film layer.
- the adhesive composition of the present invention can be suitably used for each adhesive layer of a printed wiring board.
- the adhesive composition of the present invention when used as an adhesive, it has high adhesiveness to the base material constituting the printed wiring board and can impart high heat resistance that can also be used for lead-free solder. Is possible.
- the chemical cross-linking between the resin and the resin and the physical cross-linking between the resin and the inorganic filler are provided in a well-balanced manner. It is possible to relieve stress without swelling or deformation. Therefore, it is suitable for bonding between the metal foil layer and the cover film layer, and bonding between the base film layer and the reinforcing material layer.
- the inorganic filler used in the present invention is not particularly limited.
- Silica is preferable from the viewpoint of transparency, mechanical properties, and heat resistance of the adhesive composition, and fumed silica having a three-dimensional network structure is particularly preferable.
- hydrophobic silica treated with monomethyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil or the like is more preferable for imparting hydrophobicity.
- the average diameter of the primary particles is preferably 30 nm or less, more preferably 25 nm or less. When the average diameter of the primary particles exceeds 30 nm, the interaction between the particles and the resin tends to decrease, and the heat resistance tends to decrease.
- the average diameter of a primary particle said here is an average value of the circle equivalent diameter of 100 particle
- the compounding amount of the inorganic filler is preferably 10 parts by mass or more, more preferably 13 parts by mass or more, and further preferably 15 parts by mass or more with respect to 100 parts by mass of the carboxylic acid group-containing polymer compound. If it is less than 10 parts by mass, the effect of improving heat resistance may not be exhibited. Moreover, it is preferable that it is 50 mass parts or less, More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less. If it exceeds 50 parts by mass, the inorganic filler may be poorly dispersed, the solution viscosity may become too high, resulting in problems in workability, or the adhesiveness may be lowered.
- any resin film conventionally used as a substrate for printed wiring boards can be used as the substrate film.
- a resin containing halogen may be used, or a resin not containing halogen may be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable. However, from the viewpoint of flame retardancy, a resin containing halogen can also be used.
- the base film is preferably a polyimide film or a polyamideimide film.
- any conventionally known conductive material that can be used for a circuit board can be used.
- the material for example, copper foil, aluminum foil, steel foil, nickel foil and the like can be used, and composite metal foil obtained by combining these and metal foil treated with other metals such as zinc and chromium compounds are also used. be able to.
- it is a copper foil.
- the thickness of the metal foil is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 10 ⁇ m or more. Moreover, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 20 ⁇ m or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit. On the other hand, if the thickness is too thick, the processing efficiency at the time of circuit fabrication 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.
- its length is not particularly limited.
- the width is not particularly limited, but is preferably about 250 to 1000 mm.
- any conventionally known insulating film can be used as an insulating film for a printed wiring board.
- films produced from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyimide, and polyamideimide can be used. More preferably, it is a polyimide film or a polyamidoimide film, More preferably, it is a polyimide film.
- a resin containing halogen may be used, or a resin not containing halogen may be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable. However, from the viewpoint of flame retardancy, a resin containing halogen can also be used.
- the printed wiring board of the present invention can be manufactured using any conventionally known process except that the material of each layer described above is used.
- 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”) is manufactured.
- an adhesive layer is laminated on a semi-finished product (hereinafter referred to as “base film side two-layer semi-product”) or a base film layer in which a desired circuit pattern is formed by laminating a metal foil layer on the base film layer.
- base film side three-layer semi-product having a desired circuit pattern formed by laminating a metal foil layer thereon
- base film side two-layer semi-product The base film side three-layer semi-finished product is collectively referred to as “base film side semi-finished product”.
- a four-layer or five-layer printed wiring board can be obtained by laminating the cover film side semi-finished product and the base film side semi-finished product thus obtained.
- the base film side semi-finished product includes, for example, (A) a step of applying a solution of a resin to be a base film to the metal foil, and initial drying of the coating film, and (B) the metal foil obtained in (A) It can be obtained by a production method including a step of heat-treating and drying the laminate with the initial dry coating film (hereinafter referred to as “heat treatment / solvent removal step”).
- a conventionally known method can be used to form a circuit in the metal foil layer.
- An active method may be used and a subtractive method may be used.
- the subtractive method is preferable.
- the obtained base film side semi-finished product may be used as it is for pasting with the cover film side semi-finished product. May be used.
- the cover film side semi-finished product is manufactured, for example, by applying an adhesive to the cover film. If necessary, a crosslinking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.
- the obtained cover film-side semi-finished product may be used as it is for pasting with the base-side semi-finished product, or after being laminated and stored with the release film for pasting with the base-film-side semi-finished product. May be used.
- the base film side semi-finished product and the cover film side semi-finished product are each stored, for example, in the form of a roll, and then bonded together to produce a printed wiring board.
- Arbitrary methods can be used as a method of bonding, for example, it can bond using a press or a roll. Further, the two can be bonded together while heating by a method such as using a heating press or a heating roll device.
- the base film side semi-finished product, the cover film side semi-finished product, and the reinforcing agent side semi-finished product are all laminated bodies for printed wiring boards in the present invention.
- the adhesive composition of the present invention is suitably used for each adhesive layer of a printed wiring board, it is excellent in adhesion to various base materials and moisture and heat resistance.
- conductive powder By containing conductive powder, it can be used for electromagnetic shielding applications, touch panel and electronic component circuit forming applications, terminals and lead wire conductive adhesives, and the like.
- KF-802, 804L and 806L manufactured by Showa Denko were used as the column. Monodisperse polystyrene was used as the molecular weight standard. However, when the sample did not dissolve in tetrahydrofuran, N, N-dimethylformamide was used instead of tetrahydrofuran. Low molecular compounds (oligomers and the like) having a number average molecular weight of less than 500 were omitted without counting.
- ⁇ It does not swell at less than 340 ° C, but swells at 340 ° C or more and less than 360 ° C. (Triangle
- Solder resistance (humidification): The sample for evaluation was allowed to stand at 40 ° C. and 80% humidification for 3 days, then floated in a heated solder bath for 1 minute, and the upper limit temperature at which swelling did not occur was measured at a pitch of 10 ° C. Specifically, starting from 220 ° C., the temperature was increased to 300 ° C. in steps of 230 ° C., 240 ° C. and 10 ° C. In this test, it shows that the higher the measured value has better heat resistance, but it is also necessary to suppress the impact due to evaporation of water vapor contained in each base material and adhesive layer, rather than the dry state, More severe heat resistance is required. In consideration of practical performance, 260 ° C.
- Peel strength A sample for evaluation was drawn at 25 ° C., a polyimide film was drawn, a 90 ° peel test was conducted at a tensile speed of 50 mm / min, and the peel strength was measured. This test shows the adhesive strength at room temperature. In view of practical performance, it is preferably 7 N / cm or more, more preferably 10 N / cm or more. Evaluation criteria A: 15 N / cm or more B: 10 N / cm or more, less than 15 N / cm ⁇ : 7 N / cm or more, less than 10 N / cm ⁇ : less than 7 N / cm
- the polymer polyol (B1) is polymerized by performing initial polymerization under reduced pressure while gradually reducing the pressure to 10 mmHg, raising the temperature to 250 ° C., and further performing late polymerization until a predetermined stirring torque is reached at 1 mmHg or less.
