WO2011129323A1 - 接着剤用樹脂組成物、これを含有する接着剤、接着性シートおよびこれを接着剤層として含むプリント配線板 - Google Patents
接着剤用樹脂組成物、これを含有する接着剤、接着性シートおよびこれを接着剤層として含むプリント配線板 Download PDFInfo
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- WO2011129323A1 WO2011129323A1 PCT/JP2011/059067 JP2011059067W WO2011129323A1 WO 2011129323 A1 WO2011129323 A1 WO 2011129323A1 JP 2011059067 W JP2011059067 W JP 2011059067W WO 2011129323 A1 WO2011129323 A1 WO 2011129323A1
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- resin
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- 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
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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- 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 provides a resin composition excellent in adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, adhesion to glass epoxy, heat resistance, moisture resistance, and sheet life.
- the present invention relates to an adhesive, an adhesive sheet, and a printed wiring board including the adhesive as an adhesive layer.
- adhesives have been used in various fields, but due to the diversification of the purpose of use, adhesion to various plastic films and adhesion to metals such as copper, aluminum, and stainless steel rather than conventional adhesives Performance, adhesion to glass epoxy, heat resistance, moisture resistance, sheet life, etc. are demanded.
- adhesives for circuit boards including flexible printed wiring boards hereinafter sometimes abbreviated as FPC
- FPC flexible printed wiring boards
- epoxy / acryl butadiene adhesives, epoxy / polyvinyl butyral adhesives, and the like are used for this application.
- Patent Document 1 JP-A-11-116930
- JP-A-2008-205370 Patent Document 2
- Patent Document 3 Japanese Patent Application Laid-Open No. 2007-204715
- Patent Document 1 Although the improvement in adhesiveness at high temperature is recognized, the adhesiveness at high temperature and high humidity is insufficient.
- reaction of the carboxyl group in a polyurethane resin and an epoxy group progresses gradually also at normal temperature, there existed a problem that sheet life was short.
- an adhesive composition containing two kinds of polyester resins having different glass transition temperatures is disclosed in Japanese Patent Application Laid-Open No. 2008-019375 (Patent Document 4) and Japanese Patent Application Laid-Open No. 2009-084348 (Patent Document 5). Yes.
- blending a polyester resin having a high glass transition temperature and a polyester resin having a low glass transition temperature improves the processability at room temperature, but at the storage temperature of a general adhesive sheet. Under certain conditions of 5 ° C. or lower, the flexibility was low, and the workability at low temperatures was not satisfactory. Further, since the polyester resin has a lower cohesive force than the polyurethane resin, it has poor adhesion and heat resistance, and in addition, it has a disadvantage that the flow-out amount during press working is increased and the substrate is contaminated.
- the object of the present invention is to improve each of the problems of these conventional adhesives, while maintaining adhesion to various plastic films, metals such as copper, aluminum, and stainless steel, and glass epoxy, Providing an adhesive with high moisture and heat resistance that is compatible with lead-free solder under humidity, excellent adhesiveness under high temperature and high humidity, and excellent workability during use.
- An object of the present invention is to provide an adhesive sheet having a long sheet life capable of maintaining good adhesive properties even if the adhesive sheet is used after being distributed under high temperature and high humidity. Moreover, it is providing the printed wiring board containing the adhesive bond layer obtained from the said adhesive agent or the adhesive sheet.
- this invention consists of the following structures.
- the resin composition for an adhesive of the present invention contains a carboxyl group, an acid value (unit: equivalent / 10 6 g) is 100 or more and 1000 or less, and a number average molecular weight is 5.0 ⁇ 10 3 or more and 1.0. ⁇ 10 5 or less, a polyurethane resin (a-1) having a glass transition temperature of 30 ° C. or more and 80 ° C. or less, a number average molecular weight of 5.0 ⁇ 10 3 or more and 1.0 ⁇ 10 5 or less, and a glass transition A polyester resin (a-2) having a temperature of 0 ° C.
- the epoxy resin (b) preferably has a glycidyldiamine structure.
- the blending ratio of the epoxy resin (c) is preferably 60% by mass or more and 99.9% by mass or less of the entire epoxy resin contained in the resin composition.
- the polyurethane resin (a-1) is a reaction of a polyester polyol (d), a compound (e) having one carboxylic acid group and two hydroxyl groups, and a polyisocyanate (f). It is preferable that it is obtained by.
- the resin composition for an adhesive of the present invention preferably further contains an organic solvent.
- the present invention also provides an adhesive containing the above-described resin composition of the present invention.
- the present invention also provides an adhesive sheet containing the above-described resin composition of the present invention.
- the present invention also provides a printed wiring board including an adhesive layer using the above-described resin composition of the present invention.
- the present invention provides excellent adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, adhesion to glass epoxy, adhesion at high temperatures and high humidity, and suitability for processing during production.
- a resin composition capable of obtaining an excellent adhesive and having a good sheet life of the adhesive sheet, an adhesive containing the resin composition, an adhesive sheet, and a printed wiring board including the adhesive composition as an adhesive layer it can.
- the adhesive resin composition of the present invention comprises a specific polyurethane resin (a-1), a specific polyester resin (a-2), a specific epoxy resin (b), and a specific epoxy resin (c).
- An organic solvent may be contained.
- the number average molecular weight of the polyurethane resin (a-1) used in the present invention is 5.0 ⁇ 10 3 or more and 1.0 ⁇ 10 5 .
- the number average molecular weight of the polyurethane resin (a-1) is less than 5.0 ⁇ 10 3 , the adhesion immediately after coating is insufficient and workability is deteriorated, and the flexibility is lowered and the adhesiveness is lowered. There is a tendency.
- the number average molecular weight of the polyurethane resin (a-1) exceeds 1.0 ⁇ 10 5 , the solution viscosity at the time of coating may be too high to obtain a uniform coating film.
- the lower limit of the number average molecular weight of the polyurethane resin (a-1) is preferably 8.0 ⁇ 10 5 , and more preferably 1.0 ⁇ 10 4 .
- the upper limit of the number average molecular weight of the polyurethane resin (a-1) is preferably 5.0 ⁇ 10 4 , more preferably 3.5 ⁇ 10 4 .
- the acid value (unit: equivalent / 10 6 g) of the polyurethane resin (a-1) used in the present invention is 100 or more and 1000 or less. If the acid value of the polyurethane resin (a-1) is less than 100 equivalents / 10 6 g, the adhesion to the metal substrate tends to be insufficient. Moreover, the crosslinking with the epoxy resin is insufficient, and the heat resistance tends to decrease. When the acid value of the polyurethane resin (a-1) exceeds 1000 equivalents / 10 6 g, the storage stability of the varnish when dissolved in the solvent is lowered, and the crosslinking reaction of the adhesive sheet is likely to proceed at room temperature. There is a tendency that a stable seat life cannot be obtained.
