CN101397402B - Thermosetting resin composite and cured resin - Google Patents
Thermosetting resin composite and cured resin Download PDFInfo
- Publication number
- CN101397402B CN101397402B CN2008101683378A CN200810168337A CN101397402B CN 101397402 B CN101397402 B CN 101397402B CN 2008101683378 A CN2008101683378 A CN 2008101683378A CN 200810168337 A CN200810168337 A CN 200810168337A CN 101397402 B CN101397402 B CN 101397402B
- Authority
- CN
- China
- Prior art keywords
- compound
- thermosetting resin
- resin
- hydroxyl group
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a thermosetting resin composition and the condensate thereof. The thermosetting resin composition is suitable for forming a flexible film which has excellent sealing property to substrate, excellent flexibility resistance, low warping, excellent heat resistance of solder, excellent chemical coating resistance and excellent chemical insulating property. The thermosetting resin composition comprises the following components: (A) carboxyl-containing polyurethane resin obtained from the compound which has isocyanate group which is not directly connected to aromatic nucleus, and (B) a thermosetting compound. The carboxyl-containing polyurethane resin is preferably a polyurethane resin which is obtained through the reaction of the following components: (a) a compound which has the isocyanate group which is not directly connected to aromatic nucleus, preferably aliphatic isocyanic ester compound or branched chain aliphatic isocyanic ester compound, (b) a compound which has more than two hydroxyl groups in one molecule, and (c) a compound which has one hydroxyl group and more than one phenolic hydroxyl group in one molecule.
Description
Technical field
The present invention relates to be suitable for to form and the compositions of thermosetting resin of the flexible film of excellences such as the gold-plated property of adaptation, folding resistance, low warpage properties, solder heat resistance property, the chemically-resistant of base material, electrical insulating property and the protective membrane of processing by its cured article, insulating material; In the manufacturing of PC board, particularly carry protective membrane, insulation layers such as the solder resist that uses in the manufacturing of encapsulation, interlayer dielectric at the manufacturing of flexibility printed circuit board, band, or the backplate of the electroluminescence panel that uses in the indicating meter used of backlight liquid crystal display, demonstration information etc. is with being useful in the protective membrane of the display panel of protective membrane, mobile phone, clock and watch, automobile audio etc., IC, the ultra LSI sealing material etc.
Background technology
Carry at flexibility printed circuit board, band that employed solder resist has following type in the manufacturing of encapsulation: the type of using the mould consistent with pattern to be called as to paste with caking agent again behind the Kapton stamping-out of coverlay film, the type, the formation that are coated with the resistance solder paste China ink that can form ultraviolet hardening with flexible film, thermohardening type through silk screen printing have the type of the liquid photoresist printing ink of flexible film.
But, coverlay film since with the tracing ability of Copper Foil on have problems, therefore can not form pattern with high precision.On the other hand, ultraviolet hardening resistance solder paste China ink and liquid photoresist printing ink, with base material be that the adaptation of polyimide is poor, can't obtain flexible fully.In addition, because the cure shrinkage of resistance solder paste China ink and the cooling contraction after the curing are big, thereby warpage takes place, this becomes problem.
In addition; Existing thermohardening type resistance solder paste China ink; Having disclosed in Japanese special fair 5-75032 number (patent documentation 1) is the epoxy resin etching resisting ink compsn of necessary composition with epoxy resin and dibasic acid anhydride; But be adjusted into and can giving under the flexible situation formed film, with base material be the adaptation variation of polyimide, have the problem of anti-plating property, PCT patience (pressure cooker test patience) and the reduction of solder heat resistance property.
Therefore; TOHKEMY 2006-117922 number (patent documentation 2) proposed following compositions of thermosetting resin; It contains (A) urethane, has 2 above carboxyls in its 1 molecule and has ammonia ester bond that the reaction through polycarbonate diol (a) and POLYMETHYLENE POLYPHENYLISOCYANATE (b) forms and (B) thermoset composition.Through such carboxyl urethane resin that contains is used with the epoxy resin combination as the thermoset composition, can solve the problem of aforesaid existing resistance solder paste China ink, but also have needs improvement part aspect the characteristics such as solder heat resistance property.
Patent documentation 1: Japan's special fair 5-75032 communique (claims)
Patent documentation 2: TOHKEMY 2006-117922 communique (claims)
Summary of the invention
The problem that invention will solve
Thereby; The object of the present invention is to provide compositions of thermosetting resin; It can solve aforesaid prior art problems; Be suitable for forming and flexible film that the gold-plated property of adaptation, folding resistance, low warpage properties, solder heat resistance property, the chemically-resistant of base material, electrical insulating property etc. are excellent, and the PC board that is formed with the protective membrane processed by its cured article, insulation layer can lower cost be provided, especially carries parts or goods such as encapsulation for flexibility printed circuit board, band.
The method of dealing with problems
In order to realize aforementioned purpose; According to the present invention a kind of compositions of thermosetting resin can be provided; It is characterized in that this compositions of thermosetting resin contains: (A) use have the compound of the NCO that directly is not connected aromatic nucleus and obtain contain the carboxyl urethane resin; (B) heat-curable compounds.And in this manual, " aromatic nucleus " is meant phenyl ring and comprises the condensed ring of phenyl ring.
Preferred embodiment, aforementionedly contain that carboxyl urethane resin (A) is following to be obtained: have in the compound that (a) is had directly be not connected the NCO of aromatic nucleus, (b) 1 molecule and have the compound reaction of 1 alcoholic extract hydroxyl group in the compound of 2 above alcoholic extract hydroxyl groups and (c) 1 molecule and obtain.More preferably: the compound (c) that has 1 alcoholic extract hydroxyl group in aforementioned 1 molecule has 1 above phenolic hydroxyl group.Particularly preferably be: aforementioned to have the compound (a) that directly is not connected the NCO of aromatic nucleus be aliphatic isocyanates compound (comprising the ester ring type isocyanate compound), more preferably side chain aliphatic isocyanates compound.
Preferred embodiment, above-mentioned heat-curable compounds (B) is an epoxy resin, in addition, preferably also contains (C) curing catalyst.Also inorganic and/or organic filler can be contained, also organic solvent can be contained as required.
Further, the cured article that aforementioned compositions of thermosetting resin curing is formed, the part on surface or the PC board that is all covered by this cured article also can be provided according to the present invention.
The invention effect
Compositions of thermosetting resin of the present invention is characterised in that; Its contain use have the compound of the NCO that directly is not connected aromatic nucleus and obtain contain carboxyl urethane resin (A); So its cured article low warpage properties, folding resistance excellence; Simultaneously opposite characteristic is that solder heat resistance property is also excellent, and said have the compound that directly is not connected the NCO of aromatic nucleus and be preferably aliphatic isocyanates compound (comprising the ester ring type isocyanate compound), especially be preferably side chain aliphatic isocyanates compound.Usually, urethane resin is prone to crystallization because of the strong force of cohesion of ammonia ester bond, and according to the kind of the isocyanate compound that uses, its crystalline degree is an aromatic isocyanate>aliphatic isocyanates>the side chain aliphatic isocyanates.According to inventor's etc. research, detailed is indeterminate, but the crystalline degree is consistent with its situation with the reacted warpage of thermofixation of thermosetting resins such as epoxy resin, folding resistance.That is to say that the crystallinity of ammonia ester bond is related to the warpage of cured article, folding resistance,, the cured article of low warpage can be provided through reducing crystallinity.Further; Even use is not suitable for the polyfunctional epoxy resin with high performance high glass-transition temperature (Tg) of low warpageization etc. at present; Also have excellent low warpage properties, folding resistance; During thermofixation simultaneously, contain the carboxyl of carboxyl urethane resin and the functional group of heat-curable compounds (B), the epoxy group(ing) generation crosslinking reaction of for example epoxy resin, so can improve solder heat resistance property.