- Table 1 shows the composition and characteristic values of the polymer polyol (B1) thus obtained. Each measurement evaluation item followed the above-mentioned method.
- Polymer polyols (A2) and (B2) were obtained in the same manner as the polymer polyol (A1).
- the polymer polyol (A3) was obtained by the same method as the polymer polyol (B1). These characteristic values are shown in Table 1.
- Polymer polyols (B3) and (B4) those shown below were used.
- Polymer polyol (B3) Polycarbonate diol T5652 (number average molecular weight 2000) manufactured by Asahi Kasei Corporation
- Polymer polyol (B4) Kuraray Co., Ltd. polyester polyol P2010 (number average molecular weight 2000)
- Polymer polyol (B5) Polycarbonate diol T5651 (number average molecular weight 1000) manufactured by Asahi Kasei Corporation
- Carboxylic Acid Group-Containing Polymer Compound (C2) to (C10) were obtained in the same manner as in Synthesis example (C1) of carboxylic acid group-containing polymer compound. However, for (C6), (C8), and (C9), 2,2-dimethylpropanediol was added at the charging stage. Others are the same as the synthesis example (C1) of the carboxylic acid group-containing polymer compound.
- Example 1 To 100 parts of the solid content of the carboxylic acid group-containing polymer compound (C1), 9 parts of YDCN-700-10 (Novolac type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and TETRAD manufactured by Mitsubishi Gas Chemical Co., Ltd. are used as epoxy resins. Add 0.1 part of (registered trademark) -X (N, N, N ′, N′-tetraglycidyl-m-xylenediamine), adjust the solid content concentration to 35% using methyl ethyl ketone, and adhere An agent composition was obtained. The obtained adhesive composition was evaluated by the method shown below. The results are shown in Table 3.
- the resin of the present invention has a dry solder resistance of 340 ° C. or higher and is excellent in a humid solder resistance.
- Example 6 there is no problem even if a small amount of chain extender is used.
- the carboxylic acid group-containing polymer compound of the present invention and the adhesive composition containing the carboxylic acid group-containing polymer compound are excellent in adhesion to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy. High degree of moisture and heat resistance that can be used for lead-free soldering under high humidity while maintaining its properties. Therefore, it is particularly useful as an adhesive for circuit boards including FPC.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Laminated Bodies (AREA)
Abstract
Description
高分子ポリオール(A)とは異なる数平均分子量(Mn2)が1,000以上である高分子ポリオール(B)と、
テトラカルボン酸二無水物とを少なくとも含み、下記(1)~(2)を満足するカルボン酸基含有高分子化合物。
(1)共重合成分中、高分子ポリオール(A)の数平均分子量(Mn1)が最大である
(2)カルボン酸基含有高分子化合物の数平均分子量(Mn3)が、高分子ポリオール(A)の数平均分子量(Mn1)の1.7倍以下である A polymer polyol (A) having a number average molecular weight (Mn1) of 7,000 or more as a copolymerization component;
A polymer polyol (B) having a number average molecular weight (Mn2) different from that of the polymer polyol (A) of 1,000 or more;
A carboxylic acid group-containing polymer compound comprising at least tetracarboxylic dianhydride and satisfying the following (1) to (2):
(1) The number average molecular weight (Mn1) of the polymer polyol (A) is the largest in the copolymer component (2) The number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is the polymer polyol (A) The number average molecular weight (Mn1) is 1.7 times or less
高分子ポリオール(A)は、数平均分子量(Mn1)が7,000以上であることが必要である。好ましくは7,000以上であり、より好ましくは8,000以上であり、さらに好ましくは10,000以上であり、特に好ましくは12,000以上である。Mn1が7,000未満であると架橋密度が高くなり、接着剤組成物から得られる塗膜が硬くなるため、密着力が低下する傾向がある。加えて、耐加湿ハンダ時に発生する水蒸気の応力を緩和しにくくなるため、耐加湿ハンダ性が悪化する傾向もある。また、Mn1は50,000以下であることが好ましく、40,000以下であることがより好ましく、30,000以下であることがさらに好ましい。大きすぎると架橋が不十分となり、耐熱性が低下することがある。 <Polymer polyol (A)>
The polymer polyol (A) needs to have a number average molecular weight (Mn1) of 7,000 or more. Preferably it is 7,000 or more, More preferably, it is 8,000 or more, More preferably, it is 10,000 or more, Especially preferably, it is 12,000 or more. When Mn1 is less than 7,000, the crosslinking density increases, and the coating film obtained from the adhesive composition becomes hard, so the adhesion tends to decrease. In addition, since it becomes difficult to relieve the water vapor stress generated during humidification soldering, the resistance to humidification soldering tends to deteriorate. Further, Mn1 is preferably 50,000 or less, more preferably 40,000 or less, and further preferably 30,000 or less. If it is too large, crosslinking may be insufficient and heat resistance may be reduced.
高分子ポリオール(B)は、高分子ポリオール(A)とは異なるポリオールであり、数平均分子量(Mn2)が1,000以上であることが必要である。高分子ポリオール(A)と異なるとは、少なくとも組成または物性のいずれかが異なることをいう。数平均分子量(Mn2)は、好ましくは1,200以上であり、より好ましくは1,500以上である。1,000未満であると高分子ポリオール(B)同士で結合を作りやすくなるため、低分子量かつ高酸価となりやすく、架橋後の塗膜にゲル状物が発生しやすくなる。また、10,000以下であることが好ましく、8,000以下であることがより好ましく、6,000以下であることがさらに好ましい。大きすぎると付与できるカルボン酸基の量が少なくなり、得られた塗膜の架橋密度が不足して耐熱性が不十分となることがある。 <Polymer polyol (B)>
The polymer polyol (B) is a polyol different from the polymer polyol (A), and the number average molecular weight (Mn2) needs to be 1,000 or more. The difference from the polymer polyol (A) means that at least either the composition or the physical properties are different. 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 polyol (B) can easily form a bond, so that it tends to have a low molecular weight and a high acid value, and a gel-like substance is likely to be generated in the crosslinked coating film. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and further preferably 6,000 or less. If it is too large, the amount of carboxylic acid groups that can be imparted decreases, and the resulting coating film may have insufficient crosslinking density, resulting in insufficient heat resistance.
ポリエステルポリオールは、ポリカルボン酸成分とポリオール成分からなるものであることが好ましい。ポリエステルポリオールを構成するポリカルボン酸成分として、全ポリカルボン酸を100モル%としたときに、芳香族ジカルボン酸を60モル%以上含有するものであることが好ましい。より好ましくは70モル%以上であり、さらに好ましくは80モル%以上であり、100モル%であっても差し支えない。少なすぎると塗膜の凝集力が弱く、各種基材への接着強度が低下することがある。 <Polyester polyol>
The polyester polyol is preferably composed of a polycarboxylic acid component and a polyol component. As the polycarboxylic acid component constituting the polyester polyol, when the total polycarboxylic acid is 100 mol%, the aromatic dicarboxylic acid is preferably contained in an amount of 60 mol% or more. More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, and it may be 100 mol%. If the amount is too small, the cohesive force of the coating film is weak, and the adhesive strength to various substrates may be reduced.