- the lower limit of the acid value of the polyurethane resin (a-1) is preferably 150 equivalents / 10 6 g, more preferably 200 equivalents / 10 6 g, and still more preferably 400 equivalents / 10 6 g.
- the upper limit of the acid value of the polyurethane resin (a-1) is preferably 900 equivalents / 10 6 g, more preferably 800 equivalents / 10 6 g, and still more preferably 700 equivalents / 10 6 g.
- Examples of a method for introducing an acid value include a method of copolymerizing a polyfunctional carboxylic acid having three or more functionalities with a polyester polyol constituting a polyurethane, and a method using a diol containing a carboxylic acid as a chain extender.
- the glass transition temperature of the polyurethane resin (a-1) used in the present invention is 30 ° C. or higher and 80 ° C. or lower.
- the glass transition temperature is less than 30 ° C., the adhesiveness at high temperature and high humidity tends to be insufficient.
- the glass transition temperature exceeds 80 ° C. the bonding with the substrate becomes insufficient, the elastic modulus at room temperature increases, and the adhesiveness at room temperature tends to be insufficient.
- the lower limit of the glass transition temperature is 35 ° C, more preferably the lower limit of the glass transition temperature is 40 ° C.
- a preferable upper limit is 75 ° C, and a more preferable upper limit is 70 ° C.
- the polyurethane resin (a-1) used in the present invention preferably uses polyester polyol (d), polyisocyanate (f), and a chain extender as its raw materials.
- the number average molecular weight of the polyester polyol (d) is preferably 2000 or more and 50000 or less, and more preferably 6000 or more and 35000 or less. If the number average molecular weight is less than 2,000, the number of urethane bonds in the molecule will be too large, and the solder heat resistance will be inferior, and the adhesiveness will also decrease. On the other hand, when the number average molecular weight exceeds 50,000, the distance between the crosslinking points with the epoxy resin becomes too long, and the solder heat resistance is inferior.
- the polyester polyol (d) preferably has an aromatic acid of 30 mol% or more, more preferably 45 mol%, when the total amount of all acid components constituting the polyester polyol (d) is 100 mol%. More preferably, it is 60 mol% or more. When the aromatic acid is less than 30 mol%, the cohesive strength of the coating film is weak, and a decrease in adhesive strength to various substrates is observed.
- aromatic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid, and 5-hydroxyisophthalic acid.
- sulfoterephthalic acid 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, and metal salts and ammonium salts thereof
- Aromatic dicarboxylic acid having a sulfonic acid group or sulfonic acid group, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis (p And aromatic oxycarboxylic acids such as -hydroxyphenyl) valeric acid.
- terephthalic acid, isophthalic acid, and a mixture thereof are particularly preferable in terms of increasing the cohesive strength of the coating film.
- acid components include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid And aliphatic dicarboxylic acids such as dodecanedioic acid and dimer acid.
- the glycol component preferably comprises an aliphatic glycol, an alicyclic glycol, an aromatic-containing glycol, an ether bond-containing glycol, and the like.
- the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1, 3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentane Diol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, hydroxypivalic acid neopentyl glycol ester, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol
- alicyclic glycols include 1,4-cyclohexanediol
- ether bond-containing glycol examples include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, neopentyl glycol propylene oxide adduct, and the like. be able to.
- aromatic-containing glycols include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct of bisphenol A, and 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 propylene oxide adducts.
- oxycarboxylic acid compounds having a hydroxyl group and a carboxyl group in the molecular structure can also be used as a polyester raw material, such as 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenyl.
- Examples include acetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis (p-hydroxyphenyl) valeric acid and the like.
- polyester polyol (d) used in the present invention for the purpose of introducing a branched skeleton, when the total of all the acid components or all glycol components constituting the polyester polyol (d) is 100 mol%, it is 0.
- a trifunctional or higher polycarboxylic acid and / or a trifunctional or higher polyol within the range of 1 mol% or more and 5 mol% or less may be copolymerized. Since the epoxy resin is blended in the resin composition for an adhesive of the present invention, the introduction of a branched skeleton increases the terminal group of the resin (a-1), that is, the functional group capable of reacting with the crosslinking agent, thereby causing crosslinking. A coating film with high density and high strength can be obtained.
- tri- or higher functional polycarboxylic acid examples 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′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetra Carboxylic dianhydride (BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) , 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA) You can, on the other hand, as examples of tri- or higher functional
- a trifunctional or higher polycarboxylic acid and / or a trifunctional or higher polyol When a trifunctional or higher polycarboxylic acid and / or a trifunctional or higher polyol is used, it is 0.1 mol% or more and 5 mol% or less, preferably 0.1 mol% or more, based on the total acid component or total glycol component, respectively. Copolymerization is preferably within a range of 3 mol% or less, and 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. is there.
- polyester polyol (d) used in the present invention acid addition within a range of 0.1 mol% or more and 10 mol% or less can be performed for the purpose of introducing a carboxyl group if necessary.
- a monocarboxylic acid, a dicarboxylic acid, or a polyfunctional carboxylic acid compound is used for the acid addition, the molecular weight is reduced by transesterification. Therefore, it is preferable to use an acid anhydride.
- Acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, 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).
- BSAA 2,2'-bis [(dicarboxyphen
- the total acid component constituting the polyester polyol (d) used in the present invention is 100 mol%, if acid addition of 10 mol% or more is performed, gelation may occur, and the polyester may be depolymerized. This may lower the molecular weight of the resin.
- a method of performing acid addition there are, for example, a method of directly performing in a bulk state after polyester polycondensation, and a method of adding polyester in a solution.
- the reaction in the bulk state is fast, but if it is added in a large amount, gelation may occur, and since it becomes a reaction at a high temperature, care must be taken such as blocking oxygen gas to prevent oxidation.
- the addition in the solution state is slow, but a large amount of carboxyl groups can be stably introduced.
- the polyisocyanate (f) used in the production of the polyurethane resin (a-1) used in the present invention is diisocyanate, its dimer (uretodione), its trimer (isocyanurate, triol adduct, burette), etc.
- One kind or a mixture of two or more kinds thereof may be used.
- diisocyanate component 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4 -Diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane, 4,4'-diisocyanate cyclohexyl methane Iso
- a chain extender may be used if necessary.
- the chain extender include the compound (e) having one carboxylic acid and two hydroxyl groups such as low molecular weight diol, dimethylolpropionic acid, dimethylolbutanoic acid and the like already described as a component of the polyester polyol (d). It is done.
- dimethylolbutanoic acid is preferable because of easy introduction of an acid value and solubility in a general-purpose solvent.
- the use of trimethylolpropane is preferred because of the ease of introduction of hydroxyl groups.