In addition, of the present invention preferred embodiment in the employed carboxyl urethane resin (A) that contains be following material: have the material that the compound reaction that has 1 alcoholic extract hydroxyl group in the compound of 2 above alcoholic extract hydroxyl groups and (c) 1 molecule obtains in the compound that (a) is had directly be not connected the NCO of aromatic nucleus, (b) 1 molecule.The terminal isocyanate group of this urethane resin is with above-claimed cpd (c) end-blocking, so molecular end does not have unreacted isocyanic ester residue, can improve the storage stability of urethane resin.In addition; The compound (c) that has 1 alcoholic extract hydroxyl group in aforementioned 1 molecule has under the situation of 1 above phenolic hydroxyl group; Not only can improve the storage stability of the compsn of acquisition; And have phenolic hydroxyl group at the end of urethane resin, so uprise, can further improve characteristics such as solder heat resistance property with the reactivity of the functional group of heat-curable compounds (B), for example epoxy group(ing) etc.
Thereby compositions of thermosetting resin of the present invention is suitable for forming and excellent flexible film such as the gold-plated property of adaptation, folding resistance, low warpage properties, solder heat resistance property, the chemically-resistant of base material, electrical insulating property.
Therefore, carry in the manufacturing of encapsulation protective membrane, dielectric resin material such as employed solder resist as the flexibility printed circuit board of flexible excellence, band be useful to compositions of thermosetting resin of the present invention.In addition, the film that is obtained by such compositions of thermosetting resin is not because there is warpage, so carry the encapsulation installation parts or chip is easy to flexibility printed circuit board, band after the thermofixation.Its result; The compositions of thermosetting resin of the application of the invention; In above-mentioned various fields, can low cost and high productivity ground form the flexible protective membrane of all excellents such as adaptation, folding resistance, low warpage properties, the gold-plated property of chemically-resistant, solder heat resistance property, electrical insulating property.
Embodiment
The inventor etc. further investigate in order to solve foregoing problems; The result finds; Contain simultaneously and use the compositions of thermosetting resin that contains carboxyl urethane resin (A) and heat-curable compounds (B) that has the compound of the NCO that directly is not connected aromatic nucleus and obtain; When thermofixation; The epoxy group(ing) generation crosslinking reaction of the functional group of this carboxyl and heat-curable compounds (B), for example epoxy resin; Can improve characteristics such as solder heat resistance property, said use has the compound of the NCO that directly is not connected aromatic nucleus and the carboxyl urethane resin (A) that contains that obtains is preferably: have in the compound that (a) is had directly be not connected the NCO of aromatic nucleus, (b) 1 molecule have the compound reaction of 1 alcoholic extract hydroxyl group in the compound of 2 above alcoholic extract hydroxyl groups and (c) 1 molecule and obtain contain carboxyl urethane resin (A).Usually, the cross-linking density of resin is low more, formed film flexible big more, and the warpage of the film after the thermofixation is few more., cross-linking density reduces, and characteristics such as the solder heat resistance property of the film that obtains, anti-plating property, chemical proofing are prone to reduce.In the present invention; Containing the carboxyl urethane resin has the compound of the NCO that directly is not connected aromatic nucleus by use and obtains; Through using this to contain the carboxyl urethane resin; Can reduce the crystallinity of urethane resin; As a result, be difficult to be applied in epoxy resin in the used in flexible substrate solder resist that requires warpage, folding resistance, that have high performance high glass-transition temperature (Tg), polyfunctional epoxy resin etc. and also can use, can when keeping low warpage properties, improve characteristics such as solder heat resistance property.
In addition, the compound (c) that has 1 alcoholic extract hydroxyl group in aforementioned 1 molecule further has under the situation of 1 above phenolic hydroxyl group, can obtain the urethane resin that molecular end has phenolic hydroxyl group.This molecular end has the urethane resin of phenolic hydroxyl group when thermofixation, and the epoxy group(ing) generation crosslinking reaction of the functional group of this phenolic hydroxyl group and heat-curable compounds, for example epoxy resin can further improve characteristics such as solder heat resistance property.
Each composition in the face of compositions of thermosetting resin of the present invention is elaborated down.
At first; The carboxyl urethane resin (A) that contains of the present invention is preferably following urethane resin: make to have the compound (a) that directly is not connected the NCO of aromatic nucleus, have the compound (b) of 2 above alcoholic extract hydroxyl groups in 1 molecule, also bring into play the compound (c) that has 1 alcoholic extract hydroxyl group and the phenolic hydroxyl group more than 1 in aforementioned 1 molecule of reaction terminating agent effect and react; Terminal thus urethane resin with the phenolic hydroxyl group that is imported into; But in addition, also can be by having compound (b) reaction that has 2 above alcoholic extract hydroxyl groups in the compound (a) that directly is not connected the NCO of aromatic nucleus, 1 molecule and obtaining; This compound (b) comprises and uses compound with phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups to import the urethane resin of phenolic hydroxyl group to molecular side chain, also comprises to use the compound that has carboxyl and 2 above alcoholic extract hydroxyl groups in 1 molecule to import the urethane resin etc. of carboxyl to molecular side chain.In the latter's urethane resin; As end-capped agent (reaction terminating agent); In can using above-mentioned 1 molecule, have the compound (c) of 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group; Can also use monohydroxy compounds such as fatty alcohol, monohydroxy list (methyl) acryliccompound, have the existing known various reaction terminating agents such as monocarboxylic acid that alcoholic extract hydroxyl group, amino, sulfydryl etc. can carry out the functional group of addition reaction or condensation reaction with NCO.
Aforementioned urethane resin (A) is under the situation of for example aforementioned preferred urethane resin, can have the disposable mixing of compound (c) of 1 alcoholic extract hydroxyl group in the compound (b) that have 2 above alcoholic extract hydroxyl groups in the compound (a) that directly is not connected the NCO of aromatic nucleus, 1 molecule, 1 molecule and reacts having; Can also make above-mentioned compound (b) reaction that has 2 above alcoholic extract hydroxyl groups in the compound (a) that directly is not connected the NCO of aromatic nucleus and 1 molecule that has, then with in above-mentioned 1 molecule of performance reaction terminating agent effect have compound (c) reaction of 1 alcoholic extract hydroxyl group.In addition; Under the situation of aforesaid other urethane resin; Can have phenolic hydroxyl group and/or carboxyl in the compound (a) that directly is not connected the NCO of aromatic nucleus, 1 molecule and have compound (b), the disposable mixing of reaction terminating agent of 2 above alcoholic extract hydroxyl groups and react having; But viewpoint from the adjustment molecular weight; Preferably make above-mentionedly to have the compound (a) that directly is not connected the NCO of aromatic nucleus and react, then react with reaction terminating agent with above-claimed cpd (b).