ポリカーボネートポリオールとしては、カーボネート結合を有するポリオールであり、ポリカーボネートジオールであることが好ましい。ポリカーボネートジオールとしては市販のものを使用することができる。市販のポリカーボネートジオールとしては、例えば、旭化成ケミカルズ社製の商品名デュラノール(登録商標)T-4692(数平均分子量2000)、T-5652(数平均分子量2000)、T-5651(数平均分子量1000)、T-6002(数平均分子量2000)、CD-220(数平均分子量2000)、CD-220PL(数平均分子量2000)、CD-220HL(数平均分子量2000)、クラレ社製の商品名クラレポリオールC-2050(数平均分子量2000)、C-2090(数平均分子量2000)、C-3090(数平均分子量3000)、宇部興産社製の商品名ETERNACOLL(登録商標)UH-100(数平均分子量1000)、UH-200(数平均分子量2000)、PH-100(数平均分子量1000)、PH-200(数平均分子量2000)などが挙げられる。高分子ポリオール(B)としてガラス転移温度の低いポリエステルポリオールを使用すると、加水分解性の点で不利になるが、ポリカーボネートポリオールを使用することで加水分解性の悪いエステル結合をなくすことができるため、加水分解性を改善することが可能になると考えられる。ポリカーボネートポリオールとしては、作業性の観点から液状のものが好ましく、特にデュラノール(登録商標)シリーズが好適である。 <Polycarbonate polyol>
The polycarbonate polyol is a polyol having a carbonate bond, and is preferably a polycarbonate diol. A commercially available product can be used as the polycarbonate diol. Examples of commercially available polycarbonate diol include trade names Duranol (registered trademark) T-4692 (number average molecular weight 2000), T-5562 (number average molecular weight 2000), T-5651 (number average molecular weight 1000) manufactured by Asahi Kasei Chemicals Corporation. , 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 manufactured by Kuraray Co., Ltd. -2050 (number average molecular weight 2000), C-2090 (number average molecular weight 2000), C-3090 (number average molecular weight 3000), trade name ETERNACOLL (registered trademark) UH-100 (number average molecular weight 1000) manufactured by Ube Industries, Ltd. , UH-200 (number average molecular weight 2000), PH-100 (number average minute) The amount 1000), PH-200 (average molecular weight 2000), and the like. When a polyester polyol having a low glass transition temperature is used as the polymer polyol (B), it is disadvantageous in terms of hydrolyzability, but since an ester bond having poor hydrolyzability can be eliminated by using a polycarbonate polyol, It is considered possible to improve the hydrolyzability. The polycarbonate polyol is preferably a liquid from the viewpoint of workability, and the DURANOL (registered trademark) series is particularly preferable.
テトラカルボン酸二無水物は、芳香族テトラカルボン酸二無水物、脂肪族テトラカルボン酸二無水物または脂環族テトラカルボン酸二無水物が挙げられ、芳香族テトラカルボン酸二無水物が好ましい。具体的には、例えば、無水ピロメリット酸(PMDA)、オキシジフタル酸二無水物(ODPA)、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(BTDA)、3,3’,4,4’-ジフェニルテトラカルボン酸二無水物(BPDA)、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)、4,4’-(ヘキサフロロイソプロピリデン)ジフタル酸二無水物(6FDA)、2,2’-ビス[(ジカルボキシフェノキシ)フェニル]プロパン二無水物(BSAA)が挙げられ、これらを単独で、または2種以上を併用することができる。なかでも無水ピロメリット酸が好ましい。 <Tetracarboxylic dianhydride>
Examples of the tetracarboxylic dianhydride include an aromatic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, and an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride is preferable. Specifically, for example, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalate Examples thereof include acid dianhydride (6FDA) and 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), and these can be used alone or in combination of two or more. Of these, pyromellitic anhydride is preferable.
本発明のカルボン酸基含有高分子化合物は、共重合成分として少なくとも前記高分子ポリオール(A)、高分子ポリオール(B)およびテトラカルボン酸二無水物とを含み、(1)共重合成分中、高分子ポリオール(A)の数平均分子量(Mn1)が最大であり、(2)カルボン酸基含有高分子化合物の数平均分子量(Mn3)が、高分子ポリオール(A)の数平均分子量(Mn1)の1.7倍以下のものである。 <Carboxylic acid group-containing polymer compound>
The carboxylic acid group-containing polymer compound of the present invention contains at least the polymer polyol (A), the polymer polyol (B) and tetracarboxylic dianhydride as a copolymer component, and (1) in the copolymer component, The number average molecular weight (Mn1) of the polymer polyol (A) is the largest, and (2) the number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is the number average molecular weight (Mn1) of the polymer polyol (A). 1.7 times or less.
要件(1)について説明する。カルボン酸基含有高分子化合物の共重合成分中、高分子ポリオール(A)の数平均分子量(Mn1)が最大であることが必要である。共重合成分としては、高分子ポリオール(A)、高分子ポリオール(B)、およびテトラカルボン酸二無水物の他に、例えば他のポリオール成分や後述する鎖延長剤を任意に使用することができるが、これらを含めたすべての共重合成分の数平均分子量のうちで高分子ポリオール(A)の数平均分子量(Mn1)が最大であることが必要である。高分子ポリオール(A)の数平均分子量(Mn1)が最大であることで、カルボン酸基含有高分子化合物に最大長鎖の高分子ポリオールが共重合されることになり、カルボン酸基含有高分子化合物の優れた耐加湿ハンダ性を発現することができる。 <Requirement (1)>
The requirement (1) will be described. Among the copolymer components of the carboxylic acid group-containing polymer compound, the number average molecular weight (Mn1) of the polymer polyol (A) needs to be maximum. As the copolymer component, in addition to the polymer polyol (A), the polymer polyol (B), and the tetracarboxylic dianhydride, for example, other polyol components and a chain extender described later can be arbitrarily used. However, it is necessary that the number average molecular weight (Mn1) of the polymer polyol (A) is the largest among the number average molecular weights of all copolymerization components including these. Since the number average molecular weight (Mn1) of the polymer polyol (A) is the maximum, the carboxylic acid group-containing polymer is copolymerized with the carboxylic acid group-containing polymer compound. The compound can exhibit excellent humidification soldering resistance.