- the polyester polyol (d) and the polyisocyanate (f), and if necessary, the chain extender may be charged all at once into a reaction vessel. You may prepare it. In any case, the total of the hydroxyl groups of the polyester polyol and chain extender in the system and the total of the isocyanate groups of the polyisocyanate are reacted at an isocyanate group / hydroxyl group functional group ratio of 1 or less. In addition, this reaction can be produced by reacting in the presence or absence of a solvent inert to isocyanate groups.
- the solvents include ester solvents (ethyl acetate, butyl acetate, ethyl butyrate, etc.), ether solvents (dioxane, tetrahydrofuran, diethyl ether, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic carbonization.
- ester solvents ethyl acetate, butyl acetate, ethyl butyrate, etc.
- ether solvents dioxane, tetrahydrofuran, diethyl ether, etc.
- ketone solvents cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.
- aromatic carbonization examples thereof include hydrogen-based solvents (benzene, toluene, xylene, etc.) and mixed solvents thereof, and ethy
- Catalysts used in ordinary urethane reactions to promote urethane reactions such as tin catalysts (trimethyltin laurate, dimethyltin dilaurate, trimethyltin hydroxide, dimethyltin dihydroxide, stannous octoate, etc.), lead catalysts (Red oleate, red-2-ethylhexoate, etc.), amine catalysts (triethylamine, tributylamine, morpholine, diazabicyclooctane, diazabicycloundecene, etc.) can be used. From the viewpoint, an amine-based catalyst is preferable.
- the number average molecular weight of the polyester resin (a-2) used in the present invention is preferably 5.0 ⁇ 10 3 or more and 1.0 ⁇ 10 5 or less.
- the number average molecular weight of the polyester resin (a-2) is less than 5.0 ⁇ 10 3 , the mechanical strength of the adhesive tends to be lowered, and the heat resistance and adhesiveness tend to be lowered, and the number average molecular weight is 1.0. If it exceeds ⁇ 10 5 , the solution viscosity at the time of application may be too high, and a uniform coating film may not be obtained.
- the lower limit of the number average molecular weight of the polyester resin (a-2) is preferably 8.0 ⁇ 10 5 , and more preferably 1.0 ⁇ 10 4 .
- the upper limit of the number average molecular weight of the polyester resin (a-2) is preferably 5.0 ⁇ 10 4 , more preferably 3.5 ⁇ 10 4 .
- the glass transition temperature of the polyester resin (a-2) used in the present invention is 0 ° C. or lower.
- the glass transition temperature is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 10 ° C. or lower.
- the same compounds as those mentioned as the acid component and glycol component used in the polyester polyol (d) can be suitably used. It is.
- the method of setting the glass transition temperature of the polyester resin (a-2) to 0 ° C. or less include a method of copolymerizing an aliphatic dicarboxylic acid, a method of copolymerizing a long-chain glycol, a method of copolymerizing a polyalkylene glycol, a lactone There is a method of copolymerizing.
- Examples of the aliphatic carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and the like.
- Examples of the long chain glycol include nonanediol, decanediol, dimer acid diol and the like.
- Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
- Examples of lactones include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
- ⁇ -caprolactone is preferable from the viewpoint of availability and economical reasons.
- the copolymerization method a method in which a lactone monomer is added in a bulk state after polycondensation and ring-opening polymerization is performed on a polyester resin is preferable.
- the blending ratio of the polyurethane resin (a-1) and the polyester resin (a-2) is 95/5 to 70/30 by mass ratio, preferably 95/5 to 80/20, More preferably, it is 93/7 to 85/15. If the blending amount of the polyester resin (a-2) is larger than 30% by mass, the adhesiveness at room temperature, high temperature and high temperature and high humidity tends to be lowered, and if it is less than 5% by mass, the adhesive sheet is hard and brittle. The adhesive sheet is cracked at the time of manufacture and tends to reduce workability.
- the resin composition of the present invention requires an epoxy resin (b) containing a nitrogen atom.
- an epoxy resin (b) containing a nitrogen atom By making the resin composition of the present invention into a semi-cured state, the flow-out amount of the adhesive sheet at the time of press working can be suppressed, and the contamination and defect rate of products are greatly improved.
- the coating film of the resin composition of the present invention can be semi-cured (B-stage state) at a relatively low temperature for a short time, thus greatly improving workability. To be improved.
- Examples of the epoxy resin (b) containing a nitrogen atom include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. And glycidylamine.
- the compounding quantity of the epoxy resin (b) containing these nitrogen atoms is 0.1 mass% or more and 20 mass% or less of the whole epoxy resin.
- the blending amount of the epoxy resin (b) is less than 0.1% by mass, heating for a long time is required to obtain a semi-cured state, and workability is deteriorated.
- the compounding amount of the epoxy resin (b) is more than 20% by mass, the rigidity becomes excessively high and the adhesiveness tends to be lowered. Further, the cross-linking reaction easily proceeds during storage, and the sheet life is reduced.
- the lower limit of the amount of the epoxy resin (b) is preferably 1% by mass, more preferably 2% by mass.
- the upper limit of the amount of the epoxy resin (b) is preferably 10% by mass, more preferably 5% by mass.
- the resin composition of the present invention requires an epoxy resin (c) having a dicyclopentadiene skeleton.
- Cured coatings made of epoxy resin with a bulky dicyclopentadiene skeleton have a very low moisture absorption rate, and can reduce the cross-link density of the cured coatings to relieve stress during peeling from the substrate. Further, the adhesiveness under high humidity is further improved.
- the amount of the epoxy resin having a dicyclopentadiene skeleton is preferably 60% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more based on the entire epoxy resin. By containing 60% by mass or more of an epoxy resin having a dicyclopentadiene skeleton, it is possible to exhibit better adhesiveness under high temperature and high humidity.
- epoxy can also be used together as an epoxy resin to be blended in the adhesive resin composition of the present invention.
- glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, or 3 Alicyclic or aliphatic epoxides such as 1,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, and epoxidized soybean oil.
- the total amount of the epoxy resin compounded in the resin composition of the present invention is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass in total of the polyurethane resin (a-1) and the polyester resin (a-2). It is. If the total amount of the epoxy resin is less than 5 parts by mass with respect to 100 parts by mass in total of the polyurethane resin (a-1) and the polyester resin (a-2), crosslinking is insufficient and heat resistance is lowered. When the amount exceeds 30 parts by mass, a large amount of unreacted epoxy resin remains, and heat resistance and moisture resistance tend to decrease.
- a curing catalyst can be used for the curing reaction of the epoxy resin used in the present invention.
- imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 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-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, and these tertiary amines are converted to phenol, octylic acid, quaternized tetra Compounds converted to
- 1,8-diazabicyclo (5,4,0) -undecene-7 1,5-diazabicyclo (4,3,0) -nonene-5,6-dibutylamino-1,8-diazabicyclo (5 4,0) -undecene-7 and the like, and compounds obtained by converting these tertiary amines into amine salts with phenol, octylic acid, quaternized tetraphenylborate salts, etc. From the viewpoints of adhesion, adhesion to metal, and storage stability after blending.
- the blending amount is preferably 0.01 parts by weight or more and 1.0 part by weight or less with respect to 100 parts by weight of the polyurethane resin (a-1). Within this range, the effect on the reaction between the polyurethane resin (a-1) and the epoxy compound is further increased, and strong adhesive performance can be obtained.
- the resin composition of the present invention includes hindered amine-based, hindered phenol-based, phosphorus-based antioxidants, bromine-based, phosphorus-based, nitrogen-based, metal hydroxide-based flame retardants, leveling agents, and pigments. Additives such as dyes can be appropriately blended.
- the resin composition for an adhesive of the present invention is not limited to a one-pack type, and may be a multiple-agent mixed adhesive resin composition that is divided into a plurality of agents and mixed prior to use.
- a multi-agent mixed type it is necessary to uniformly mix a plurality of agents at an accurate blending ratio when used as an adhesive, and the difficulty of the process increases as the number of agents increases. Therefore, it is preferable to use the two-component mixed type or the three-component mixed type among the multiple agent mixed types.
- Preferred examples of the two-component mixed type include an agent comprising a polyurethane resin (a-1), a polyester resin (a-2) and an organic solvent, a nitrogen atom-containing epoxy resin (b), and a dicyclopentadiene skeleton. It can be mentioned that the epoxy resin (c) and the agent composed of an organic solvent are used as two agents.
- Preferred examples of the three-component mixed type include an agent comprising a polyurethane resin (a-1) and an organic solvent, an agent comprising a polyester resin (a-2) and an organic solvent, and an inorganic epoxy resin containing a nitrogen atom.
- a filler (b) an epoxy resin (c) having a dicyclopentadiene skeleton, and an agent composed of an organic solvent.
- an organic solvent it is possible to use no organic solvent for some or all of the agents.
- the adhesive sheet is composed of a substrate and the resin composition of the present invention, or a substrate, the resin composition of the present invention, and a release substrate.
- the adhesive sheet has a function of bonding the base material to the adherend with the resin composition of the present invention.
- the base material of the adhesive sheet functions as a protective layer for the adherend after adhesion.
- the releasable base material can be released and the adhesive layer can be transferred to another material to be adhered.
- the adhesive sheet of the present invention can be obtained by applying the resin composition of the present invention to various substrates according to a conventional method and drying.
- a release substrate is pasted to the adhesive layer after drying, it can be rolled up without causing any back-off to the substrate, and it is excellent in operability and the adhesive layer is protected so that it can be stored. Excellent and easy to use.
- the adhesive layer itself can be transferred to another substrate.
- the adhesive sheet is preferably in a semi-cured state (B stage state) in which at least a part of the resin composition of the present invention has reacted. By making it a semi-cured state, the flow-out amount of the adhesive sheet at the time of press working can be suppressed, and the contamination of the product and the increase in the defective rate can be prevented.
- the substrate on which the resin composition of the present invention is applied 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.
- the material for the metal plate and the metal foil include various metals such as SUS, copper, aluminum, iron, and zinc, and alloys and plated products thereof.
- the paper include high-quality paper, kraft paper, roll paper, and glassine paper.
- a glass epoxy etc. can be illustrated as a composite material.
- the base material to which the resin composition of the present invention is applied includes polyester resin, polyamide resin, polyimide resin, polyamideimide resin, SUS steel sheet, copper foil, aluminum foil. Glass epoxy is preferred.
- the release substrate to which the resin composition of the present invention is applied is not particularly limited, but for example, on both surfaces of paper such as fine paper, kraft paper, roll paper, glassine paper, clay, polyethylene, A coating layer of a sealant such as polypropylene is provided, and a silicone-based, fluorine-based, or alkyd-based release agent is coated on each coated layer, and polyethylene, polypropylene, ethylene- ⁇ -olefin Examples include various olefin films such as polymers and propylene- ⁇ -olefin copolymers, and polyethylene terephthalate films coated with the above release agent. For reasons such as adversely affecting electrical properties, polypropylene seals were applied to both sides of the high-quality paper, and an alkyd release agent was used on it. And those using an alkyd release agent on polyethylene terephthalate are preferred.
- the method for coating the substrate with the resin composition of the present invention is not particularly limited, and examples thereof include a method using a comma coater, a reverse roll coater and the like.
- 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 ⁇ m to 200 ⁇ m. When the thickness of the adhesive layer is less than 5 ⁇ m, the adhesive strength is insufficient. When the thickness of the adhesive layer exceeds 200 ⁇ m, there is a problem that drying is insufficient, the residual solvent is increased, and swelling occurs during pressing of printed wiring board manufacture.
- the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% or less. In the case where the residual solvent ratio after drying exceeds 1%, there is a problem that the residual solvent foams at the time of pressing the printed wiring board and causes swelling.
- the “printed wiring board” in the present invention includes a laminate formed from a metal foil and a resin layer forming a conductor circuit as constituent elements.
- 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 with a cover film, screen printing ink, etc.) covered with a conductor circuit formed of metal foil partially or entirely. TAB) circuit board and the like.
- FPC flexible circuit board
- TAB tape automated bonding
- 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 resin composition of the present invention can be suitably used for each adhesive layer of a printed wiring board.
- the resin composition of the present invention when used as an adhesive, it has high adhesiveness to the substrate constituting the printed wiring board, and has high heat resistance that can cope with lead-free solder, and also has a high temperature. It is possible to maintain high adhesiveness even under high humidity.
- a high crosslink density can be obtained while maintaining a low storage modulus, so the impact due to evaporation of moisture in the solder resistance test in a humidified state must be sufficiently mitigated. It is suitable for bonding between the metal foil layer and the cover film layer and between the base film layer and the reinforcing material layer.
- 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 in the range of 250 mm to 500 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.
- the polyimide film has a polyimide resin as a main component as its resin component.
- a polyimide resin as a main component as its resin component.
- 90% by mass or more is preferably polyimide, more preferably 95% by mass or more is polyimide, more preferably 98% by mass or more is polyimide, and 99% by mass or more is polyimide. It is particularly preferred. Any conventionally known resin can be used as the polyimide resin.
- 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.
- a metal plate such as a SUS plate or an aluminum plate, a polyimide film, a plate obtained by curing glass fiber with an epoxy resin, or the like is 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.
- a semi-finished product in which an adhesive layer is laminated on a reinforcing material layer (hereinafter referred to as “reinforcing material-side semi-finished product”) can be manufactured and bonded to a substrate film layer of a printed wiring board and reinforced as necessary.