Through mixing, under catalyst-free, carry out previous reaction, but preferably be heated to 70～100C in order to improve speed of response at room temperature～100C.In addition, that the reactive ratio (mol ratio) of above-mentioned (a)～(c) composition is suitable is (a): (b)=1:1～2:1, be preferably 1:1～1.5:1, and (a+b): (c)=1:0.01～0.5, be preferably the ratio of 1:0.02～0.3.
Have a compound (a) that directly is not connected the NCO of aromatic nucleus as aforementioned, can use at present knownly variously to have the compound that directly is not connected the NCO of aromatic nucleus, but be not limited to specific compound.As concrete example with the compound (a) that directly is not connected the NCO of aromatic nucleus; For example can enumerate out side chain aliphatic diisocyanates such as aliphatic diisocyanate, trimethyl hexamethylene diisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, neighbour's (hydrogenation) XDI, (hydrogenation) XDI, to (hydrogenation) XDI to), methylene-bis (cyclohexyl isocyanate), hexanaphthene-1; 3-dimethylene diisocyanate, hexanaphthene-1, ester ring type vulcabond such as 4-dimethylene diisocyanate.In the middle of these, the trimethyl hexamethylene diisocyanate in the hexamethylene diisocyanate in the preferred fat (cyclo) aliphatic diisocyanates, the side chain aliphatic diisocyanate.These compounds with the NCO that directly is not connected aromatic nucleus can use separately or mix more than 2 kinds and use.When using these diisocyanate cpds, can obtain low warpage properties excellent in curing thing.In addition, in the scope of not damaging effect of the present invention, can use aromatic diisocyanate.
Then; As the compound with 2 above alcoholic extract hydroxyl groups (b); Can use known various polyvalent alcohols at present; But be not limited to specific compound, can suitably use polycarbonate-based polyvalent alcohol, polyethers such as polycarbonate diol is that polyvalent alcohol, polyester are that polyvalent alcohol, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, polyhutadiene are that polyvalent alcohol, TR 301 are that polyvalent alcohol, hydrogenated butadiene polymer are that polyvalent alcohol, hydrogenated isoprene polyvalent alcohol, phosphorous glycol, dihydroxyphenyl propane are the alkylene oxide adducts glycol, have the compound of carboxyl and alcoholic extract hydroxyl group, the compound with phenolic hydroxyl group and alcoholic extract hydroxyl group, a phosphorus-containing polyol etc.As polycarbonate diol, can enumerate out following material: comprise from the repeating unit of straight chain shape aliphatic diol more than a kind or 2 kinds as the polycarbonate diol (b-1) of structural unit, comprise from the repeating unit of ester ring type glycol more than a kind or 2 kinds as the polycarbonate diol (b-2) of structural unit or comprise from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol polycarbonate diol (b-3) as structural unit.In addition, use compound (b-4) and use under the situation of compound (b-5) with phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups etc., can make molecular side chain have functional group's (phenolic hydroxyl group, carboxyl) with carboxyl and 2 above alcoholic extract hydroxyl groups.Use under the situation of phosphorus-containing polyol (b-6), can give flame retardant resistance the urethane resin.These compounds (b-1)～(b-6) can use separately or mix more than 2 kinds and use.
Can enumerate for example by 1 as the concrete example of the polycarbonate diol (b-1) of structural unit aforementioned comprising from the repeating unit of straight chain shape aliphatic diol more than a kind or 2 kinds; 6-pinakon deutero-polycarbonate diol, by 1,5-pentanediol and 1,6-pinakon deutero-polycarbonate diol, by 1; 4-butyleneglycol and 1; 6-pinakon deutero-polycarbonate diol, by the 3-methyl isophthalic acid, 5-pentanediol and 1,6-pinakon deutero-polycarbonate diol, by 1; 9-nonanediol and 2-methyl isophthalic acid, 8-ethohexadiol deutero-polycarbonate diol etc.
Aforementioned containing from the repeating unit of ester ring type glycol more than a kind or 2 kinds can enumerate for example by 1,4 cyclohexane dimethanol deutero-polycarbonate diol etc. as the concrete example of the polycarbonate diol (b-2) of structural unit.
Can enumerate for example by 1 as the concrete example of the polycarbonate diol (b-3) of structural unit aforementioned comprising from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol; 6-pinakon and 1,4 cyclohexane dimethanol deutero-polycarbonate diol etc.
Aforementioned concrete example with compound (b-4) of carboxyl and 2 above alcoholic extract hydroxyl groups can be enumerated dimethylol propionic acid, dimethylolpropionic acid etc.Through using these compounds, can easily in urethane resin, import carboxyl with carboxyl and 2 above alcoholic extract hydroxyl groups.
Aforementioned concrete example with compound (b-5) of phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups can be enumerated 6-hydroxy-5-methyl base-1,3-xylyl alcohol, 2,4-two (methylol)-6-cyclohexylphenol, 3,3 '-methylene-bis (2-hydroxy-5-methyl base-phenylcarbinol), 4; 4 '-(1-methyl ethylidene) two [2-methyl-6-methylolphenol], 4,4 '-[1,4-phenylene two (1-methyl ethylidene)] two [2-methyl-6-methylolphenol], 2-hydroxyl-5-fluoro-1,3-xylyl alcohol, 4; 4 '-methylene-bis (2-methyl-6-methylolphenol), 4,4 '-methylene-bis (2,5-dimethyl--3-methylolphenol), 4,4 '-cyclohexylidene two (2-methyl-6-methylolphenol), 4; 4 '-cyclohexylidene two (2-cyclohexyl-6-methylolphenol), 2, two [(2-hydroxyl-3-methylol-5-aminomethyl phenyl) the methyl]-4-methylphenols of 6-, 2-hydroxyl-5-ethyl-1,3-xylyl alcohol, 2-hydroxyl-4,5-dimethyl--1; 3-xylyl alcohol, 2-hydroxyl-5-(1-methyl-propyl)-1,3-xylyl alcohol, 4-(1, the 1-dimethyl ethyl)-2-hydroxyl-1,3-xylyl alcohol, 2-hydroxyl-5-cyclohexyl-1; 3-xylyl alcohol, 2-hydroxyl-5-(1,1,3, the 3-tetramethyl butyl)-1; 3-xylyl alcohol, 2, two [(4-hydroxyl-3-methylol-2, the 5-3,5-dimethylphenyl) methyl]-3 of 6-, 4-xylenol, 2; Two [(4-hydroxyl-3-methylol-2,5-3,5-dimethylphenyl) the methyl]-4-cyclohexylphenol of 6-, 2-hydroxyl-1,3,5-benzene three methyl alcohol, 3; 5-dimethyl--2,4,6-tri hydroxy methyl phenol, 4,4 '; 4 "-loefiant gas three (2-methyl-6-methylolphenol), 2,3,5,6-four (methylol)-1; 4-Benzenediol, 4,4 '-methylene-bis [2, two (methylol) phenol of 6-] etc.Through using these compounds, can easily in urethane resin, import phenolic hydroxyl group with phenolic hydroxyl group and alcoholic extract hydroxyl group.