要件(2)について説明する。カルボン酸基含有高分子化合物の数平均分子量(Mn3)が、高分子ポリオール(A)の数平均分子量(Mn1)の1.7倍以下であることが必要である。すなわち、Mn3/Mn1≦1.7である。好ましくは1.6倍以下である。1.7倍を超える場合は分子量の差が小さい、またはテトラカルボン酸二無水物の量が過剰であることが考えられる。そのため、カルボン酸基含有高分子化合物のカルボン酸基含有量が不足して耐熱性が低下したり、硬化塗膜の弾性率が高くなり過ぎて、接着性が低下しやすくなる。Mn3/Mn1の下限は0.8倍以上であることが好ましく、より好ましくは0.9倍以上であり、さらに好ましくは1.0倍以上である。小さすぎると高分子ポリオール(B)と鎖延長剤(テトラカルボン酸二無水物)のみの反応が多く起こっている可能性があるため、高分子ポリオール(A)のブロックが十分にカルボン酸二無水物と反応せず、耐加湿ハンダ性不足となる可能性がある。なお、カルボン酸基含有高分子化合物は、上記数平均分子量(Mn3/Mn1)の範囲内であれば、高分子ポリオール(A)とカルボン酸二無水物のみの樹脂や、高分子ポリオール(B)とカルボン酸二無水物のみの樹脂が含まれていても差し支えない。 <Requirement (2)>
The requirement (2) will be described. It is necessary that the number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is 1.7 times or less than the number average molecular weight (Mn1) of the polymer polyol (A). That is, Mn3 / Mn1 ≦ 1.7. Preferably 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 heat resistance is lowered, or the elastic modulus of the cured coating film is too high, and the adhesiveness is likely to be lowered. The lower limit of Mn3 / Mn1 is preferably 0.8 times or more, more preferably 0.9 times or more, and further preferably 1.0 times or more. If it is too small, there is a possibility that a large amount of reaction between the polymer polyol (B) and the chain extender (tetracarboxylic dianhydride) has occurred. There is a possibility that it will not react with the product, resulting in insufficient resistance to humidification soldering. As long as the carboxylic acid group-containing polymer compound is within the range of the number average molecular weight (Mn3 / Mn1), the polymer polyol (A) and the resin containing only the carboxylic dianhydride, or the polymer polyol (B) And a resin containing only carboxylic acid dianhydride.
カルボン酸基含有高分子化合物は、本発明の効果を損ねない範囲で、共重合成分として、高分子ポリオール(A)、高分子ポリオール(B)、およびテトラカルボン酸二無水物の他に、鎖延長剤を任意に使用することができる。鎖延長剤を用いることで効率的に酸価を付与することができる。鎖延長剤を用いる場合の共重合量は、高分子ポリオール(A)100質量部に対して、0.1質量部以上であることが好ましく、より好ましくは0.5質量部以上であり、さらに好ましくは1質量部以上である。また、5質量部以下であることが好ましく、より好ましくは4質量部以下であり、さらに好ましくは3質量部以下である。共重合量が多すぎると分子量が上がり難くなる、鎖延長剤同士の反応が進行しワニスが白濁する、等の現象が発生することがある。 <Chain extender>
The carboxylic acid group-containing polymer compound has a chain in addition to the polymer polyol (A), polymer polyol (B), and tetracarboxylic dianhydride as a copolymerization component as long as the effects of the present invention are not impaired. An extender can optionally be used. An acid value can be efficiently provided by using a chain extender. When the chain extender is used, the amount of copolymerization is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the polymer polyol (A). Preferably it is 1 part by mass or more. Moreover, it is preferable that it is 5 mass parts or less, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less. If the amount of copolymerization is too large, the molecular weight may be difficult to increase, the reaction between chain extenders may progress, and the varnish may become cloudy.
本発明の接着剤組成物は、少なくとも前記カルボン酸基含有高分子化合物を含有するものであり、好ましくは有機溶剤やエポキシ樹脂(D)を含有するものである。 <Adhesive composition>
The adhesive composition of the present invention contains at least the carboxylic acid group-containing polymer compound, and preferably contains an organic solvent or an epoxy resin (D).
有機溶剤は、カルボン酸基含有高分子化合物を溶解させるものであれば、特に限定されず、エポキシ樹脂(D)も溶解させるものがより好ましい。有機溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロへキサン等の脂環族炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール系溶剤、アセトン、メチルイソブチルケトン、メチルエチルケトン、ペンタノン、ヘキサノン、シクロヘキサノン、イソホロン、アセトフェノン等のケトン系溶剤、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ギ酸ブチル等のエステル系溶剤、トリクロルエチレン、ジクロルエチレン、クロルベンゼン、クロロホルム等のハロゲン化炭化水素等を使用することができ、これら1種または2種以上を併用することができる。なかでも芳香族系炭化水素とケトン系溶剤の混合溶剤が好ましく、トルエンとメチルエチルケトンの混合溶剤がより好ましい。 <Organic solvent>
The organic solvent is not particularly limited as long as it dissolves the carboxylic acid group-containing polymer compound, and more preferably dissolves the epoxy resin (D). Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, cycloaliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, Alcohol solvents such as propanediol and phenol, acetone solvents such as methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone , Ester solvents such as butyl acetate, methyl propionate and butyl formate, and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform Can be used, it can be used in combination of these one or more. Of these, a mixed solvent of an aromatic hydrocarbon and a ketone solvent is preferable, and a mixed solvent of toluene and methyl ethyl ketone is more preferable.
エポキシ樹脂(D)は、カルボン酸基含有高分子化合物のカルボキシル基と硬化反応して、架橋するものであれば特に限定されないが、一分子中にエポキシ基を複数有する多官能エポキシ樹脂であることが好ましい。多官能エポキシ樹脂を用いることで接着剤組成物から得られる硬化塗膜は3次元架橋を形成しやすく耐熱性を向上することが可能となる。
多官能エポキシ樹脂として、例えばクレゾールノボラック型エポキシ樹脂やジシクロペンタジエン骨格を有するエポキシ樹脂、フェノールノボラック型エポキシ樹脂が挙げられる。クレゾールノボラック型エポキシ樹脂やフェノールノボラック型エポキシ樹脂であると、硬化塗膜の架橋密度を下げて剥離時の応力を緩和させることができるため耐加湿ハンダ特性が向上する。クレゾールノボラック型エポキシ樹脂の市販品としては、DIC社製のYDCN-700等が挙げられる。一方、ジシクロペンタジエン骨格を有するエポキシ樹脂であると、ジシクロペンタジエン骨格が剛直であるため、硬化塗膜の吸湿性が極めて小さくなり、硬化塗膜の架橋密度を下げて、剥離時の応力を緩和させることができる。そのため、耐加湿ハンダ性が向上する。ジシクロペンタジエン骨格を有するエポキシ樹脂の市販品としてはDIC社製HP7200シリーズが挙げられる。これらを単独でまたは2種以上を併用することができる。 <Epoxy resin (D)>
The epoxy resin (D) is not particularly limited as long as it cures and crosslinks with the carboxyl group of the carboxylic acid group-containing polymer compound, but is a polyfunctional epoxy resin having a plurality of epoxy groups in one molecule. Is preferred. By using a polyfunctional epoxy resin, a cured coating film obtained from the adhesive composition can easily form a three-dimensional cross-link and improve heat resistance.
Examples of the polyfunctional epoxy resin include a cresol novolac type epoxy resin, an epoxy resin having a dicyclopentadiene skeleton, and a phenol novolac type epoxy resin. When it is a cresol novolac type epoxy resin or a phenol novolac type epoxy resin, the crosslink density of the cured coating film can be lowered to relieve the stress at the time of peeling, so that the moisture resistance soldering property is improved. Examples of commercially available cresol novolac epoxy resins include YDCN-700 manufactured by DIC Corporation. On the other hand, an epoxy resin having a dicyclopentadiene skeleton has a rigid dicyclopentadiene skeleton, so the hygroscopic property of the cured coating becomes extremely small, the crosslinking density of the cured coating is lowered, and the stress at the time of peeling is reduced. Can be relaxed. Therefore, humidification solder resistance improves. As a commercially available product of an epoxy resin having a dicyclopentadiene skeleton, HP7200 series manufactured by DIC can be mentioned. These can be used alone or in combination of two or more.