- the adhesive agent used between a reinforcing material and a base film can be apply
- the base film side semi-finished product is, for example, 1) The process of apply
- 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 to produce a printed wiring board.
- any method can be used, and for example, bonding can be performed using a press or a roll. Moreover, both can also be bonded together, heating by the method of using a heating press or a heating roll apparatus.
- the reinforcing material-side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material.
- an adhesive for example, in the case of a reinforcing plate that cannot be rolled up hard, such as a metal plate such as SUS or aluminum, or a plate obtained by curing glass fibers with an epoxy resin, the adhesive previously applied to the release substrate is transferred and applied. It is preferred to be manufactured.
- coated adhesive agent can be performed as needed.
- the adhesive layer is semi-cured.
- the obtained reinforcing material-side semi-finished product may be used as it is for pasting with the back side of the printed wiring board, and after being used for pasting with the base film-side semi-finished product after storing the release film. May be.
- 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.
- parts means “parts by mass”.
- Epoxy value In accordance with JIS K 7236, the equivalent per 10 6 g of resin (equivalent / 10 6 ) from the epoxy equivalent (mass of resin containing 1 equivalent of epoxy group) obtained using the perchloric acid titration method. g) was calculated.
- the adhesive sheet was allowed to stand for 14 days at 40 ° C. and a relative humidity of 80%, and then cured with a SUS304 plate and pressed, heat-treated in the same manner as the initial evaluation sample, and the sample for evaluation over time. Got. One end of the obtained sample was peeled off from the SUS304 plate, and a 200 g weight was hung so that the peeling form would be 180 ° peeling, held in a 60 ° C. ⁇ 90% atmosphere for 30 minutes, and the peeled distance was measured. .
- This test shows the adhesive strength under high temperature and high humidity, and preferably has no peeling. The longer the peeling distance, the lower the adhesive strength.
- polyester resin A ⁇ Polymerization example of polyester resin A>
- terephthalic acid 203 parts terephthalic acid 203 parts, isophthalic acid 203 parts, trimellitic anhydride 9.6 parts, ethylene glycol 158 parts, neopentyl glycol 177 parts, tetrabutyl 0.2 part of titanate was charged and the temperature was gradually raised to 250 ° C. over 4 hours, and the esterification reaction was carried out while removing distilled water out of the system.
- polyester resin B ⁇ Polymerization example of polyester resin B>
- terephthalic acid 125 parts terephthalic acid 120 parts, sebacic acid 202 parts, trimellitic anhydride 4.8 parts, 2-methyl-1,3- 311 parts of propanediol, 140 parts of 1,4-butanediol and 0.2 part of tetrabutyl titanate were charged, gradually heated to 230 ° C over 4 hours, and the esterification reaction was carried out while removing the distilled water out of the system. Went.
- Polyester resins C, D, F, G, and I were obtained in the same manner as in the polymerization examples of polyester resins A and B, using the raw materials shown in Table 1 with appropriate selection of temperature and time. The composition and characteristic values of this resin are shown in Table 1.
- polyester resin E ⁇ Polymerization example of polyester resin E>
- a reaction vessel equipped with a stirrer, a thermometer, and an outflow condenser 208 parts of terephthalic acid, 208 parts of isophthalic acid, 158 parts of ethylene glycol, 177 parts of neopentyl glycol, and 0.2 part of tetrabutyl titanate are charged.
- the temperature was gradually raised to 240 ° C. over time, and the esterification reaction was performed while removing distilled water out of the system.
- polyester resin E After completion of the esterification reaction, initial polymerization under reduced pressure was carried out to 10 mmHg over 30 minutes, the temperature was raised to 250 ° C., and further late polymerization was conducted at 1 mmHg or less for 1 hour to obtain polyester resin E.
- the composition and characteristic values of the polyester resin thus obtained are shown in Table 1. Each measurement evaluation item followed the above-mentioned method.
- polyurethane resins B, C, D, E, and F ⁇ Polymerization examples of polyurethane resins B, C, D, E, and F> Using the raw materials shown in Table 2, polyurethane resins B, C, D, E, and F were obtained in the same manner as in the polymerization example of polyurethane resin A. The characteristic values are shown in Table 2. Each measurement evaluation item followed the above-mentioned method.
- epoxy resin A HP 7200-H (Daicyclopentane Diene, manufactured by Dainippon Ink & Chemicals, Inc.) Type epoxy resin
- epoxy value 3540 equivalent / 10 6 g] 15.11 parts
- epoxy resin B [TETRAD-X (N, N, N
- the epoxy resin was blended as a MEK 70% solution.
- the compounding amount of the epoxy resin was determined by calculating so as to include a glycidyl group 1.6 times the total acid value of the polyurethane resin A and the polyester resin A.
- Table 3 shows the evaluation results of the adhesion evaluation samples prepared by the above-described method. Both the initial evaluation and the time evaluation showed good results. Moreover, the flow-out property and the low-temperature bendability also show good results.
- Example 2 As in Example 1, samples were prepared with the resin types and blending amounts shown in Tables 3 and 4, and the resin properties were evaluated.
- the evaluation results are shown in Tables 3 and 4. Both the initial evaluation and the time evaluation showed good results. Moreover, the flow-out property and the low-temperature bendability also show good results.
- Comparative Example 1 is not blended with a polyester resin having a glass transition temperature of 0 ° C. or lower, and is outside the scope of the present invention.
- the flexibility is insufficient and the low temperature bendability is poor.
- Comparative Example 2 does not contain a nitrogen-containing epoxy resin and is outside the scope of the present invention.
- the flowability of the adhesive sheet is high and the flowability is poor.
- Comparative Example 3 has a high glass transition temperature of the blended polyester resin and is outside the scope of the present invention. The flexibility is insufficient and the low temperature bendability is poor.
- Comparative Example 4 has a large amount of polyester resin and is outside the scope of the present invention. Since the cohesive force is small, the peel strength is poor. Moreover, the heat resistance of the adhesive sheet is low, and the flowability is poor.
- Comparative Example 5 does not contain an epoxy resin having a dicyclopentadiene skeleton and is outside the scope of the present invention. Since the crosslinking density of the cured coating film is increased, the ability to relieve stress at the time of peeling is reduced, the peeling strength is low, and the hygroscopicity is high, so that the creep characteristics that are an index of adhesiveness at high temperature and high humidity are also poor. is there.
- Comparative Example 6 has a large amount of epoxy resin and is outside the scope of the present invention.
- the reactivity is high, the stability of the adhesive sheet is poor, and the peel strength and creep characteristics are significantly lowered over time.
- Comparative Example 7 has a large amount of nitrogen-containing epoxy resin and is outside the scope of the present invention.
- the rigidity becomes excessively high, and both the peel strength at room temperature and the creep properties are poor.