The aforementioned trend that has low warpage properties, flexible excellence from the repeating unit of straight chain shape aliphatic diol as the polycarbonate diol of structural unit that contains.In addition, contain the trend that has anti-zinc-plated property, solder heat resistance property excellence from the repeating unit of ester ring type glycol as the polycarbonate diol of structural unit.From above viewpoint, these polycarbonate diols can make up 2 kinds with on use, or use and to contain from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol polycarbonate diol as structural unit.In order to show the balance of low warpage properties, flexible and solder heat resistance property, anti-zinc-plated property better, the copolymerization ratio of preferably using straight chain shape aliphatic diol and ester ring type glycol is the polycarbonate diol of 3:7～7:3 by quality ratio.
Aforementioned polycarbonate diol preferred number average molecular weight is 200～5000; But polycarbonate diol contains from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol as the copolymerization ratio of structural unit, straight chain shape aliphatic diol and ester ring type glycol by quality ratio under the situation of 3:7～7:3, and preferred number average molecular weight is 400～2000.
Aforementioned dihydroxyphenyl propane is the alkylene oxide adducts ethylene oxide adduct that can enumerate dihydroxyphenyl propane, propylene oxide adduct, butylene oxide ring affixture etc., propylene oxide adducts of preferred dihydroxyphenyl propanes in the middle of these.
The concrete example of aforementioned phosphorus-containing polyol can be enumerated out FC-450 (rising sun electrochemical industry (strain) system), M-Ester (three light (strain) system), M-Ester-HP (three light (strain) system) etc.Through using this phosphorus-containing polyol, can in urethane resin, import phosphorus compound, can give flame retardant resistance.
Then; As the compound with 1 alcoholic extract hydroxyl group (c); Can use known various monohydroxy compounds at present; Be not limited to specific compound; If any the caprolactone of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol, octanol, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, cyclohexanedimethanol list (methyl) propenoate, aforementioned each (methyl) propenoate or alkylidene oxide affixture, two (methyl) vinylformic acid glyceryl ester, two (methyl) vinylformic acid trishydroxymethyl ester, three (methyl) vinylformic acid pentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, three (methyl) vinylformic acid, two trihydroxymethylpropanyl esters, allyl alcohol, allyloxyethanol, oxyacetic acid, NSC 115936 etc., but be not limited to these.
Has the compound (c) that has 1 alcoholic extract hydroxyl group in aforementioned 1 molecule of phenolic hydroxyl group; Use in order in urethane, to import phenolic hydroxyl group; It also brings into play the effect of the end-capped agent of urethane; Particularly, so long as have the effect that just can bring into play reaction terminating agent with the compound of 1 alcoholic extract hydroxyl group of isocyanate reaction and phenolic hydroxyl group in the molecule.Concrete example as such compound (c); For example can enumerate out methylolphenol, methylol cresols, methylol-DI-tert-butylphenol compounds, p-hydroxybenzene-2-methyl alcohol, p-hydroxybenzene-3-propyl alcohol, p-hydroxybenzene-4-butanols, hydroxyethyl cresols, 2; 6-dimethyl--4-methylolphenol, 2,4-dimethyl--6-methylolphenol, 2,3; 6-trimethylammonium-4-methylolphenol, 2-cyclohexyl-4-methylol-5-methylphenol, 4-methyl-6-methylol benzene-1; 2-glycol, 4-(1, the 1-dimethyl ethyl)-6-methylol benzene-1, hydroxyalkyl phenol or hydroxyalkyl cresols such as 2-glycol; Has the carboxylate that the phenol that contains carboxyl substituent and terepthaloyl moietie, Ucar 35, Diethylene Glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc. form by Para Hydroxy Benzoic Acid, hydroxy phenyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. or hydroxyphenoxy TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. etc.; The monocycle oxidative ethane affixture of bis-phenol, the monocycle Ethylene Oxide affixture of bis-phenol, p-hydroxyphenylethanol etc., but be not limited to these.These compounds (c) can use separately or use mixing more than 2 kinds.
The aforementioned weight-average molecular weight that contains carboxyl urethane resin (A) is preferably 500～100000, further is preferably 8000～50000.At this, weight-average molecular weight is the value in PS with gel permeation chromatography.When containing the weight-average molecular weight less than 500 of carboxyl urethane resin (A), can damage the stretchiness of cured film, flexible and intensity, on the other hand; Above 100000 o'clock; Solvability to solvent reduces, even dissolving viscosity is also too high, so the use aspect receives restriction greatly.
The aforementioned acid number that contains carboxyl urethane resin (A) is preferably the scope of 10～120mgKOH/g, further is preferably 20～80mgKOH/g.During acid number deficiency 10mgKOH/g, the reactivity reduction with the thermoset composition can damage thermotolerance.On the other hand, when acid number surpasses 120mgKOH/g, can reduce the characteristics against corrosion such as alkali resistance, electrical characteristic of cured film.Moreover the acid number of resin is the value that records according to JIS K5407.
In the compositions of thermosetting resin of the present invention; As containing the heat-curable compounds (B) that carboxyl urethane resin (A) cooperates with aforementioned; Can suitably use have in 1 molecule more than 2 can with epoxy resin, the oxetane compound of the epoxy group(ing) of the aforementioned carboxyl that contains carboxyl urethane resin (A) (or also and phenolic hydroxyl group) reaction, oxetanyl etc., special preferred epoxy.
As the concrete example of epoxy resin, for example: can enumerate out bisphenol A type epoxy resin, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-toluene phenol-type epoxy resin, united phenol-type epoxy resin etc. by epoxy resin as 2 officials; Can enumerate out phenolic resin varnish type epoxy resin as polyfunctional epoxy resin; Phenol novolak type epoxy resin; The cresols phenolic resin varnish type epoxy resin; N-Racemic glycidol type epoxy resin; The phenolic resin varnish type epoxy resin of dihydroxyphenyl propane; Di-toluene phenol-type epoxy resin; The xenol phenolic resin varnish type epoxy resin; Chelating type epoxy resin; Oxalic dialdehyde type epoxy resin; Contain aminoepoxy resin; Rubber modified epoxy resin; The Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin; The 2-glycidyl phthalide resin; The heterocyclic ring epoxy resins; Four glycidyl group xylyl ethane (tetraglycidyl xylenoyl ethane) resin; The silicone modified epoxy; 6-caprolactone modified epoxy etc.Further; Epoxy resin as the cured article of the high Tg that preferably is easy to get; Can enumerate out N-Racemic glycidol type epoxy resin, di-toluene phenol-type epoxy resin, bisphenol-type epoxy resin, four glycidyl group xylyl ethane resin, four phenol ethane type epoxy resin, Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin, contain naphthalene framework ring epoxy resins etc.; Specifically; Like the ESN-175 (Dongdu changes into (strain) system) of the GTR-1800 (Japanese chemical drug (strain) system) of four phenol ethane type epoxy resin, the HP-7200H of Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin (big Japanese ink chemical industry (strain) system), HP-4032D, EXA-7240, EXA-4700, EXA-4770 (big Japanese ink chemical industry (strain) system), naphthols aralkyl-type epoxy resin, EXA-7335 (big Japanese ink chemical industry (strain) system), the NC-3000 (Japanese chemical drug (strain) system) of xenol phenolic resin varnish with epoxy resin of cluck ton skeleton with epoxy resin of naphthalene skeleton; Through using these polyfunctional epoxy resins, other 3 official ability and 4 officials ability epoxy resin etc., can improve characteristics such as solder heat resistance property.
