WO2015015889A1 - Polyester contenant un groupe carboxyle et composition de résine thermodurcissable le comprenant - Google Patents

Polyester contenant un groupe carboxyle et composition de résine thermodurcissable le comprenant Download PDF

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Publication number
WO2015015889A1
WO2015015889A1 PCT/JP2014/064453 JP2014064453W WO2015015889A1 WO 2015015889 A1 WO2015015889 A1 WO 2015015889A1 JP 2014064453 W JP2014064453 W JP 2014064453W WO 2015015889 A1 WO2015015889 A1 WO 2015015889A1
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Prior art keywords
resin composition
carboxyl group
polycarbonate diol
group
thermosetting resin
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PCT/JP2014/064453
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English (en)
Japanese (ja)
Inventor
良輔 神田
知裕 青山
智晴 栗田
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東洋紡株式会社
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Priority to JP2014541444A priority Critical patent/JP5692476B1/ja
Publication of WO2015015889A1 publication Critical patent/WO2015015889A1/fr

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • Patent Document 3 for a carboxyl group-containing polyester obtained by esterifying a hydroxyl group of a polycarbonate diol obtained by polycarbonateizing only tetracarboxylic dianhydride and 1,6-hexanediol, the resin acid value is 1200 equivalents / Some 10 6 g or more high acid value carboxyl-containing polyester resins have been reported. However, since the number average molecular weight of the resin is as low as 10,000 or less and the polycarbonate diol having only one type of alkylene group increases the crystallinity of the resin, there is a problem that the flexibility of the cured solder resist is lowered. .
  • Patent Document 4 for a carboxyl group-containing polyester obtained by esterifying a hydroxyl group of a polycarbonate diol obtained by polycarbonate-forming a tetracarboxylic dianhydride and a phosphorus-containing diol, long-term insulation reliability is obtained by hydrolysis of the phosphorus-containing diol. There was a problem that the flexibility was insufficient because the number average molecular weight of the resin was as low as 10,000 or less.
  • the present invention was devised in view of the current state of the prior art as described above, and its purpose is to provide a thermosetting resin composition exhibiting excellent thermosetting properties as an adhesive or coating agent around an electronic material, and to it.
  • the object is to provide a carboxyl group-containing polyester to be used. Moreover, it is providing the cured film excellent in copper foil adhesiveness, long-term insulation reliability, and plating resistance in addition to the flexibility obtained from this thermosetting resin composition.
  • thermosetting resin composition comprising a combination of this polyester resin and a thermosetting agent exhibits good thermosetting properties as an adhesive or coating agent around electronic materials, and is obtained from this thermosetting resin composition. It was also found that the cured film obtained is excellent in copper foil adhesion, long-term insulation reliability, and plating resistance in addition to flexibility.
  • the present invention has the following configurations (1) to (9).
  • Carboxyl group-containing polyester having the following characteristics (a) to (d): (A) having a repeating structure of the general formula [I], wherein R 1 and R 2 are the following (i) to (ii): (I) R 1 is an organic group obtained by removing an acid anhydride group from tetracarboxylic dianhydride, may contain a substituent, and is an aromatic group having 1 to 30 carbon atoms, an alicyclic group, An aliphatic group or a group having a heterocyclic ring, (Ii) R 2 is an organic group obtained by removing hydroxyl groups from a polycarbonate diol, provided that the polycarbonate diol has a plurality of types alkylene group of number average molecular weight of the polycarbonate diol is from 700 to 2300 and (B) the number average molecular weight is more than 10,000 and less than or equal to 50,000, (C) The resin acid value is 1200 equivalent
  • polycarbonate diol is any of the following (i) to (iii): (I) a copolymerized polycarbonate diol in which the glycol component comprises 3-methyl-1,5-pentanediol and 1,6-hexanediol; (Ii) a copolymerized polycarbonate diol in which the glycol component comprises 1,5-pentanediol and 1,6-hexanediol; (Iii) A copolymer polycarbonate diol in which the glycol component comprises 2-methyl-1,8-octanediol and 1,9-nonanediol.
  • thermosetting resin composition comprising the carboxyl group-containing polyester according to (1) or (2) and a compound having an oxirane ring.
  • the content of the repeating structure of the general formula [I] contained in all solid components of the thermosetting resin composition is 40% by mass or more and 71% by mass or less (3) to (5) ).