- Comparative Example 8 has a low glass transition temperature of the polyurethane resin and is outside the scope of the present invention. Since the heat resistance is low, the creep characteristics are poor. In addition, the stability of the adhesive sheet is poor, and the peel strength at room temperature significantly decreases with time.
- Comparative Example 9 has a large acid value of the polyurethane resin and is outside the scope of the present invention. Since the rigidity of the cured product becomes excessively high, the peel strength at room temperature is also low, and the creep characteristics that serve as an index of adhesion under high temperature and high humidity are also poor.
- Comparative Example 10 has a low acid value of the polyurethane resin and is outside the scope of the present invention. Since the cured product is insufficiently cross-linked and the cohesive strength and heat resistance are lowered, the peel strength and creep characteristics are poor. Further, the flowability of the adhesive sheet is high, and the flowability is poor.
- Comparative Example 11 has a small molecular weight of the polyurethane resin and is outside the scope of the present invention. Since the flexibility is low, the peel strength at room temperature is also low, and the creep characteristics that serve as an index of adhesion under high temperature and high humidity are also poor.
- Comparative Example 12 has a low molecular weight of the blended polyester resin and is outside the scope of the present invention. Insufficient heat resistance and poor flowability and creep characteristics.
- Polyester resin 1 and polyester resin 2 were synthesized in the same manner as Synthesis Example 1 and Synthesis Example 5 in Patent Document 4. Using the obtained polyester resin 1 and polyester resin 2, a dispersion solution (adhesive) was obtained in the same manner as in Example 1 of Patent Document 4.
- polyester resin 2 The characteristic values of the polyester resin 2 thus obtained are shown below. Each measurement evaluation item followed the above-mentioned method.
- the present invention provides excellent adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, adhesion to glass epoxy, adhesion at high temperatures and high humidity, and suitability for processing during production.
- a resin composition capable of obtaining an excellent adhesive and having a good sheet life of the adhesive sheet, an adhesive containing the resin composition, an adhesive sheet, and a printed wiring board including the adhesive composition as an adhesive layer it can.
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Abstract
Description
本発明は、上述した本発明の樹脂組成物を含有する接着剤についても提供する。
本発明は、上述した本発明の樹脂組成物を用いてなる接着剤層を含むプリント配線板についても提供する。
1) 前記金属箔に基材フィルムとなる樹脂の溶液を塗布し、塗膜を初期乾燥する工程、
2) 1)で得られた金属箔と初期乾燥塗膜との積層物を熱処理・乾燥する工程(以下、「熱処理・脱溶剤工程」という)、
を含む製造法により得られる。
(1)ポリエステル樹脂の組成
ポリエステル樹脂を重クロロホルムに溶解し、1H-NMR分析により、酸成分、グリコール成分のモル比を求めた。
試料を、樹脂濃度が0.5質量%程度となるようにテトラヒドロフランで溶解および/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て、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。カラムには昭和電工製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。
測定試料10mgをアルミパンに入れ、蓋を押さえて密封し、セイコーインスツルメンツ(株)製示差走査熱量分析計(DSC)DSC-200を用いて、20℃/minの昇温速度で測定し、低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になる点で引いた接線との交点をガラス転移温度とした。
試料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、樹脂106gあたりの当量(当量/106g)を算出した。
JIS K 7236に準拠し、過塩素酸滴定法を用いて得られたエポキシ当量(1当量のエポキシ基を含む樹脂の質量)から樹脂106gあたりの当量(当量/106g)を算出した。
(1)接着性
後述する接着剤組成物を厚さ25μmのポリイミドフィルム(株式会社カネカ製、アピカル)に、乾燥後の厚みが25μmとなるように塗布し、130℃で3分乾燥した。この様にして得られた接着性シートの接着剤組成物を塗布した面と500μmのSUS304板とを160℃で30kgf/cm2の加圧下に1分間プレスし、接着した。次いで140℃で4時間熱処理して硬化させて、剥離強度評価用サンプルを得た(初期評価用サンプル)。また、接着性シートを、40℃、相対湿度80%加湿下にて3週間放置後、SUS304板を圧延銅箔に変更するほかは初期評価用サンプルの場合と同様にしてプレスおよび熱処理を行い、経時評価用のサンプルを得た。