In addition, in order to give flame retardant resistance, can use in its structure, to import has halogen, the equiatomic epoxy resin of phosphorus such as chlorine, bromine.
In compositions of thermosetting resin of the present invention, aforementioned heat-curable compounds (B) can use separately or use with the form of mixtures more than 2 kinds.With respect to the aforementioned carboxyl urethane resin (A) that contains of 100 mass parts, its use level is 5～150 mass parts, is preferably the ratio of 10～80 mass parts.During less than 5 mass parts; The inadequate situation of solder heat resistance property that has the cured film of compositions of thermosetting resin; On the other hand, when surpassing 150 mass parts, all characteristics when existing insulating protective film as flexibility printed circuit substrate (FPC) to use, be the tendency of electrical insulating property deterioration by it.
The curing catalyst (C) that the present invention uses be for can promoting the material of thermofixation reaction, uses in order further to improve characteristic such as adaptation, chemical proofing, thermotolerance.As the concrete example of such curing catalyst, can enumerate out imidazoles and verivate thereof (for example four countries change into industry (strain) system, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ etc.); Guanamines such as acetoguanamine, benzoguanamine class; Polyamines classes such as diaminodiphenyl-methane, m-phenylenediamine, m-xylene diamine, diamino diphenyl sulfone, Dyhard RU 100, urea, urea derivative, melamine, polynary hydrazides; These organic acid salt and/or epoxy adduct; The amine complex of boron trifluoride; Ethyl diamino--s-triazine, 2,4-diamino--s-triazine, 2,4-diamino--pyrrolotriazine derivatives classes such as 6-xylyl-s-triazine; Trimethylamine, trolamine, N, N-dimethyl-octylame, N-benzyl dimethyl amine, pyridine, N-methylmorpholine, six (N-methyl) melamine, 2,4, amines such as 6-three (dimethylamino phenol), tetramethyl guanidine, Metha Amino Phenon; Polyvinylphenol, gather Polyphenols such as ethylene bromide base phenol, phenolic varnish, alkyl phenolic varnish; Organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyano ethyl phosphine; Three normal-butyls (2, phosphonium salt classes such as 5-dihydroxy phenyl) phosphonium bromide, phosphonium hexadecanyl-3-butyl chloride; Quaternary ammonium salts such as phenmethyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride; Aforementioned multi-anhydride; Phenylbenzene iodine a tetrafluoro borate, triphenylsulfonium hexafluoro antimonate, 2; 4, the light cationic polymerisation catalysts such as OPTOMER SP-170 of the Irgacure261 of 6-triphenyl thiapyran inner salt (Thiopyrylium) hexafluorophosphate, Ciba Geigy corporate system, rising sun electrification (strain) system; The phenylethylene-maleic anhydride resin; The known curing catalyst commonly used or the solidifying agent classes such as reaction with same mole thing of organic multiple isocyanates such as the reaction with same mole thing of phenyl isocyanate and dimethyl amine, tolylene diisocyanate, isophorone diisocyanate and dimethyl amine.
These curing catalysts (C) can use separately or mix more than 2 kinds and use.Curing catalyst (C) and nonessential use are wanted to promote can preferably in the scope of 0.1～25 mass parts, use with respect to the aforementioned heat-curable compounds of 100 mass parts (B) under the solidified situation especially.Surpass 25 mass parts, the sublimability composition of its cured article increases, so not preferred.
Compositions of thermosetting resin of the present invention can contain carboxyl urethane resin (A), heat-curable compounds (B) and curing catalyst as required (C) for example dispersion mill (dispersion mill), kneader, three roller roller mills, ball mill etc. dissolve or disperse and make with mixing machine aforementioned.At this moment, can use epoxy group(ing), phenolic hydroxyl group are the inert solvent.The preferred organic solvent of such inert solvent.
Organic solvent dissolves easily or disperses or use in order to be adjusted to the viscosity that is suitable for being coated with in order to make aforementioned carboxyl urethane resin (A), the heat-curable compounds (B) of containing.Organic solvent can be enumerated for example toluene, YLENE, ethylbenzene, oil of mirbane, hexanaphthene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, Trivalin SF acetic ester, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic ester, dipropylene glycol methyl ether acetate, diethylene glycol ether acetic ester, methoxypropionic acid methyl esters, methoxy propyl acetoacetic ester, ethoxy-propionic acid methyl esters, ethoxyl ethyl propionate, vinyl acetic monomer, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methylethylketone, pimelinketone, N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, gamma-butyrolactone, DMSO 99.8MIN., chloroform and methylene dichloride etc.The use level of organic solvent can suitably be set according to the viscosity of expecting.
In order to improve the adaptation with base materials such as polyimide, in case of necessity, can also contain known sulfhydryl compound commonly used in the compositions of thermosetting resin of the present invention.Sulfhydryl compound can be enumerated 2 mercaptopropionic acid, trimethylolpropane tris (2-sulfo-propyl ester), 2 mercapto ethanol, 2-aminothiophenol, 3-sulfydryl-1,2, and 4-triazole, 3-sulfydryl-propyl trimethoxy silicane etc. contains mercaptosilane coupling agents etc.These both can use separately separately also can make up more than 2 kinds and use.It is the scope below 10 mass parts that its use level is suitably for the aforementioned carboxyl urethane resin (A) that contains of per 100 mass parts.The use level of sulfhydryl compound exceeds under the situation of above-mentioned scope, the epoxy group(ing) (with epoxy reaction) that consumes the necessary aforementioned epoxy resins of crosslinking reaction, cross-linking density is descended, so not preferred.
In order to improve characteristics such as adaptation, hardness, thermotolerance, in case of necessity, can also contain at least a filler that is selected from the group of forming by inorganic and organic filler in the compositions of thermosetting resin of the present invention.Mineral filler can be enumerated out permanent white, lime carbonate, barium titanate, silicon-dioxide, soft silica, talcum, clay, mica powder etc., and organic filler can be enumerated out silica flour, nylon powder, fluorine powder (Fluorine Powder) etc.In the above-mentioned filler, what agent of low hygroscopicity, low volumetric expansion property were excellent especially is silicon-dioxide.Though silicon-dioxide its dissolve, crystallinity, even these mixture is also no problem, but carried out under the situation of surface-treated silicon-dioxide through coupling agent etc., can improve electrical insulating property, so preferred especially.The median size of filler is preferably below the 25 μ m, more preferably below the 10 μ m, further below the preferred 3 μ m.It is below 300 mass parts that the use level of these mineral fillers and/or organic filler is suitably for the aforementioned carboxyl urethane resin (A) that contains of per 100 mass parts, the ratio of preferred 5～150 mass parts.The use level of filler surpasses aforementioned proportion, and the folding resistance of curing overlay film will reduce and not preferred.