  • thermosetting resin composition according to any one of the above.
  • a film forming material comprising the thermosetting resin composition according to any one of (3) to (6).
  • a solder resist agent comprising the thermosetting resin composition according to any one of (3) to (6).
  • a cured film characterized by that.
  • the carboxyl group-containing polyester of the present invention has a carboxyl group in the main chain, it can form a highly crosslinked structure when combined with a thermosetting agent, and exhibits excellent thermosetting properties. Furthermore, the cured film obtained from this thermosetting resin composition is excellent in copper foil adhesion, long-term insulation reliability, and plating resistance in addition to flexibility. Accordingly, it can be suitably used for resist inks and adhesives, automobile parts using these, printed circuit boards such as electrical appliances, and the like.
  • FIG. 1 is an explanatory diagram showing the reaction mode of the acid anhydride group of the component (C) and the hydroxyl group of the component (D).
  • FIG. 2 is an explanatory view showing a comb substrate obtained by etching a flexible copper-clad laminate for measuring long-term insulation reliability in an example.
  • the carboxyl group-containing polyester of the present invention has the following characteristics (a) to (d).
  • R 1 is an organic group obtained by removing an acid anhydride group from tetracarboxylic dianhydride, may contain a substituent, and is an aromatic group having 1 to 30 carbon atoms, an alicyclic group, An aliphatic group or a group having a heterocyclic ring
  • (Ii) R 2 is an organic group obtained by removing a hydroxyl group from a polycarbonate diol, provided that the polycarbonate diol has a plurality of types of alkylene groups, and the number average molecular weight of the polycarbonate diol is 700 to 2300.
  • the number average molecular weight is more than 10,000 and less than or equal to 50,000
  • the resin acid value is 1200 equivalents / 10 6 g or more
  • the content of the repeating structure of the general formula [I] in the carboxyl group-containing polyester is 68% by mass or more.
  • the carboxyl group-containing polyester (A) of the present invention is synthesized by esterifying the acid anhydride group of the tetracarboxylic dianhydride (C) and the hydroxyl group of the polycarbonate diol (D).
  • a thermosetting agent such as the component (B) containing an oxirane ring
  • a highly crosslinked structure can be formed at low temperatures, and excellent thermosetting Indicates.
  • the cured film obtained from the thermosetting resin composition combining the component (A) and the component (B) is an electron that requires flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance. It can be suitably used around the material.
  • tetracarboxylic dianhydride (C) is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′.
  • component (C) is ethylene glycol bis (trimellitic anhydride) (TMEG), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 4,4′-oxydiphthalic dianhydride (ODPA).
  • TMEG ethylene glycol bis (trimellitic anhydride)
  • BPDA 4,4′-diphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BTDA 4,4′-benzophenone tetracarboxylic dianhydride
  • ODPA 4,4′-oxydiphthalic dianhydride
  • These components (C) may be used alone or in combination of two or more.
  • the polycarbonate diol (D) has a number average molecular weight of 700 to 2300.
  • the number average molecular weight is preferably 800 to 2200, more preferably 900 to 2100.
  • the mass ratio of the alkylene chain derived from the polycarbonate in the carboxyl group-containing polyester is decreased, the flexibility of the cured film is decreased, This is not preferable because the acid value of the contained polyester decreases and the crosslink density of the cured film decreases.
  • the number average molecular weight of the polycarbonate diol (D) is measured by dissolving and / or diluting the component (D) with tetrahydrofuran so that the resin concentration is about 0.5% by mass, and polytetrafluoroethylene having a pore size of 0.5 ⁇ m.
  • GPC gel permeation chromatography
  • the flow rate is 1 mL / min and the column temperature is 30 ° C.
  • KF-802, 804L and 806L manufactured by Showa Denko are used for the column.
  • Monodisperse polystyrene may be used for the molecular weight standard.
  • the component (D) is a polycarbonate diol having a plurality of types of alkylene groups obtained by copolymerizing at least two types of diols (hereinafter also referred to as “raw material diols”) as the glycol component of the raw materials.
  • the glycol component is a copolymerized polycarbonate diol composed of 3-methyl-1,5-pentanediol and 1,6-hexanediol, or a copolymer composed of 1,5-pentanediol and 1,6-hexanediol.