後述する接着剤用樹脂組成物を厚さ125μmのポリイミドフィルム(東レ・デュポン株式会社製、カプトン)に、乾燥後の厚みが30μmとなるように塗布し、130℃で3分乾燥した。このようにして得られた接着性シートを5mm幅に切断し、接着剤用樹脂組成物を塗布した面と500μmのSUS304板とを、160℃で30kgf/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、クリープ特性評価用サンプルを得た(初期評価用サンプル)。また、上記接着性シートを、40℃、相対湿度80%加湿下にて14日間放置後、初期評価用サンプルの場合と同様にしてSUS304板とプレス、熱処理して硬化させ、経時評価用のサンプルを得た。得られたサンプルの一端をSUS304板から剥がし、200gの錘をぶら下げて剥離形態が180°剥離となるようにし、60℃×90%雰囲気下に30分間保持し、その間に剥がれた距離を測定した。この試験は、高温高湿下での接着強度を示すもので、剥離のないものが好ましく、剥離距離が大きくなるほど、接着強度が低い。
前記クリープ特性評価用サンプル(初期評価用サンプル)のポリイミドフィルムからの接着剤の流れ出し量を測定した。
a:0.15mm未満、
b:0.15mm以上0.3mm未満、
c:0.3mm以上。
後述する接着剤用樹脂組成物を厚さ50μmのポリプロピレンフィルム(東洋紡績株式会社製、パイレン)に、乾燥後の厚みが30μmとなるように塗布し、130℃で3分乾燥し接着性シートを得た。該接着性シートを5℃雰囲気下で24時間以上放置後、5℃雰囲気下のまま、接着剤組成物の層が外側になるように折り曲げ、亀裂、割れの有無を確認した。亀裂、割れの無いものは、製造時の打ち抜き加工、スリット加工の際に亀裂、割れが抑制され、また低温下においても作業性を向上し、不良品率を低下できる。
a:亀裂、割れなし、
b:亀裂、割れあり。
撹拌器、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203部、イソフタル酸203部、無水トリメリット酸9.6部、エチレングリコール158部、ネオペンチルグリコール177部、テトラブチルチタネート0.2部を仕込み、4時間かけて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30分かけて10mmHgまで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30分後期重合を行った。その後、窒素にて常圧に戻し、ε-カプロラクトン399部を投入し、200℃で1時間反応させることによってポリエステル樹脂Cを得た。このようにして得られたポリエステル樹脂C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。
撹拌器、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125部、イソフタル酸120部、セバシン酸202部、無水トリメリット酸4.8部、2-メチル-1,3-プロパンジオール311部、1,4-ブタンジオール140部、テトラブチルチタネート0.2部を仕込み、4時間かけて230℃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30分かけて10mmHgまで減圧初期重合を行うと共に温度を240℃まで昇温し、更に1mmHg以下で1時間後期重合を行った。その後、窒素にて常圧に戻し、無水トリメリット酸4.8部を投入し、220℃で30分間反応させることによってポリエステル樹脂Aを得たこのようにして得られたポリエステルの組成、特性値を表1に示した。各測定評価項目は先述の方法に従った。
ポリエステル樹脂A,Bの重合例と同様にして、また温度、時間を適宜選択し表1に示す原料を用いて、ポリエステル樹脂C,D,F,G,Iを得た。この樹脂の組成、特性値を表1に示した。
撹拌器、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208部、イソフタル酸208部、エチレングリコール158部、ネオペンチルグリコール177部、テトラブチルチタネート0.2部を仕込み、4時間かけて240℃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30分かけて10mmHgまで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1時間後期重合を行い、ポリエステル樹脂Eを得た。このようにして得られたポリエステル樹脂の組成、特性値を表1に示した。各測定評価項目は先述の方法に従った。
ポリエステル樹脂Eの重合例と同様にして、また温度、時間を適宜選択し表1に示す原料を用いて、ポリエステル樹脂Hを得た。この樹脂の組成、特性値を表1に示した。
温度計、攪拌機、還流式冷却管および蒸留管を具備した反応容器に表1に記載したポリエステル樹脂D650部、トルエン650部を仕込み溶解後、トルエン413部を蒸留させ、トルエン/水の共沸により反応系を脱水した。60℃まで冷却後、2,2-ジメチロールブタン酸(DMBA)を29.3部、メチルエチルケトン237部を加えた。DMBAが溶解後、ヘキサメチレンジイソシアネートを30.6部、さらに反応触媒としてジアザビシクロウンデセン(DBU)を0.03部加え、80℃で7時間反応させてから、メチルエチルケトン444部、トルエン148部を投入して固形分濃度を40重量%に調整し、ポリウレタン樹脂A溶液を得た。ポリウレタン樹脂Aの溶液を120℃で1時間乾燥することにより溶剤を除いたフィルムを用いて、上述した各測定評価項目に従い測定した。ポリウレタン樹脂の特性を表2に示した。
ポリウレタン樹脂Aの重合例と同様にして、表2に示す原料を用いて、ポリウレタン樹脂B,C,D,E,Fを得た。特性値を表2に示した。各測定評価項目は上述の方法に従った。
ポリウレタン樹脂Aを95部(固形分のみの質量、溶剤は含まない。以下同様)、ポリエステル樹脂Aを5部、エポキシ樹脂A[大日本インキ化学工業(株)製 HP7200-H(ジシクロペンタンジエン型エポキシ樹脂)、エポキシ価=3540当量/106g]15.11部、エポキシ樹脂B[三菱瓦斯化学(株)製 TETRAD-X(N,N,N’,N’-テトラグリシジル-m-キシレンジアミン)、エポキシ価=10000当量/106g]]0.43部、を配合し、目的とする接着剤用樹脂組成物を得た。なお、エポキシ樹脂は、MEK70%溶液として配合した。エポキシ樹脂の配合量は、ポリウレタン樹脂Aおよびポリエステル樹脂Aの酸価の総量の1.6倍グリシジル基を含むように算出して決定した。接着評価試料を上述の方法で作製し、評価した結果を表3に示す。初期評価、経時評価ともに良好な結果を示している。また、流れ出し性、低温折り曲げ性も良好な結果を示している。
実施例1と同じく、表3、表4に示される樹脂種、配合量で試料を作製し、樹脂特性を評価した。なお、エポキシ樹脂Cは、東都化成社製 YDCN703(o-クレゾールノボラック型エポキシ樹脂、エポキシ価=4651当量/106g])である。評価した結果を表3、表4に示す。初期評価、経時評価ともに良好な結果を示している。また、流れ出し性、低温折り曲げ性も良好な結果を示している。
実施例1~12と同様にして、表5、表6に示される、樹脂種、配合量で試料を作製し、樹脂特性を評価した。
特許文献4の合成例1、合成例5と同様にして、ポリエステル樹脂1、ポリエステル樹脂2を合成した。得られたポリエステル樹脂1、ポリエステル樹脂2を用いて特許文献4の実施例1と同様にして分散溶液(接着剤)を得た。
撹拌器、温度計、流出用冷却機を装備した反応缶内に、テレフタル酸83部、イソフタル酸81部、無水トリメリット酸2部、エチレングリコール77部、ネオペンチルグリコール79部を仕込み、加圧下4時間かけて230℃まで徐々に上昇し、留出する水を系外に除きつつエステル化反応を行った。続いて重合触媒としてテトラブチルチタネート0.08部を入れ、常圧で10分間攪拌した後、1時間かけて10mmHgまで減圧初期重合を行うと共に温度を250℃まで上昇し、更に1mmHg以下で30分後期重合を行った。その後、窒素雰囲気下中、200℃まで冷却した後、無水トリメリット酸2部を仕込み、30分間攪拌を行い、ポリエステル樹脂1を得た。この様にして得られたポリエステル樹脂1の特性値を以下に示した。各測定評価項目は先述の方法に従った。
・酸価:100当量/106g。
・樹脂組成:テレフタル酸/イソフタル酸/トリメリット酸//エチレングリコール/ネオペンチルグリコール///トリメリット酸=50/49/1//50/50///1(モル比)。