Further, in the compositions of thermosetting resin of the present invention, only otherwise damage effect of the present invention, can also add other additive, tinting material beyond the aforementioned composition.Additive can be enumerated thickening materials such as asbestos, ORBEN, wilkinite, and silicone-based, fluorine are skimmer, flow agent, fiber-reinforced materials such as spun glass, charcoal fiber, boron nitride fibre etc.; Tinting material can enumerate that phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, titanium oxide, carbon black etc.Further, can add known hot stopper commonly used, UV light absorber, silane coupling agent, softening agent, whipping agent, fire retardant, static inhibitor, anti-aging agent, antibacterial mildew inhibitor etc. as required.
Compositions of thermosetting resin with above such composition can also be used for various forms, purposes such as dry film or prepreg except being coated with existing known the whole bag of tricks such as method, rolling method, spraying method and dip coating is applied on the PC board through curtain.Can use all kinds of SOLVENTS according to its method of use, purposes, but according to circumstances not only can use good solvent but also can use poor solvent.
In addition; Compositions of thermosetting resin of the present invention is applied to the flexibility printed circuit board, the band that are formed with circuit through silk screen print method and carries on encapsulation or the electroluminescence panel; The temperature that for example is heated to 120～180 ℃ to be to carry out thermofixation, can form no cure shrinkage and cooling thus and shrink excellent solder resist film, protective membranes such as the warpage that caused, the gold-plated property of adaptation, folding resistance, low warpage properties, chemically-resistant with base material, solder heat resistance property, electrical insulating property.
Embodiment
Embodiment and comparative example below are shown, come to explain particularly the present invention, but the present invention is not limited to following embodiment.In addition, following " part " and " % " is quality criteria when not specifying.
Synthetic example 1
In the reaction vessel that is equipped with whipping appts, TM, condensing surface; Drop into 360g (0.45mol) as the compound with 2 above alcoholic extract hydroxyl groups by 1; 5-pentanediol and 1, the polycarbonate diol that the 6-pinakon derives (Asahi Chemical Corp's system, number-average molecular weight 800), 81.4g (0.55mol) dimethylolpropionic acid and 11.8g (0.16mol) are as the propyl carbinol of molecular weight adjustment agent (reaction terminating agent).Then; Drop into 151.2g (1.08mol) as hexamethylene diisocyanate with compound of the NCO that directly is not connected aromatic nucleus; Be heated to 60 ℃ while stirring, stop, the moment that the temperature in reaction vessel begins to reduce heats once more; Continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of NCO with infrared spectrum
-1) disappear termination reaction.Then, adding Trivalin SF acetic ester to solids component is 50wt%, obtain to contain thinner thick liquid contain carboxyl urethane resin (varnish A).The acid number of the solids component that contains the carboxyl urethane resin that obtains is 51.0mgKOH/g.
Synthetic example 2
In the reaction vessel of being furnished with whipping appts, TM, condensing surface; Drop into 360g (0.45mol) as the compound with 2 above alcoholic extract hydroxyl groups by 1; 5-pentanediol and 1, the polycarbonate diol that the 6-pinakon derives (Asahi Chemical Corp's system, number-average molecular weight 800), 81.4g (0.55mol) dimethylolpropionic acid and 11.8g (0.16mol) are as the propyl carbinol of molecular weight adjustment agent (reaction terminating agent).Then; Drop into 200.9g (1.08mol) as trimethyl hexamethylene diisocyanate with compound of the NCO that directly is not connected aromatic nucleus; Be heated to 60 ℃ while stirring, stop, the moment that the temperature in reaction vessel begins to reduce heats once more; Continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of NCO with infrared spectrum
-1) disappear termination reaction.Then, adding Trivalin SF acetic ester to solids component is 50wt%, obtain to contain thinner thick liquid contain carboxyl urethane resin (varnish B).The acid number of the solids component that contains the carboxyl urethane resin that obtains is 49.8mgKOH/g.
Synthetic example 3
In the reaction vessel of being furnished with whipping appts, TM, condensing surface; Drop into 360g (0.45mol) as the compound with 2 above alcoholic extract hydroxyl groups by 1; 5-pentanediol and 1, the polycarbonate diol that the 6-pinakon derives (Asahi Chemical Corp's system, number-average molecular weight 800), 81.4g (0.55mol) dimethylolpropionic acid and 22.1g (0.16mol) are as the hydroxy phenyl ethanol of the compound that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule.Then; Drop into 200.9g (1.08mol) as trimethyl hexamethylene diisocyanate with compound of the NCO that directly is not connected aromatic nucleus; Be heated to 60 ℃ while stirring, stop, the moment that the temperature in reaction vessel begins to reduce heats once more; Continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of NCO with infrared spectrum
-1) disappear termination reaction.Then, adding Trivalin SF acetic ester to solids component is 50wt%, and what the end that obtains to contain the thick liquid of thinner had a phenolic hydroxyl group contains carboxyl urethane resin (varnish C).The acid number that the end that obtains has the solids component that contains the carboxyl urethane resin of phenolic hydroxyl group is 48.8mgKOH/g.
Relatively more synthetic example 1
In the reaction vessel of being furnished with whipping appts, TM, condensing surface; Drop into 360g (0.45mol) as the compound with 2 above alcoholic extract hydroxyl groups by 1; 5-pentanediol and 1, the polycarbonate diol that the 6-pinakon derives (Asahi Chemical Corp's system, number-average molecular weight 800), 81.4g (0.55mol) dimethylolpropionic acid and 11.8g (0.16mol) are as the propyl carbinol of molecular weight adjustment agent (reaction terminating agent).Then; Drop into the tolylene diisocyanate of 187.9g (1.08mol) as aromatic isocyanate; Be heated to 60 ℃ while stirring, stop, the moment that the temperature in reaction vessel begins to reduce heats once more; Continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of NCO with infrared spectrum
-1) disappear termination reaction.Then, adding Trivalin SF acetic ester to solids component is 50wt%, obtain to contain thinner thick liquid contain carboxyl urethane resin (varnish D).The acid number of the solids component that contains the carboxyl urethane resin that obtains is 49.5mgKOH/g.
Embodiment 1～8 and comparative example 1,2
With each composition shown in the table 1 and cooperation ratio, at room temperature go out compositions of thermosetting resin with three roller roller mill mixed preparing.The compositions of thermosetting resin that obtains is coated on the substrate with silk screen printing and makes under 150 ℃, carry out 60 minutes thermofixation by the about 20 μ m of thickness.
Table 1
About the cured film of aforementioned each compositions of thermosetting resin, following various characteristics is estimated as follows.Its result is as shown in table 2.