  • Examples thereof include polycarbonate diol, and copolymer polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol.
  • Copolymer polycarbonate diol composed of 1,5-pentanediol and 1,6-hexanediol
  • glycol component here is a raw material for synthesizing a polycarbonate diol by a reaction with a carbonate ester or phosgene, and has two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon.
  • the component (D) includes 1,5-pentane skeleton, 1,6-hexane skeleton, 1,8-octane skeleton, A copolymer polycarbonate diol having an alkylene group represented by a 1,9-nonane skeleton is preferred.
  • examples of the carbonate ester as a raw material include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate and propylene carbonate. Can be mentioned.
  • a polycarbonate diol is produced by transesterification of these raw material diols and carbonates at 100 to 230 ° C.
  • This transesterification reaction can be performed under any pressure of normal pressure or reduced pressure depending on the progress of the reaction.
  • a catalyst is not always necessary, but it is desirable to use a catalyst when it is desired to speed up the reaction.
  • a transesterification catalyst used in ordinary polycarbonate production can be used, and titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium; di-n-butyltin laurate, di-n -Tin compounds such as butyltin oxide and dibutyltin diacetate; and combinations with acetic acid matane compounds can be exemplified.
  • These catalysts are preferably used in such an amount that they are in the range of 1 to 300 ppm relative to the product.
  • the component (D) is preferably a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol).
  • a polycarbonate diol or polybutadiene diol using a diol having 4 or less carbon atoms as a raw material may be used in an amount of, for example, 5 to 80 parts by mass with respect to 100 parts by mass of the polycarbonate diol.
  • a polycarbonate having a hydroxyl group only at one end may be by-produced.
  • a polycarbonate diol containing such a by-product in a very small amount, for example, 5% by mass or less may be used. When it exceeds 5 mass%, it becomes difficult to increase the molecular weight of the carboxyl group-containing polyester.
  • the charged molar ratio of the raw material of the carboxyl group-containing polyester (A) component is adjusted according to the molecular weight and acid value of the target (A) component.
  • the component (A) can be obtained by a conventionally known method.
  • the component (C) and the component (D) are preferably reacted at 70 ° C. or more and 150 ° C. or less in the presence of a solvent in a reaction vessel equipped with a stirrer and a thermometer. More preferably, the reaction is performed at 90 ° C. or higher and 130 ° C. or lower. When the temperature is 70 ° C. or more and 150 ° C.
  • the reaction time is as short as about 4 to 6 hours, the monomer component is hardly decomposed, and gelation due to a three-dimensional reaction is hardly generated.
  • the reaction temperature may be performed in multiple stages.
  • the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, particularly the reaction concentration.
  • Organic solvent used when manufacturing a component, the solvent which does not contain basic compounds, such as an amine, is preferable.
  • solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl.
  • the solvent is triethylene glycol dimethyl ether or ⁇ -butyrolactone having good solubility. Particularly preferred is ⁇ -butyrolactone.
  • the produced resin can be dissolved by 10% by mass or more in either a single solvent or a solvent in which two or more kinds are mixed. Is preferred. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more.
  • the resin is in a solid state, whether or not it has been dissolved is determined by adding a specified weight of resin powder passing through 80 mesh into a 200 ml beaker and gently stirring at 25 ° C. for 24 hours. Is left to stand at 25 ° C. for 24 hours, and it is determined by visual observation that any of gelation, non-uniformity, white turbidity, and precipitation has been dissolved.
  • reaction catalyst used when producing the component (A) include amines, quaternary ammonium salts, imidazoles, amides, pyridines, phosphines, and organometallic salts. More preferred are amine, pyridine and phosphine. More specifically, amines such as triethylamine and benzyldimethylamine; pyridines such as 4-dimethylaminopyridine; phosphines such as triphenylphosphine; Particularly preferred is 4-dimethylaminopyridine.
  • the carboxyl group-containing polyester (A) of the present invention has the following characteristics. (1) can be sufficiently high molecular weight without gelation, (2) having a number of carboxyl groups in the main chain;
  • the thermosetting resin composition in which the compound (B) containing an oxirane ring is blended with the high molecular weight component (A) exhibits good thermosetting properties. Since the cured film obtained from such a thermosetting resin composition has toughness and high cohesive force, it exhibits good adhesion to substrates such as films and metal foils.