撹拌器、温度計、流出用冷却機を装備した反応缶内に、テレフタル酸105部、イソフタル酸17部、セバシン酸55部、エチレングリコール90部、ネオペンチルグリコール68部を仕込み、4時間かけて230℃まで徐々に上昇し、留出する水を系外に除きつつエステル化反応を行った。続いて重合触媒としてテトラブチルチタネート0.08部を入れ、常圧で10分間攪拌した後、1時間かけて10mmHgまで減圧初期重合を行うと共に温度を250℃まで上昇し、更に1mmHg以下で30分後期重合を行い、ポリエステル樹脂2を得た。この様にして得られたポリエステル樹脂2の特性値を以下に示した。各測定評価項目は先述の方法に従った。
・酸価:40当量/106g、
・ガラス転移温度:10℃、
・樹脂組成:テレフタル酸/イソフタル酸/セバシン酸//エチレングリコール/ネオペンチルグリコール=63/10/27//58/42(モル比)。
得られたポリエステル樹脂1及びポリエステル樹脂2をそれぞれ固形分濃度が30%となるように、メチルエチルケトン/トルエン=1/4(重量比)にて溶解した。これらの溶解したポリエステル樹脂を固形分量で100部(ポリエステル樹脂1/ポリエステル樹脂2=28/72[重量比])、デカブロモジフェニルエーテルを50部、三酸化アンチモンを36部、二酸化チタンを14部、二酸化ケイ素を4部、ガラスビーズを100部、250mlマヨネーズ瓶に入れて、シェーカーで6時間分散し、分散溶液を得た。
得られた分散溶液を上述の特性評価方法に従い、評価した。評価結果を以下に示した。
初期:8N/cm
40℃80%RH3週間放置後:7N/cm
・クリープ特性
初期:>40mm
40℃80%RH3週間放置後:>40mm
・流れ出し量
判定:×
・低温折り曲げ試験
判定:×
比較例13は、ポリウレタン樹脂が含まれず、凝集力が低いため、剥離強度、流れ出し量が不良である。また、エポキシ樹脂が配合されていないため、非架橋(熱可塑性)の塗膜となり、耐熱性が低く、クリープ特性も不良である。加えて、配合されるポリエステル樹脂のガラス転移温度が高いため、柔軟性が不十分となり、低温折り曲げ性が不良である。
Claims (8)
- カルボキシル基を含有し、酸価(単位:当量/106g)が100以上1000以下であり、数平均分子量が5.0×103以上1.0×105以下であり、ガラス転移温度が30℃以上80℃以下であるポリウレタン樹脂(a-1)、
数平均分子量が5.0×103以上1.0×105以下であり、ガラス転移温度が0℃以下であるポリエステル樹脂(a-2)、
窒素原子を含有するエポキシ樹脂(b)、
ジシクロペンタジエン骨格を有するエポキシ樹脂(c)、
からなり、
前記ポリウレタン樹脂(a-1)と前記ポリエステル樹脂(a-2)の合計に対する前記ポリウレタン樹脂(a-1)の含有率が70質量%以上95質量%以下であり、
前記ポリウレタン樹脂(a-1)と前記ポリエステル樹脂(a-2)の合計に対する樹脂組成物に含まれるエポキシ樹脂全体の含有率が5質量%以上30質量%以下であり、
前記エポキシ樹脂(b)の配合比率が、樹脂組成物に含まれるエポキシ樹脂全体の0.1質量%以上20質量%以下である、
接着剤用樹脂組成物。 - 前記エポキシ樹脂(b)がグリシジルジアミン構造を有する、請求項1記載の接着剤用樹脂組成物。
- 前記エポキシ樹脂(c)の配合比率が、樹脂組成物に含まれるエポキシ樹脂全体の60質量%以上99.9質量%以下である、請求項1に記載の接着剤用樹脂組成物。
- 前記ポリウレタン樹脂(a-1)が、
ポリエステルポリオール(d)、
1つのカルボン酸基と2つの水酸基を有する化合物(e)、
ポリイソシアネート(f)
の反応によって得られるものである、請求項1に記載の接着剤用樹脂組成物。 - さらに有機溶剤を含有する請求項1に記載の接着剤用樹脂組成物。
- 請求項1~5のいずれかに記載の接着剤用樹脂組成物を含有する接着剤。
- 請求項1~5のいずれかに記載の接着剤用樹脂組成物を含有する接着性シート。
- 請求項1~5のいずれかに記載の接着剤用樹脂組成物を用いてなる接着剤層を含むプリント配線板。
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JP2010084005A (ja) * | 2008-09-30 | 2010-04-15 | Toyobo Co Ltd | 接着剤用樹脂組成物、これを含有する接着剤、接着シート及びこれを接着層として含むプリント配線板 |
WO2015050251A1 (ja) * | 2013-10-04 | 2015-04-09 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | 硬化性ポリオルガノシロキサン組成物の硬化物、硬化性ポリオルガノシロキサン組成物を用いた接着体、硬化性ポリオルガノシロキサン組成物を用いた接着体の製造方法、並びにその使用 |
JP2015091948A (ja) * | 2013-10-04 | 2015-05-14 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | 硬化性ポリオルガノシロキサン組成物の硬化物、硬化性ポリオルガノシロキサン組成物を用いた接着体、硬化性ポリオルガノシロキサン組成物を用いた接着体の製造方法、並びにその使用 |
JP2016121285A (ja) * | 2014-12-25 | 2016-07-07 | 日東シンコー株式会社 | 絶縁紙 |
JP5953391B1 (ja) * | 2015-03-30 | 2016-07-20 | 株式会社フジクラ | 熱硬化性接着剤組成物、カバーレイフィルム、接着剤フィルム、金属張積層板及びフレキシブルプリント配線板 |
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JP2017117627A (ja) * | 2015-12-24 | 2017-06-29 | 住友電気工業株式会社 | 絶縁シート及びフラットケーブル |
JP2019513885A (ja) * | 2016-04-04 | 2019-05-30 | テーザ・ソシエタス・ヨーロピア | 暗反応を用いた放射線で活性化可能な感圧接着テープ及びその使用 |
JP6170211B1 (ja) * | 2016-07-15 | 2017-07-26 | 株式会社フジクラ | 熱硬化性接着剤組成物、カバーレイフィルム、接着剤フィルム、金属張積層板及びフレキシブルプリント配線板 |
JP2018009122A (ja) * | 2016-07-15 | 2018-01-18 | 株式会社フジクラ | 熱硬化性接着剤組成物、カバーレイフィルム、接着剤フィルム、金属張積層板及びフレキシブルプリント配線板 |
WO2019017366A1 (ja) * | 2017-07-19 | 2019-01-24 | 東洋紡株式会社 | 接着剤組成物 |
WO2021128250A1 (en) * | 2019-12-27 | 2021-07-01 | 3M Innovative Properties Company | High temperature resistant b-stageable epoxy adhesive and article manufactured therefrom |
WO2023008333A1 (ja) * | 2021-07-29 | 2023-02-02 | 東洋紡株式会社 | 接着剤組成物、接着シート、積層体およびプリント配線板 |
JPWO2023008333A1 (ja) * | 2021-07-29 | 2023-02-02 | ||
JP7318838B2 (ja) | 2021-07-29 | 2023-08-01 | 東洋紡エムシー株式会社 | 接着剤組成物、接着シート、積層体およびプリント配線板 |
Also Published As
Publication number | Publication date |
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KR101727353B1 (ko) | 2017-04-14 |
CN102822304B (zh) | 2014-04-30 |
US9133300B2 (en) | 2015-09-15 |
TWI504712B (zh) | 2015-10-21 |
JP5688077B2 (ja) | 2015-03-25 |
US20130020118A1 (en) | 2013-01-24 |
KR20130086117A (ko) | 2013-07-31 |
CN102822304A (zh) | 2012-12-12 |
JPWO2011129323A1 (ja) | 2013-07-18 |
TW201141977A (en) | 2011-12-01 |
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