(1) adaptation
Respectively the whole face of each compositions of thermosetting resin of the foregoing description 1～8 and comparative example 1,2 is printed onto kapton100EN (DUP ONT-TORAYCO. with silk screen printing; LTD. make polyimide film, thickness 25 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).Have or not through resist layer in the stripping test of using cellophane tape and to peel off the adaptation of confirming its cured film, estimate with following benchmark.
Zero: all do not peel off
△: have a little to peel off
*: peel off
(2) folding resistance
Use silk screen printing; The whole face of each compositions of thermosetting resin with the foregoing description 1～8 and comparative example 1,2 is printed onto kapton100EN (DUPONT-TORAY CO. respectively; LTD. make polyimide film, thickness 25 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).The cured film that obtains is bent 180 °, and estimate with following benchmark.
Zero: cured film does not have crackle
△: cured film has a little crackle
*: cured film has crackle
(3) low warpage properties
Use silk screen printing; The whole face of each compositions of thermosetting resin with the foregoing description 1～8 and comparative example 1,2 is printed onto kapton100EN (DUPONT-TORAY CO. respectively; LTD. make polyimide film, thickness 25 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).After the cooling, the cured film that obtains is cut into 50 * 50mm, measures 4 jiaos warpage and try to achieve MV, estimate with following benchmark.
◎: the not enough 1mm of warpage
Zero: warpage is more than the 1mm, below the 4mm
△: warpage is more than the 4mm, below the 7mm
*: warpage is more than 7mm
(4) the gold-plated property of chemically-resistant
Each compositions of thermosetting resin pattern with the foregoing description 1～8 and comparative example 1,2 is printed onto on the PC board (thickness 1.6mm) respectively, under 150 ℃, carries out thermofixation in 60 minutes and obtains test film (dry film thickness 15 μ m).Use the test film that obtains, the operation of stating after using is carried out chemical gilding, with the gold-plated property of following benchmark evaluation chemically-resistant.
Zero: cured film does not expand, peels off, variable color
△: cured film has a little expansion, peels off, variable color
*: cured film has expansion, peels off, variable color
The chemical gilding operation:
1. degreasing: test film was flooded 3 minutes in 30 ℃ acid degreasing fluid (Nippon MacDermid Co., Inc., the 20vol% aqueous solution of Ltd. system, Metex L-5B).
2. washing: test film was flooded in flowing water 3 minutes.
3. soft etching: at room temperature test film was flooded 1 minute in the ammonium persulfate aqueous solution of 14.3wt%.
4. washing: test film was flooded in flowing water 3 minutes.
5. acid dipping: at room temperature test film was flooded 1 minute in the aqueous sulfuric acid of 10vol%.
6. washing: test film was flooded in flowing water 30 seconds～1 minute.
7. catalyzer is given: test film was flooded 3 minutes in 30 ℃ catalyzer liquid (the 10vol% aqueous solution of Meltex Inc. system, Melplate Activator350).
8. washing: test film was flooded in flowing water 3 minutes.
9. chemical nickel plating: with test film dipping 30 minutes in 85 ℃, the nickel plating bath (MeltexInc. system, Melplate Ni-865M, the 20vol% aqueous solution) of pH=4.6.
10. acid dipping: at room temperature, test film was flooded 1 minute in the aqueous sulfuric acid of 10vol%.
11. washing: test film was flooded in flowing water 30 seconds～1 minute.
12. chemical gilding: with test film dipping 30 minutes in 85 ℃, the golden plating bath (MeltexInc. system, Aurolectroless UP15vol%, the potassium auric cyanide 3wt% aqueous solution) of pH=6.
13. washing: test film was flooded in flowing water 3 minutes.
14. Warm Wash: test film is immersed in 60 ℃ the warm water, fully wash 3 minutes after, finish-drying removes water.
(5) solder heat resistance property
Each compositions of thermosetting resin pattern with the foregoing description 1～8 and comparative example 1,2 is printed onto on the PC board (thickness 1.6mm) respectively, carries out thermofixation in 60 minutes (dry film thickness 15 μ m) at 150 ℃.Coating rosin series solder flux (flux) on the cured film that obtains, and being immersed in 260 ℃ the solder bath, remove deflux, drying after, be with stripping test, with the state of following benchmark evaluation cured film.
Zero: peel off even flood also not have for 10 seconds
△: peel off for 10 seconds but flood not have for 5 seconds and peel off
*: after flooding for 5 seconds, cured film is peeled off
(6) electrical insulating property
Respectively each compositions of thermosetting resin of the foregoing description 1～8 and comparative example 1,2 is coated on polyimide substrate (the DUPONT-TORAY CO. of L/S (line/at interval)=20/20 μ m; LTD. make kaptonEN, ESPANEX) go up to make and film, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).The electrical insulating property of the cured film that obtains with following benchmark evaluation.
Humidified condition: 120 ℃ of temperature, humidity 85%RH, apply voltage 60V, 100 hours.
Test conditions: measure under minute 60 seconds, auxiliary voltage 60V, the room temperature.
◎: the insulating resistance value 10 behind the humidification
12The migration that Ω is above, do not have copper
Zero: the insulating resistance value less than 10 behind the humidification
12Ω, 10
9More than the Ω, there is not the migration of copper
△: the insulating resistance value 10 behind the humidification
9The migration that Ω is above, have copper
*: the insulating resistance value 10 behind the humidification
8Below the Ω, the migration of copper arranged
Table 2
Result by shown in the above-mentioned table 2 can know: the cured film that is formed by compositions of thermosetting resin of the present invention and the gold-plated property of adaptation, folding resistance, low warpage properties, chemically-resistant of base material, solder heat resistance property are excellent.In addition, insulating reliability also is good result.Especially; Under embodiment 2～4 that contains carboxyl urethane resin (varnish B and C) that application use side chain aliphatic isocyanates compound obtains and 6～8 the situation; Low warpage properties is excellent especially; In addition, use under the situation of the terminal embodiment 3,7,8 that contains carboxyl urethane resin (varnish C) with phenolic hydroxyl group, electrical insulating property is also excellent.With respect to this, use to use aromatic isocyanate and under the situation of the comparative example 1,2 that contains carboxyl urethane resin (varnish D) that obtains, no problem with the gold-plated property of adaptation, folding resistance, the chemically-resistant of base material, electrical insulating property, but low warpage properties is poor.
Claims (7)
1. a compositions of thermosetting resin is characterized in that, what contain that (A) use that compound with the NCO that directly is not connected aromatic nucleus obtains contains carboxyl urethane resin and (B) heat-curable compounds,
The said carboxyl urethane resin (A) that contains contains the carboxyl urethane resin for what have in the compound that (a) had directly be not connected the NCO of aromatic nucleus, (b) 1 molecule that the compound reaction that has 1 alcoholic extract hydroxyl group in the compound of 2 above alcoholic extract hydroxyl groups and (c) 1 molecule obtains, and the compound (c) that has 1 alcoholic extract hydroxyl group in said 1 molecule has 1 above phenolic hydroxyl group.
2. compositions of thermosetting resin according to claim 1 is characterized in that, said to have the compound (a) that directly is not connected the NCO of aromatic nucleus be the aliphatic isocyanates compound.