本発明の接着剤組成物は、本発明の効果を損なわない範囲で、さらに各種硬化性樹脂や添加剤を配合することができる。硬化性樹脂としてはフェノール系樹脂、アミノ樹脂、イソシアネート化合物、またはシリコーン樹脂などが挙げられる。 <Other additives>
The adhesive composition of the present invention can further contain various curable resins and additives as long as the effects of the present invention are not impaired. Examples of the curable resin include phenolic resins, amino resins, isocyanate compounds, and silicone resins.
本発明において、接着シートとは、本発明の接着剤組成物を硬化させて得られる接着剤組成物の塗膜(以下、接着剤層ともいう)を含有するものである。接着シートは接着剤層によって基材を被接着材に接着させる機能を有する。接着シートの基材は、接着後、被接着材の保護層として機能する。また離型基材を使用すると、離型基材を離型して、さらに別の被接着材に接着剤層を転写することができる。接着シートは、接着剤組成物を基材または離型基材に塗布し、乾燥し、硬化することによって得られる。具体的な構成としては、基材/接着剤層、離型基材/接着剤層、離型基材/接着剤層/基材、離型基材/接着剤層/離型基材、等が挙げられる。また、場合よっては離型基材を剥離した接着剤層単独であってもよい。また、接着シートには、微量または少量の有機溶剤が含有されていても良い。 <Adhesive sheet>
In this invention, an adhesive sheet contains the coating film (henceforth an adhesive bond layer) of the adhesive composition obtained by hardening the adhesive composition of this invention. The adhesive sheet has a function of adhering a base material to an adherend by an adhesive layer. The base material of the adhesive sheet functions as a protective layer for the adherend after adhesion. When a release substrate is used, the release substrate can be released and the adhesive layer can be transferred to another adherend. The adhesive sheet is obtained by applying the adhesive composition to a substrate or a release substrate, drying, and curing. Specific configurations include a base material / adhesive layer, a release base material / adhesive layer, a release base material / adhesive layer / base material, a release base material / adhesive layer / release base material, etc. Is mentioned. Moreover, depending on the case, the adhesive agent layer which peeled the mold release base material independently may be sufficient. The adhesive sheet may contain a trace amount or a small amount of an organic solvent.
本発明におけるプリント配線板は、接着シートを構成要素として含むものであり、より詳しくは導体回路を形成する金属箔と樹脂基材とから形成された積層体(金属箔/接着剤層/樹脂基材)を構成要素として含むものである。プリント配線板は、例えば、金属張積層体を用いてサブトラクティブ法などの従来公知の方法により製造される。必要に応じて、金属箔によって形成された導体回路を部分的、或いは全面的にカバーフィルムやスクリーン印刷インキ等を用いて被覆した、いわゆるフレキシブル回路板(FPC)、フラットケーブル、テープオートメーティッドボンディング(TAB)用の回路板などを総称している。 <Printed wiring board>
The printed wiring board in the present invention includes an adhesive sheet as a constituent element, and more specifically, a laminate (metal foil / adhesive layer / resin base) formed of a metal foil and a resin base material forming a conductor circuit. Material) as a component. A printed wiring board is manufactured by conventionally well-known methods, such as a subtractive method, using a metal-clad laminated body, for example. If necessary, a so-called flexible circuit board (FPC), flat cable, tape automated bonding (covered by using a cover film or screen printing ink, etc., partially or entirely covered with a conductor circuit formed of metal foil (tape automated bonding) TAB) circuit board and the like.
(1)カルボン酸基含有高分子化合物の組成
カルボン酸基含有高分子化合物を重クロロホルムに溶解し、1H-NMR分析により、各成分のモル比を求めた。 (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 the molar ratio of each component was determined by 1H-NMR analysis.
試料(カルボン酸基含有高分子化合物、高分子ポリオール(A)または高分子ポリオール(B))を、試料濃度が0.5質量%程度となるようにテトラヒドロフランに溶解または希釈し、孔径0.5μmのポリ四フッ化エチレン製メンブランフィルターで濾過したものを測定用試料とした。テトラヒドロフランを移動相とし示差屈折計を検出器とするゲル浸透クロマトグラフィーにより数平均分子量を測定した。流速は1mL/分、カラム温度は30℃とした。カラムは昭和電工製KF-802、804L、806Lを用いた。分子量標準には単分散ポリスチレンを使用した。但し、試料がテトラヒドロフランに溶解しない場合は、テトラヒドロフランに変えてN,N-ジメチルホルムアミドを用いた。数平均分子量500未満の低分子化合物(オリゴマー等)はカウントせずに省いた。 (2) Number average molecular weight (Mn)
A sample (carboxylic acid group-containing polymer compound, polymer polyol (A) or polymer polyol (B)) was dissolved or diluted in tetrahydrofuran so that the sample concentration was about 0.5% by mass, and the pore size was 0.5 μm. A sample for measurement was filtered through a polytetrafluoroethylene membrane filter. The number average molecular weight was measured by gel permeation chromatography using tetrahydrofuran as the mobile phase and a differential refractometer as the detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. As the column, KF-802, 804L and 806L manufactured by Showa Denko were used. Monodisperse polystyrene was used as the molecular weight standard. However, when the sample did not dissolve in tetrahydrofuran, N, N-dimethylformamide was used instead of tetrahydrofuran. Low molecular compounds (oligomers and the like) having a number average molecular weight of less than 500 were omitted without counting.
セイコー電子工業株式会社製の示差走査熱量分析計「DSC220型」にて、測定試料5mgをアルミパンに入れ、蓋を押さえて密封し、一度250℃で5分ホールドした後、液体窒素で急冷して、その後-150℃から250℃まで、20℃/minの昇温速度で測定した。得られた曲線の変曲点をガラス転移温度とした。なお、変曲点が2個以上ある場合は、ブロック共重合していると見なし、各々の変異点を読み取り、複数のガラス転移温度を持つものとして扱った。
(4)酸価
試料(カルボン酸基含有高分子化合物、高分子ポリオール(A)または高分子ポリオール(B))0.2gを20mlのクロロホルムに溶解し、指示薬としてフェノールフタレインを用い、0.1Nの水酸化カリウムエタノール溶液で滴定した。この滴定量から、中和に消費されたKOHのmg数を樹脂1gあたりの量に換算して酸価(mgKOH/g)を算出した。 (3) Glass transition temperature With a differential scanning calorimeter “DSC220 type” manufactured by Seiko Denshi Kogyo Co., Ltd., 5 mg of a measurement sample is put in an aluminum pan, sealed with a lid, and once held at 250 ° C. for 5 minutes. The sample was quenched with liquid nitrogen and then measured from −150 ° C. to 250 ° C. at a temperature increase rate of 20 ° C./min. The inflection point of the obtained curve was taken as the glass transition temperature. When there were two or more inflection points, it was considered that block copolymerization was performed, and each mutation point was read and handled as having a plurality of glass transition temperatures.
(4) Acid value 0.2 g of a sample (carboxylic acid group-containing polymer compound, polymer polyol (A) or polymer polyol (B)) is dissolved in 20 ml of chloroform, and phenolphthalein is used as an indicator. Titrated with 1N potassium hydroxide ethanol solution. From this titration amount, the acid number (mgKOH / g) was calculated by converting the number of mg of KOH consumed for neutralization into the amount per 1 g of resin.
(5)-1 評価用サンプル作製方法
後述する接着剤組成物を厚さ12.5μmのポリイミドフィルム(株式会社カネカ製、アピカル(登録商標))に、乾燥後の厚みが25μmとなるように引っ張り代を残して塗布し、140℃で5分乾燥して、接着性フィルム(Bステージ品)を得た。接着性フィルムの接着剤層面に20μmの圧延銅箔の光沢面が接するように貼り合わせ、160℃で35kgf/cm2の加圧下に30秒間プレスし、接着した。次いで140℃で4時間熱処理して硬化させて、耐ハンダ性及び剥離強度の評価用サンプルを得た。 (5) Solder resistance, peel strength (5) -1 Evaluation sample preparation method After drying an adhesive composition described later on a polyimide film having a thickness of 12.5 μm (manufactured by Kaneka Corporation, Apical (registered trademark)) The adhesive film (B stage product) was obtained by applying the coating material leaving a tensile allowance so that the thickness of the film became 25 μm and drying at 140 ° C. for 5 minutes. The adhesive film was bonded so that the glossy surface of 20 μm rolled copper foil was in contact with the adhesive layer surface of the adhesive film, and pressed and bonded at 160 ° C. under a pressure of 35 kgf / cm 2 for 30 seconds. Subsequently, it was cured by heat treatment at 140 ° C. for 4 hours to obtain a sample for evaluation of solder resistance and peel strength.
各特性の評価は以下の方法で行った。
耐乾燥ハンダ性:評価用サンプルを120℃の環境下にて30分放置後、加熱したハンダ浴に1分間浮かべて、膨れが発生しない上限の温度を10℃ピッチで測定した。具体的には、260℃から開始して、270℃、280℃と10℃刻みで360℃まで加温した。
この試験において、測定値の高い方が良好な耐熱性を持つことを示す。実用的性能から考慮すると350℃以上が好ましく、より好ましくは360℃以上である。
評価基準
◎:360℃以上でも膨れなし。
○:340℃未満では膨れないが、340℃以上360℃未満で膨れ発生。
△:330℃未満では膨れないが、330℃以上340℃未満で膨れ発生。
×:330℃未満で膨れ発生。 (5) -2 Evaluation method of each characteristic The evaluation of each characteristic was performed by the following method.
Dry solder resistance: The sample for evaluation was allowed to stand in an environment of 120 ° C. for 30 minutes, then floated in a heated solder bath for 1 minute, and the upper limit temperature at which swelling did not occur was measured at a pitch of 10 ° C. Specifically, starting from 260 ° C., the temperature was increased to 360 ° C. in steps of 270 ° C., 280 ° C. and 10 ° C.
In this test, a higher measured value indicates better heat resistance. In consideration of practical performance, 350 ° C. or higher is preferable, and 360 ° C. or higher is more preferable.
Evaluation criteria A: No swelling even at 360 ° C. or higher.
○: It does not swell at less than 340 ° C, but swells at 340 ° C or more and less than 360 ° C.
(Triangle | delta): Although it does not swell at less than 330 degreeC, it swells at 330 degreeC or more and less than 340 degreeC.
×: Swelling occurs at less than 330 ° C.
評価基準
○:270℃以上でも膨れなし。
△:260℃以上270℃未満で膨れ発生。
×:260℃未満で膨れあり。 Solder resistance (humidification): The sample for evaluation was allowed to stand at 40 ° C. and 80% humidification for 3 days, then floated in a heated solder bath for 1 minute, and the upper limit temperature at which swelling did not occur was measured at a pitch of 10 ° C. Specifically, starting from 220 ° C., the temperature was increased to 300 ° C. in steps of 230 ° C., 240 ° C. and 10 ° C. In this test, it shows that the higher the measured value has better heat resistance, but it is also necessary to suppress the impact due to evaporation of water vapor contained in each base material and adhesive layer, rather than the dry state, More severe heat resistance is required. In consideration of practical performance, 260 ° C. or higher is preferable, and 270 ° C. or higher is more preferable.
Evaluation criteria ○: No swelling even at 270 ° C or higher.
Δ: Swelling occurs at 260 ° C. or higher and lower than 270 ° C.
X: Swells at less than 260 ° C.
評価基準
◎:15N/cm以上
○:10N/cm以上、15N/cm未満
△:7N/cm以上、10N/cm未満
×:7N/cm未満 Peel strength: A sample for evaluation was drawn at 25 ° C., a polyimide film was drawn, a 90 ° peel test was conducted at a tensile speed of 50 mm / min, and the peel strength was measured. This test shows the adhesive strength at room temperature. In view of practical performance, it is preferably 7 N / cm or more, more preferably 10 N / cm or more.
Evaluation criteria A: 15 N / cm or more B: 10 N / cm or more, less than 15 N / cm Δ: 7 N / cm or more, less than 10 N / cm ×: less than 7 N / cm
撹拌機、温度計、流出用冷却器を装備した反応缶内に、テレフタル酸189部、イソフタル酸435部、無水トリメリット酸7部、2-メチル-1,3-プロパンジオール110部、1,6-ヘキサンジオール483部、テトラブチルチタネート0.2部を仕込み、250℃まで徐々に昇温し、留出する水を系外に除きつつエステル化反応を行った。エステル化反応終了後10mmHgまで徐々に減圧しながら初期重合を行うと共に温度を250℃まで昇温し、更に1mmHg以下で所定の撹拌トルクとなるまで後期重合を行った。その後、窒素にて常圧に戻し、無水トリメリット酸28部を投入し、220℃で30分間反応させることによって高分子ポリオール(A1)を得た。この様にして得られた高分子ポリオール(A1)の組成、特性値を表1に示した。各測定評価項目は前述の方法に従った。 Polymerization Example of Polymer Polyol (A1) In a reaction can equipped with a stirrer, a thermometer, and an outlet condenser, 189 parts of terephthalic acid, 435 parts of isophthalic acid, 7 parts of trimellitic anhydride, 2-methyl-1, Charge 110 parts of 3-propanediol, 483 parts of 1,6-hexanediol and 0.2 part of tetrabutyl titanate, gradually raise the temperature to 250 ° C., and perform the esterification reaction while removing the distilled water out of the system. It was. After completion of the esterification reaction, initial polymerization was carried out while gradually reducing the pressure to 10 mmHg, the temperature was raised to 250 ° C., and further, late polymerization was carried out at 1 mmHg or less until a predetermined stirring torque was reached. Thereafter, the pressure was returned to normal pressure with nitrogen, 28 parts of trimellitic anhydride was added, and the mixture was reacted at 220 ° C. for 30 minutes to obtain a polymer polyol (A1). The composition and characteristic values of the polymer polyol (A1) thus obtained are shown in Table 1. Each measurement evaluation item followed the above-mentioned method.
撹拌機、温度計、流出用冷却器を装備した反応缶内に、テレフタル酸390部、イソフタル酸390部、エチレングリコール367部、2,2-ジメチル-1,3-プロパンジオール362部、テトラブチルチタネート0.2部を仕込み、250℃まで徐々に昇温し、留出する水を系外に除きつつエステル化反応を行った。エステル化反応終了後10mmHgまで徐々に減圧しながら減圧初期重合を行うと共に温度を250℃まで昇温し、更に1mmHg以下で所定の撹拌トルクとなるまで後期重合を行うことによって高分子ポリオール(B1)を得た。この様にして得られた高分子ポリオール(B1)の組成、特性値を表1に示した。各測定評価項目は前述の方法に従った。 Polymerization Example of Polymer Polyol (B1) In a reaction vessel equipped with a stirrer, a thermometer and an outflow condenser, 390 parts of terephthalic acid, 390 parts of isophthalic acid, 367 parts of ethylene glycol, 2,2-dimethyl-1, 362 parts of 3-propanediol and 0.2 part of tetrabutyl titanate were added, the temperature was gradually raised to 250 ° C., and the esterification reaction was carried out while removing the distilled water out of the system. After completion of the esterification reaction, the polymer polyol (B1) is polymerized by performing initial polymerization under reduced pressure while gradually reducing the pressure to 10 mmHg, raising the temperature to 250 ° C., and further performing late polymerization until a predetermined stirring torque is reached at 1 mmHg or less. Got. Table 1 shows the composition and characteristic values of the polymer polyol (B1) thus obtained. Each measurement evaluation item followed the above-mentioned method.
高分子ポリオール(B3):旭化成(株)製ポリカーボネートジオールT5652(数平均分子量2000)
高分子ポリオール(B4):クラレ(株)製ポリエステルポリオールP2010(数平均分子量2000)
高分子ポリオール(B5):旭化成(株)製ポリカーボネートジオールT5651(数平均分子量1000) As the polymer polyols (B3) and (B4), those shown below were used.
Polymer polyol (B3): Polycarbonate diol T5652 (number average molecular weight 2000) manufactured by Asahi Kasei Corporation
Polymer polyol (B4): Kuraray Co., Ltd. polyester polyol P2010 (number average molecular weight 2000)
Polymer polyol (B5): Polycarbonate diol T5651 (number average molecular weight 1000) manufactured by Asahi Kasei Corporation
撹拌機、温度計、還流管を具備した反応缶内に、高分子ポリオール(A1)160部、高分子ポリオール(B1)40部、無水ピロメリット酸5.2部、トルエン200部を仕込み、80℃まで徐々に昇温させつつトルエンに溶解させた。溶解完了後、反応触媒としてトリエチルアミン0.1部を添加したのち、105℃まで徐々に昇温して24時間反応させた。IRにて反応終了を確認した後、トルエン108部で希釈することによって、カルボン酸基含有高分子化合物(C1)の固形分濃度40%の溶解液を得た。このようにして得られたカルボン酸基含有高分子化合物(C1)の組成、特性値を表2に示した。各測定評価項目は前述の方法に従った。
Synthesis Example of Carboxylic Acid Group-Containing Polymer Compound (C1) In a reaction can equipped with a stirrer, thermometer, and reflux tube, 160 parts of polymer polyol (A1), 40 parts of polymer polyol (B1), pyromellitic anhydride 5.2 parts of acid and 200 parts of toluene were charged and dissolved in toluene while gradually raising the temperature to 80 ° C. 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 reacted for 24 hours. After confirming the completion of the reaction by IR, a solution with a solid content concentration of 40% of the carboxylic acid group-containing polymer compound (C1) was obtained by diluting with 108 parts of toluene. The composition and characteristic values of the carboxylic acid group-containing polymer compound (C1) thus obtained are shown in Table 2. Each measurement evaluation item followed the above-mentioned method.
カルボン酸基含有高分子化合物の合成例(C1)と同様にカルボン酸基含有高分子化合物(C2)~(C10)を得た。ただし、(C6)、(C8)、(C9)については、仕込み段階で2,2-ジメチルプロパンジオールを添加している。その他はカルボン酸基含有高分子化合物の合成例(C1)と同じである。 <Synthesis Examples of Carboxylic Acid Group-Containing Polymer Compound (C2) to (C10)>
Carboxylic acid group-containing polymer compounds (C2) to (C10) were obtained in the same manner as in Synthesis example (C1) of carboxylic acid group-containing polymer compound. However, for (C6), (C8), and (C9), 2,2-dimethylpropanediol was added at the charging stage. Others are the same as the synthesis example (C1) of the carboxylic acid group-containing polymer compound.
カルボン酸基含有高分子化合物(C1)の固形分100部に、エポキシ樹脂として、新日鉄住金化学(株)製YDCN-700-10(ノボラック型エポキシ樹脂)9部と三菱ガス化学(株)製TETRAD(登録商標)-X(N,N,N’,N’-テトラグリシジル-m-キシレンジアミン)を0.1部加え、メチルエチルケトンを用いて固形分濃度が35%になるように調整し、接着剤組成物を得た。得られた接着剤組成物を下記に示した方法で評価を行った。結果を表3に示す。 <Example 1>
To 100 parts of the solid content of the carboxylic acid group-containing polymer compound (C1), 9 parts of YDCN-700-10 (Novolac type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and TETRAD manufactured by Mitsubishi Gas Chemical Co., Ltd. are used as epoxy resins. Add 0.1 part of (registered trademark) -X (N, N, N ′, N′-tetraglycidyl-m-xylenediamine), adjust the solid content concentration to 35% using methyl ethyl ketone, and adhere An agent composition was obtained. The obtained adhesive composition was evaluated by the method shown below. The results are shown in Table 3.
カルボン酸基含有高分子化合物、エポキシ樹脂を表3に示すものに変更し、実施例1と同様な方法で、表3に示す各配合量となるように変更し、実施例2~8、比較例1~6を行った。結果を表3に示す。 <Examples 2 to 8, Comparative Examples 1 to 6>
The carboxylic acid group-containing polymer compound and the epoxy resin were changed to those shown in Table 3 and changed to the respective compounding amounts shown in Table 3 in the same manner as in Example 1. Examples 1-6 were performed. The results are shown in Table 3.
比較例5にあるように、カルボン酸基含有高分子化合物(C)の分子量が大きすぎると流動性が低くなり、塗膜を作成することができなかった。 As in Comparative Example 4, when the polymer polyol (A) was not used, a coating film could not be produced (film formation).
As in Comparative Example 5, when the molecular weight of the carboxylic acid group-containing polymer compound (C) was too large, the fluidity was lowered and a coating film could not be created.
Claims (6)
- 共重合成分として数平均分子量(Mn1)が7,000以上である高分子ポリオール(A)と、
高分子ポリオール(A)とは異なる数平均分子量(Mn2)が1,000以上である高分子ポリオール(B)と、
テトラカルボン酸二無水物とを少なくとも含み、
下記(1)~(2)を満足するカルボン酸基含有高分子化合物。
(1)共重合成分中、高分子ポリオール(A)の数平均分子量(Mn1)が最大である
(2)カルボン酸基含有高分子化合物の数平均分子量(Mn3)が、高分子ポリオール(A)の数平均分子量(Mn1)の1.7倍以下である A polymer polyol (A) having a number average molecular weight (Mn1) of 7,000 or more as a copolymerization component;
A polymer polyol (B) having a number average molecular weight (Mn2) different from that of the polymer polyol (A) of 1,000 or more;
At least tetracarboxylic dianhydride,
Carboxylic acid group-containing polymer compound satisfying the following (1) to (2).
(1) The number average molecular weight (Mn1) of the polymer polyol (A) is the largest in the copolymer component (2) The number average molecular weight (Mn3) of the carboxylic acid group-containing polymer compound is the polymer polyol (A) The number average molecular weight (Mn1) is 1.7 times or less - 高分子ポリオール(A)および/または高分子ポリオール(B)が、ポリエステルポリオールまたはポリカーボネートポリオールである請求項1に記載のカルボン酸基含有高分子化合物。 The carboxylic acid group-containing polymer compound according to claim 1, wherein the polymer polyol (A) and / or the polymer polyol (B) is a polyester polyol or a polycarbonate polyol.
- 酸価が5~100mgKOH/gである請求項1または2に記載のカルボン酸基含有高分子化合物。 The carboxylic acid group-containing polymer compound according to claim 1 or 2, wherein the acid value is 5 to 100 mgKOH / g.
- 請求項1~3のいずれかに記載のカルボン酸基含有高分子化合物を含有する接着剤組成物。 An adhesive composition containing the carboxylic acid group-containing polymer compound according to any one of claims 1 to 3.
- 請求項4に記載の接着剤組成物の硬化物を含有する接着シート。 An adhesive sheet containing a cured product of the adhesive composition according to claim 4.
- 請求項5に記載の接着シートを構成要素として含むプリント配線板。 A printed wiring board comprising the adhesive sheet according to claim 5 as a constituent element.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780074899.3A CN110036054B (en) | 2016-12-06 | 2017-12-04 | Carboxylic acid group-containing polymer compound and adhesive composition containing same |
JP2018513399A JP6380710B1 (en) | 2016-12-06 | 2017-12-04 | Carboxylic acid group-containing polymer compound and adhesive composition containing the same |
KR1020197018697A KR102502362B1 (en) | 2016-12-06 | 2017-12-04 | High molecular compound containing carboxylic acid group and adhesive composition containing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-236480 | 2016-12-06 | ||
JP2016236480 | 2016-12-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018105543A1 true WO2018105543A1 (en) | 2018-06-14 |
Family
ID=62491127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/043420 WO2018105543A1 (en) | 2016-12-06 | 2017-12-04 | High-molecular-weight compound containing carboxylic acid group, and adhesive agent composition containing same |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6380710B1 (en) |
KR (1) | KR102502362B1 (en) |
CN (1) | CN110036054B (en) |
TW (1) | TWI748014B (en) |
WO (1) | WO2018105543A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022080470A1 (en) | 2020-10-16 | 2022-04-21 | 東洋紡株式会社 | Crosslinked polyester resin |
WO2023063386A1 (en) * | 2021-10-14 | 2023-04-20 | 東洋紡株式会社 | Crosslinked polyester resin, adhesive composition, and adhesive sheet |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02138333A (en) * | 1988-11-17 | 1990-05-28 | Toyo Ink Mfg Co Ltd | Polyester resin composition |
JPH05287068A (en) * | 1992-04-09 | 1993-11-02 | Showa Highpolymer Co Ltd | Production of saturated polyester resin |
JPH1069126A (en) * | 1996-04-26 | 1998-03-10 | Tomoegawa Paper Co Ltd | Polyester resin for toner, its production and electrophotographic toner using it |
JP2006137793A (en) * | 2004-11-10 | 2006-06-01 | Toyobo Co Ltd | Adhesive and circuit board using it |
JP2010013527A (en) * | 2008-07-02 | 2010-01-21 | Toyobo Co Ltd | Polyester resin, photo curable-thermosetting resin composition, photo curable-thermosetting layer, ink, adhesive and printed circuit board |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4423513B2 (en) | 1997-10-20 | 2010-03-03 | 東洋紡績株式会社 | Adhesive resin composition and adhesive film |
JP2008205370A (en) | 2007-02-22 | 2008-09-04 | Sumitomo Bakelite Co Ltd | Resin composition, adhesive with supporting base, and printed circuit board with reinforcing plate |
KR101605221B1 (en) * | 2008-12-26 | 2016-03-21 | 도요보 가부시키가이샤 | Resin composition for adhesive, adhesive comprising same, adhesive sheet, and printed wiring board including same as adhesive layer |
-
2017
- 2017-12-04 WO PCT/JP2017/043420 patent/WO2018105543A1/en active Application Filing
- 2017-12-04 CN CN201780074899.3A patent/CN110036054B/en active Active
- 2017-12-04 TW TW106142314A patent/TWI748014B/en active
- 2017-12-04 JP JP2018513399A patent/JP6380710B1/en active Active
- 2017-12-04 KR KR1020197018697A patent/KR102502362B1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02138333A (en) * | 1988-11-17 | 1990-05-28 | Toyo Ink Mfg Co Ltd | Polyester resin composition |
JPH05287068A (en) * | 1992-04-09 | 1993-11-02 | Showa Highpolymer Co Ltd | Production of saturated polyester resin |
JPH1069126A (en) * | 1996-04-26 | 1998-03-10 | Tomoegawa Paper Co Ltd | Polyester resin for toner, its production and electrophotographic toner using it |
JP2006137793A (en) * | 2004-11-10 | 2006-06-01 | Toyobo Co Ltd | Adhesive and circuit board using it |
JP2010013527A (en) * | 2008-07-02 | 2010-01-21 | Toyobo Co Ltd | Polyester resin, photo curable-thermosetting resin composition, photo curable-thermosetting layer, ink, adhesive and printed circuit board |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022080470A1 (en) | 2020-10-16 | 2022-04-21 | 東洋紡株式会社 | Crosslinked polyester resin |
WO2023063386A1 (en) * | 2021-10-14 | 2023-04-20 | 東洋紡株式会社 | Crosslinked polyester resin, adhesive composition, and adhesive sheet |
Also Published As
Publication number | Publication date |
---|---|
TWI748014B (en) | 2021-12-01 |
CN110036054B (en) | 2021-11-02 |
TW201833172A (en) | 2018-09-16 |
CN110036054A (en) | 2019-07-19 |
JP6380710B1 (en) | 2018-08-29 |
JPWO2018105543A1 (en) | 2018-12-06 |
KR102502362B1 (en) | 2023-02-21 |
KR20190090831A (en) | 2019-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7156267B2 (en) | Carboxylic acid group-containing polyester adhesive composition | |
JP6032318B2 (en) | RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND A PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER | |
TWI614306B (en) | Polyurethane resin composition and adhesive composition, laminate and printed circuit board using the same | |
JP5304152B2 (en) | RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER | |
JP5688077B2 (en) | RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND A PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER | |
KR101660083B1 (en) | Resin composition for adhesive agent, adhesive agent comprising the resin composition, adhesive sheet, and printed wiring board involving the adhesive sheet as adhesive layer | |
JP6380710B1 (en) | Carboxylic acid group-containing polymer compound and adhesive composition containing the same | |
WO2020218114A1 (en) | Resin composition, bonding film, laminate having resin composition layer, laminate, and electromagnetic wave shield film | |
JP7318838B2 (en) | Adhesive composition, adhesive sheet, laminate and printed wiring board | |
WO2024090291A1 (en) | Adhesive composition, and adhesive sheet, layered body and printed circuit board containing same | |
WO2023063386A1 (en) | Crosslinked polyester resin, adhesive composition, and adhesive sheet | |
JP2024007384A (en) | Adhesive agent composition and adhesive agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018513399 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17879252 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197018697 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17879252 Country of ref document: EP Kind code of ref document: A1 |