  • the ring opening reaction of the acid anhydride group proceeds by reacting the acid anhydride group of the component (C) with the hydroxyl group of the component (D).
  • an ester bond can be formed, and on the other hand, two carboxyl groups (residual carboxyl groups) can be formed in the main chain of the component (A). Due to the presence of this carboxyl group, an excellent thermosetting property can be expressed by using an appropriate amount of the component (B) as a thermosetting agent (see FIG. 1).
  • R 1 is an organic group obtained by removing an acid anhydride group from tetracarboxylic dianhydride, which may contain a substituent, and is an aromatic group or alicyclic group having 1 to 30 carbon atoms.
  • the blending amount of the component (C) and the component (D) is important for controlling the molecular weight of the component (A).
  • the ratio of C / D 60/100 to 99/100 or 140/100 to 101/100 is good.
  • the number average molecular weight of the component (A) of the present invention is more than 10,000 and 50,000 or less. Thereby, a carboxyl group-containing thermosetting polyester having a good balance between heat resistance and solvent solubility can be obtained.
  • the number average molecular weight is preferably 10200 to 49000, and more preferably 10300 to 47900.
  • the number average molecular weight of the component (A) is not more than the above range, the flexibility of the cured film is lowered.
  • the number exceeds the above range the solution viscosity of the resin varnish becomes high and post-processing to a solder resist becomes difficult. It is not preferable.
  • the component (A) of the present invention preferably has a repeating structure represented by the following general formula [I].
  • R 1 is an organic group obtained by removing an acid anhydride group from tetracarboxylic dianhydride, which may contain a substituent, an aromatic group having 1 to 30 carbon atoms, A group having an alicyclic group, an aliphatic group, or a heterocyclic ring.
  • the acid value of the component (A) of the present invention is 1200 equivalents / 10 6 g or more.
  • a sufficient cross-linked structure is obtained, and thermosetting, long-term insulation reliability, copper foil adhesion, and the like are particularly good. Also, curing shrinkage is less likely to occur.
  • the resin acid value is less than 1200 equivalent / 10 6 g
  • the amount of the thermosetting agent is less than 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing polyester, which is not preferable because the copper foil adhesion of the cured film is lowered.
  • limiting in particular about the upper limit of an acid value It is preferable that it is about 2500 equivalent / 10 ⁇ 6 > g.
  • the content (% by mass) of the repeating structure of the general formula [I] in the carboxyl group-containing polyester of the present invention may be 68% by mass or more, and preferably 70% by mass or more. If it is 68% by mass or more, the cured film obtained from the thermosetting resin composition containing the carboxyl group-containing polyester of the present invention has copper foil adhesion, long-term insulation reliability, and plating resistance in addition to flexibility. Especially excellent in properties.
  • thermosetting resin composition of the present invention comprises at least a “carboxyl group-containing polyester (A)” and an “oxirane ring-containing compound (B)”, which will be described later, an organic solvent used for producing the component (A). Is dissolved in the organic solvent exemplified above.
  • the thermosetting resin composition of the present invention may contain a “thermosetting agent other than the component (B)”, “curing accelerator”, and / or “other additives” described later.
  • the solid content concentration of the thermosetting resin composition is preferably 40% by mass to 60% by mass, more preferably 45% by mass to 55% by mass. If it is 40% by mass to 60% by mass, the screen printability is particularly excellent.
  • the “compound (B) containing an oxirane ring”, “thermosetting agent other than the component (B)”, “curing accelerator”, and “other additives” will be described as examples.
  • the compound (B) containing an oxirane ring is a compound having a functional group capable of reacting with the carboxyl group of the component (A).
  • the component (B) is not particularly limited as long as an oxirane ring is contained in the molecule.
  • an epoxy group containing compound, an oxetane group containing compound, etc. are mentioned.
  • Examples of the epoxy group-containing compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, o-cresol novolak type epoxy resin, Flexible epoxy resin, amine type epoxy resin, heterocyclic ring containing epoxy resin, alicyclic epoxy resin, bisphenol S type epoxy resin, dicyclopentadiene type epoxy resin, triglycidyl isocyanurate, bixylenol type epoxy resin, glycidyl group Compound etc. are mentioned.
  • the oxetane group-containing compound is not particularly limited as long as it has an oxetane ring in the molecule and can be cured.
  • 3-ethyl-3-hydroxymethyloxetane, 1,4-bis- ⁇ [(3 -Ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene 3-ethyl 3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxy) Methyl) oxetane, 3-ethyl-3- ⁇ [3- (triethoxyl) propoxy] methyl ⁇ oxetane, 3,3-bis (hydroxymethyl) oxetane, di [1-hydroxymethyl (3-oxetanyl)] methyl ether, 3,3-bis (hydroxymethyl) oxetane,
  • components (B) may be used alone or in combination of two or more.
  • a phenol novolac type epoxy resin or an o-cresol novolac type epoxy resin it is preferable to use a phenol novolac type epoxy resin or an o-cresol novolac type epoxy resin.
  • components (B) may further contain an epoxy compound having only one epoxy group in one molecule as a diluent.
  • the component (B) to be added in advance may be dissolved in the same solvent as the component (A), or may be added directly to the component (A). It may be added.
  • thermosetting property can be set in a desired range by adjusting the ratio of the oxirane ring and the carboxyl group involved in thermosetting.
  • the oxirane ring / carboxyl group (molar ratio) is in the range of 2/1 to 1/2, the curability and the crosslinkability are particularly excellent.
  • the usage-amount of a component should just be determined in consideration of the use etc. of (A) component of this invention, although it does not specifically limit, It is with respect to 100 mass parts of carboxyl group-containing polyester of this invention. 40 parts by weight to 90 parts by weight is preferable, and 40 parts by weight to 80 parts by weight is more preferable.
  • the crosslinking density of the cured film obtained from the component (A) of the present invention can be adjusted to an appropriate value, so that various physical properties of the cured film can be further improved. Can be improved.
  • the amount of the component (B) is less than the above range, the crosslinkability is deteriorated. Also, when the amount is more than the above range, the crosslinkability is deteriorated, so that the heat resistance and solvent resistance may be deteriorated. is there.
  • thermosetting resin composition of the present invention in addition to the component (B), a compound having a functional group capable of reacting with a hydroxyl group, a carboxyl group or the like can also be used as a thermosetting agent.
  • a compound having a functional group capable of reacting with a hydroxyl group, a carboxyl group or the like can also be used as a thermosetting agent.
  • thermosetting resin composition of the present invention a curing accelerator can be used in order to further improve properties such as thermosetting, heat resistance, and solvent resistance.
  • the curing accelerator is not particularly limited as long as it can accelerate the curing reaction between the components (A) and (B).
  • Examples include a molar reaction product, an equimolar reaction product of organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate, and dimethylamine. You may use these individually or in combination of 2 or more types.
  • a curing accelerator having latent curability is preferable, and examples thereof include organic acid salts of DBU and DBN and / or tetraphenylboronate and a photocationic polymerization catalyst.
  • the usage-amount of a hardening accelerator 30 mass parts or less are preferable with respect to 100 mass parts of compounds (B) containing an oxirane ring.
  • the amount exceeds 30 parts by mass, the storage stability of the carboxyl group-containing polyester and the heat resistance and solvent resistance of the cured film are unfavorable.
  • thermosetting resin composition of the present invention is suitably used as various film forming materials.
  • the thermosetting resin composition of the present invention includes a defoamer, a leveling agent, a phenolic resin, a dye such as a dye or a pigment, a dye or a pigment, Stabilizers, antioxidants, flame retardants, lubricants and the like can also be added.
  • Other inorganic fine particles include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4).
  • thermosetting resin composition according to the present invention is suitably used as a film forming resin composition or a film forming material.
  • film forming materials include electronic component overcoat materials, liquid encapsulants, enameled wire varnishes, electrical insulation impregnating varnishes, cast varnishes, mica, and glass cloth varnishes, It can be used for varnishes for MCL laminates, varnishes for friction materials, interlayer insulating films, surface protective films, solder resist layers, adhesive layers and the like in the field of printed circuit boards.
  • the film-forming resin composition or film-forming material can also be used for electronic components such as semiconductor elements.
  • thermosetting the thermosetting resin composition, film forming material, or solder resist agent of the present invention By thermosetting the thermosetting resin composition, film forming material, or solder resist agent of the present invention, a cured film having excellent flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance is obtained. be able to.
  • the thermosetting resin composition according to the present invention is used for a protective film (solder resist agent) of a flexible wiring board for COF in which a wiring pattern portion is tin-plated
  • the heating temperature condition for thermosetting is a tin plating layer.
  • the temperature is preferably 80 to 130 ° C, and preferably 90 to 120 ° C. It is particularly preferred.
  • the heating time for thermosetting is 30 to 150 minutes from the viewpoint of preventing the diffusion of the tin plating layer and obtaining flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance suitable as a protective film. It is preferable that it is 45 to 120 minutes.
  • composition in carboxyl group-containing polyester (A) The component (A) is dissolved in deuterated chloroform or deuterated dimethyl sulfoxide and subjected to 1 H-NMR analysis using an NMR apparatus 400-MR manufactured by VARIAN, and each component contained in the carboxyl group-containing polyester (A) is analyzed. The molar ratio was determined and converted to the content (% by mass).
  • the component (A) was dissolved and / or diluted with tetrahydrofuran so that the resin concentration was about 0.5% by mass, and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 ⁇ m as a measurement sample.
  • the molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. KF-802, 804L and 806L manufactured by Showa Denko were used for the column. Monodisperse polystyrene was used as the molecular weight standard.
  • thermosetting resin compositions obtained in Examples and Comparative Examples have a thickness of 20 ⁇ m after drying. , Upilex-50S).
  • a laminate hereinafter referred to as a laminate
  • a laminate was formed by heating at 120 ° C. for 60 minutes in an air atmosphere to form a cured coating. What cut out this laminated body into the magnitude
  • thermosetting resin composition was applied by screen printing with a # 100 mesh polyester plate to what was dried at 70 ° C. for 3 minutes. This was dried at 80 ° C. for 30 minutes, heat cured at 120 ° C. for 1 hour, washed with water, then immersed in ICP Clean 91 at 23 ° C. for 1 minute, washed with water and immersed in a 10% sulfuric acid aqueous solution at 23 ° C. for 1 minute. And then washed with water.
  • ⁇ Content of repeating structure of general formula [I] in all solid components of thermosetting resin composition The content ratio (% by mass) of the carboxyl group-containing polyester (A) in the total solid component of the thermosetting resin composition is determined, and the molar ratio of the repeating structure of the general formula [I] contained in the carboxyl group-containing polyester (A) From this, the content (% by mass) of the repeating structure of the general formula [I] in the total solid component of the thermosetting resin composition was calculated.
  • TMEG Ethylene glycol bis (trimellitic anhydride) BPDA: 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BTDA 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride
  • ODPA 4, 4′-oxydiphthalic dianhydride
  • C1065N Kuraray Co., Ltd.
  • ⁇ Comparative Synthesis Example 2-1> In a four-necked flask equipped with a stirrer and a thermometer, as a tetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride) (Rikacide TMEG-100 manufactured by Shin Nippon Rika Co., Ltd.) 170.89 g (0 .42 mol), 35.01 g (0.20 mol) of 2,4-toluene diisocyanate (Coronate T-100 manufactured by Nippon Polyurethane Co., Ltd.) as a diisocyanate compound, and ⁇ -butyrolactone (Mitsubishi Chemical Corporation) as a solvent.
  • ethylene glycol bis (trimellitic anhydride) (Rikacide TMEG-100 manufactured by Shin Nippon Rika Co., Ltd.) 170.89 g (0 .42 mol)
  • the reaction system After heating up to 220 ° C. and confirming the distillation of phenol, the reaction system was depressurized from normal pressure to 5 mmHg over 20 minutes. While maintaining the reaction system at 200 ° C. under a reduced pressure of 5 mmHg, phenol was distilled out of the reaction system, and a polycondensation reaction was carried out for 80 minutes. The number average molecular weight of the obtained polycarbonate diol was 690.
  • TMEG Ethylene glycol bis (trimellitic anhydride)
  • IPA Isophthalic acid
  • TDI 2,4-toluene diisocyanate
  • T5650E polycarbonate diol (1,5-pentanediol / 1,6-hexanediol) manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight of about 500 C3090: Kuraray Co., Ltd.
  • Example 1 To 100 parts by mass of the carboxyl group-containing polyester obtained in Synthesis Example 1-1, 50 parts by mass of HP-7200H (trade name of dicyclopentadiene-containing phenol novolac epoxy resin manufactured by DIC Corporation) was added. , Diluted with ⁇ -butyrolactone. Further, 2.1 parts by mass of UCAT-5002 (San Apro Co., Ltd.) was added as a curing accelerator and adjusted with ⁇ -butyrolactone, and a three-roll mill (manufactured by Kodaira Seisakusho Co., Ltd., model: RIII-1RM-2) And kneaded three times to obtain a thermosetting resin composition having a solid content concentration of 52% by mass.
  • HP-7200H trade name of dicyclopentadiene-containing phenol novolac epoxy resin manufactured by DIC Corporation
  • thermosetting resin composition was applied to a glossy surface of an electrolytic copper foil having a thickness of 18 ⁇ m and a polyimide film (UPILEX-50S manufactured by Ube Industries, Ltd.) so that the thickness after drying was 20 ⁇ m. . After drying at 80 ° C. for 30 minutes with hot air, the laminate was heated in air at 120 ° C. for 60 minutes to form a cured coating. Table 3 shows the composition of the obtained thermosetting resin composition and the physical properties of the cured film.
  • thermosetting resin composition was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3, and a laminate having a cured coating film was obtained.
  • Table 3 shows the composition of the obtained thermosetting resin composition and the physical properties of the cured film.
  • HP-7200H DIC Corporation, dicyclopentadiene-containing phenol novolac type epoxy resin JER-152: Mitsubishi Chemical Corporation, phenol novolac type epoxy resin YDCN-701: Nippon Steel Chemical Co., Ltd., cresol novolak Type epoxy resin UCAT-5002: Curing accelerator made by San Apro Co., Ltd., DBU tetraphenylborate salt
  • thermosetting properties were all 90% by mass or more, and the long-term insulation reliability was all good. Moreover, flexibility, plating resistance, and copper foil adhesion were all good. That is, a cured film obtained from a thermosetting resin composition containing a carboxyl group-containing polyester that satisfies the requirements of the present invention is thermosetting, long-term insulation reliability, flexibility, plating resistance, and copper foil adhesion. Good evaluation results were shown in all of the above.
  • Comparative Example 1 since the polymer acid value is slightly low, the compounding amount of the epoxy resin contributing to the copper foil adhesion cannot be made 40 parts by mass or more with respect to 100 parts by mass of the resin content. Therefore, the intermolecular force acting between the copper foil and the cured film was reduced, resulting in poor copper foil adhesion. Furthermore, the penetration of the plating solution from the interface between the copper foil and the cured film was confirmed, and the plating resistance was poor.
  • Comparative Example 2 the copper foil adhesion and plating resistance were poor for the same reason as in Comparative Example 1.
  • Comparative Example 3 since the carboxyl group in the polymer was only at the resin end, the acid value was low and the thermosetting property was 73% by mass, resulting in failure. The copper foil adhesion, plating resistance, and long-term insulation reliability were also poor as in Comparative Example 2.
  • PTMG1000 polytetramethylene ether glycol manufactured by Mitsubishi Chemical Corporation, number average molecular weight of about 1000
  • P-1010 Polyester diol (3-methyl-1,5-pentanediol // adipic acid) manufactured by Kuraray Co., Ltd., number average molecular weight of about 1000
  • P-1050 Kuraray Co., Ltd. polyester diol (3-methyl-1,5-pentanediol // sebacic acid), number average molecular weight of about 1000
  • the meanings of the other abbreviations are the same as the meanings of the abbreviations described in Tables 1 to 3.
  • PTXG1000 Tetrahydrofuran / neopentyl glycol copolymer polyether glycol manufactured by Asahi Kasei Fibers Co., Ltd., number average molecular weight of about 1000
  • the meanings of the other abbreviations are the same as the meanings of the abbreviations described in Tables 1 to 4.
  • thermosetting properties were 90% by mass or more, and the long-term insulation reliability was all good. Moreover, flexibility, plating resistance, and copper foil adhesion were all good. That is, a cured film obtained from a thermosetting resin composition containing a carboxyl group-containing polyester that satisfies the requirements of the present invention is thermosetting, long-term insulation reliability, flexibility, plating resistance, and copper foil adhesion. Good evaluation results were shown in all of the sexes.
  • a carboxyl group-containing polyester that provides a cured product having high thermosetting, long-term insulation reliability, plating resistance, copper foil (base material) adhesion, flexibility, and workability at the same time. can do. Furthermore, if the carboxyl group-containing polyester of the present invention is used in combination with a thermosetting agent, a highly crosslinked structure can be formed, and a tough cured film can be obtained. Therefore, since the carboxyl group-containing polyester of the present invention satisfies the above properties to a high degree, it is preferably used for resist inks and adhesives, automobile parts using these, printed circuit boards used for electrical appliances, and the like. It is expected to contribute greatly to industry.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un polyester contenant un groupe carboxyle qui fournit un produit durci qui satisfait simultanément des propriétés de thermodurcissement, une fiabilité d'isolement de longue durée, une souplesse, une résistance à l'écrasement et une adhérence sur feuille de cuivre. Le polyester contenant un groupe carboxyle présente une masse moléculaire moyenne en nombre supérieure à 10 000 50 000 ou moins et présente une valeur acide de résine de 1200 équivalents/106 g ou plus, et un diol de polycarbonate qui est une matière première présente plusieurs types de chaînes d'alkylène dans lesquelles au moins deux types de diols de départ sont copolymérisés et a une masse moléculaire moyenne en nombre de 700 à 2300.
PCT/JP2014/064453 2013-07-29 2014-05-30 Polyester contenant un groupe carboxyle et composition de résine thermodurcissable le comprenant WO2015015889A1 (fr)

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WO2018179707A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Composition adhésive de polyester contenant un groupe acide carboxylique
CN109722918A (zh) * 2017-10-30 2019-05-07 Dic株式会社 聚氨酯树脂组合物、覆膜及合成皮革
CN111607066A (zh) * 2020-07-01 2020-09-01 山西生物质新材料产业研究院有限公司 一种星型聚酯改性木质素环氧树脂及其碳纤维复合预浸料
CN116262820A (zh) * 2022-12-02 2023-06-16 浙江恒逸石化研究院有限公司 一种可逆交联呋喃二甲酸基聚酯的制备方法及其应用

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JPH0249025A (ja) * 1988-05-26 1990-02-19 Daicel Chem Ind Ltd ポリカーボネートジオール
JPH02138333A (ja) * 1988-11-17 1990-05-28 Toyo Ink Mfg Co Ltd ポリエステル樹脂組成物
JP2008019368A (ja) * 2006-07-14 2008-01-31 Toyo Ink Mfg Co Ltd 顔料組成物
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Publication number Priority date Publication date Assignee Title
WO2018179707A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Composition adhésive de polyester contenant un groupe acide carboxylique
CN110268030A (zh) * 2017-03-28 2019-09-20 东洋纺株式会社 含有羧酸基的聚酯系粘合剂组合物
JPWO2018179707A1 (ja) * 2017-03-28 2020-02-06 東洋紡株式会社 カルボン酸基含有ポリエステル系接着剤組成物
CN110268030B (zh) * 2017-03-28 2021-12-28 东洋纺株式会社 含有羧酸基的聚酯系粘合剂组合物
JP7156267B2 (ja) 2017-03-28 2022-10-19 東洋紡株式会社 カルボン酸基含有ポリエステル系接着剤組成物
CN109722918A (zh) * 2017-10-30 2019-05-07 Dic株式会社 聚氨酯树脂组合物、覆膜及合成皮革
CN111607066A (zh) * 2020-07-01 2020-09-01 山西生物质新材料产业研究院有限公司 一种星型聚酯改性木质素环氧树脂及其碳纤维复合预浸料
CN111607066B (zh) * 2020-07-01 2022-10-14 山西生物质新材料产业研究院有限公司 一种星型聚酯改性木质素环氧树脂及其碳纤维复合预浸料
CN116262820A (zh) * 2022-12-02 2023-06-16 浙江恒逸石化研究院有限公司 一种可逆交联呋喃二甲酸基聚酯的制备方法及其应用
CN116262820B (zh) * 2022-12-02 2024-06-07 浙江恒逸石化研究院有限公司 一种可逆交联呋喃二甲酸基聚酯的制备方法及其应用

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