3. compositions of thermosetting resin according to claim 1 is characterized in that, said to have the compound (a) that directly is not connected the NCO of aromatic nucleus be side chain aliphatic isocyanates compound.
4. compositions of thermosetting resin according to claim 1 is characterized in that, said heat-curable compounds (B) is an epoxy resin.
5. compositions of thermosetting resin according to claim 1, wherein, the use level of said heat-curable compounds (B) is the ratio of 5～150 mass parts with respect to the said carboxyl urethane resin (A) that contains of 100 mass parts.
6. cured article, it forms for each described compositions of thermosetting resin of said claim 1～5 solidified.
7. PC board, the part on its surface or all covered by the cured article of said each described compositions of thermosetting resin of claim 1～5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-251053 | 2007-09-27 | ||
| JP2007251053 | 2007-09-27 | ||
| JP2007251053A JP5043577B2 (en) | 2007-09-27 | 2007-09-27 | Thermosetting resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101397402A CN101397402A (en) | 2009-04-01 |
| CN101397402B true CN101397402B (en) | 2012-01-18 |
Family
ID=40516259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101683378A Active CN101397402B (en) | 2007-09-27 | 2008-09-26 | Thermosetting resin composite and cured resin |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5043577B2 (en) |
| KR (1) | KR100961823B1 (en) |
| CN (1) | CN101397402B (en) |
| TW (1) | TWI381004B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120305295A1 (en) * | 2010-02-03 | 2012-12-06 | Showa Denko K.K. | Thermosetting composition |
| CN103459504B (en) * | 2011-04-13 | 2015-12-09 | 太阳油墨制造株式会社 | Curable resin composition, its cured article and use their printed circuit board (PCB) |
| TWI534256B (en) * | 2011-05-16 | 2016-05-21 | Showa Denko Kk | Hardened heat dissipation composition |
| CN102586765B (en) * | 2012-03-20 | 2014-09-10 | 深圳市景旺电子股份有限公司 | Method for chemical nickel-plating and gold immersion on FPC (Flexible Printed Circuit) |
| CN104031231A (en) * | 2014-06-19 | 2014-09-10 | 合肥工业大学 | Ultraviolet-curing waterborne epoxy-polyurethane-acrylate copolymer resin anticorrosive coating and preparation method thereof |
| CN104592714A (en) * | 2015-01-13 | 2015-05-06 | 潮州三环（集团）股份有限公司 | Molding compound composition and preparation method thereof |
| CN105440911B (en) * | 2015-12-18 | 2018-11-16 | 江苏兰陵高分子材料有限公司 | A kind of polymer composite of crosslinked at low temperature and preparation method thereof for MDF plate |
| JP6948196B2 (en) * | 2017-09-14 | 2021-10-13 | 株式会社クラレ | Polyurethane, polyurethane moldings for polishing layers and polishing pads |
| CN112898926B (en) * | 2021-01-21 | 2022-12-02 | 西安航天三沃化学有限公司 | Epoxy resin glue solution and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023112A (en) * | 2004-09-21 | 2007-08-22 | 昭和电工株式会社 | Heat-curable urethane resin composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4423513B2 (en) * | 1997-10-20 | 2010-03-03 | 東洋紡績株式会社 | Adhesive resin composition and adhesive film |
| AU769763B2 (en) * | 1999-09-30 | 2004-02-05 | Basf Aktiengesellschaft | Aqueous polyurethane dispersions which can be hardened with mit UV-radiation and thermally, and use thereof |
| JP5190976B2 (en) * | 2004-09-21 | 2013-04-24 | 昭和電工株式会社 | Thermosetting resin composition using urethane resin |
| JP5174325B2 (en) | 2005-03-15 | 2013-04-03 | 昭和電工株式会社 | (Meth) acryloyl group-containing aromatic isocyanate compound and method for producing the same |
| KR100984605B1 (en) * | 2006-02-27 | 2010-09-30 | 쇼와 덴코 가부시키가이샤 | Thermosetting resin composition containing low-chlorine multifunctional aliphatic glycidyl ether compound, cured product of such composition and use thereof |
-
2007
- 2007-09-27 JP JP2007251053A patent/JP5043577B2/en active Active
-
2008
- 2008-09-26 CN CN2008101683378A patent/CN101397402B/en active Active
- 2008-09-26 KR KR1020080094680A patent/KR100961823B1/en active IP Right Grant
- 2008-09-26 TW TW097137258A patent/TWI381004B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023112A (en) * | 2004-09-21 | 2007-08-22 | 昭和电工株式会社 | Heat-curable urethane resin composition |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平5－75032A 1993.03.26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5043577B2 (en) | 2012-10-10 |
| TW200932777A (en) | 2009-08-01 |
| TWI381004B (en) | 2013-01-01 |
| CN101397402A (en) | 2009-04-01 |
| KR100961823B1 (en) | 2010-06-08 |
| KR20090033108A (en) | 2009-04-01 |
| JP2009079179A (en) | 2009-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101397402B (en) | Thermosetting resin composite and cured resin | |
| CN101343345B (en) | Polyurethane resin, heat solidifying resin composition containing the same and its solidifying article | |
| CN101023112B (en) | Heat-curable urethane resin composition | |
| US8575280B2 (en) | Thermosetting resin composition, thermosetting resin composition solution, film forming material and their cured product | |
| CN101213231B (en) | Carboxyl group-containing polyurethane and uses thereof | |
| CN101400716B (en) | Heat curable resin composition, overcoating agent for flexible circuit board, and surface protective film | |
| TWI495662B (en) | Thermosetting composition for protective film of wiring board | |
| CN101133096A (en) | Carboxyl group-containing polyurethane and thermosetting resin composition using the same | |
| TW200804510A (en) | Resin composition | |
| TWI541281B (en) | A thermosetting resin composition, a hardened product thereof, and a printed circuit board using the same | |
| JP5164090B2 (en) | Thermosetting resin composition containing carboxylic group-containing urethane resin and cured product thereof | |
| JP5130795B2 (en) | Thermosetting polyimide resin composition | |
| JP5398754B2 (en) | Urethane resin, thermosetting resin composition containing the same, and cured product thereof | |
| JP5303860B2 (en) | Thermosetting polyimide resin composition | |
| TW201035172A (en) | Polyimide resin, method for producing the same, polyimide resin composition and cured product | |
| KR101184552B1 (en) | Urethane oligomer, thermosetting resin composition containing the same and cured product thereof | |
| CN100512605C (en) | Thermosetting resin composition for multilayer printed wiring board, thermosetting adhesive film and printed circuit substrate | |
| CN107003609A (en) | Photosensitive development for flexible printed circuit board covers film composition | |
| JP5701949B2 (en) | Thermosetting resin composition, cured product thereof and printed wiring board using the same | |
| JP2023036726A (en) | Carboxyl Group-Containing Polyester Resin, Carboxyl Group-Containing Ester Urethane Resin, Resin Composition, and Adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20090401 Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Thermosetting resin composition and cured product thereof Granted publication date: 20120118 License type: Common License Record date: 20110302 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |