CN104892905A - Thermosetting resin composition,condensate and manufactur method for modified urushiol resin - Google Patents
Thermosetting resin composition,condensate and manufactur method for modified urushiol resin Download PDFInfo
- Publication number
- CN104892905A CN104892905A CN201510067709.8A CN201510067709A CN104892905A CN 104892905 A CN104892905 A CN 104892905A CN 201510067709 A CN201510067709 A CN 201510067709A CN 104892905 A CN104892905 A CN 104892905A
- Authority
- CN
- China
- Prior art keywords
- resin
- compositions
- thermosetting resin
- modified phenolic
- phenolic resin
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The invention discloses a Thermosetting resin composition,condensate and manufactur method for modified urushiol resinSubject of the present invention is to provide available when curing thermosetting resins with high shrinkage of cured composite with excellent heat resistance and flame retardancy as well as with the curing. A thermosetting resin combination, its contains the general formula (I) is shown in (A) modified phenolic resin and epoxy resin (B), the modified phenolic resin (A) of the total content of alkali, alkaline earth metal relative to the amount of phenolic resin (A) above 0.1 mass % the following, and the modified phenolic resin (A) the amine series compounds content relative to the amount of phenolic resin (A) above 0.1 mass %. (img file = 'DDA0000669439150000011. TIF wi =' 1536 'he =' 411 '/) (type, the R1 for hydrogen atoms or groups as shown in the following type (II), all R1, R1 for hydrogen atom is more than 20% and less than 80%. The proportion of the R2 and R3 independently of hydrogen or carbon atom number 1 ~ 20 aliphatic or aromatic hydrocarbon. An integer n is 0 ~ 40.) (img file = 'DDA0000669439150000012. TIF wi =' 1752 'he =' 373 '/) (type, R4 to hydrogen atoms or methyl.
Description
Technical field
The present invention relates to the manufacture method of compositions of thermosetting resin, cured article and modified phenolic resin.
Background technology
About the compositions of thermosetting resin being combined with epoxy resin and phenol resins (solidifying agent), due to the excellence such as thermotolerance, adaptation, electrical insulating property of the cured article of such compositions of thermosetting resin, be therefore used in various field.Such as, interlayer dielectic resin combination that printed base plate resin combination, printed base plate and the Copper Foil with resin use, the sealing material resin combination of electronic unit, resist ink, conductive paste, coating, caking agent, matrix material etc. containing conductive filler agent is used in.
Semi-conductor improves year by year with the mode integrated level following Moore's Law.And highly integrated corresponding due to semiconductor packages also with semi-conductor, therefore, except the encapsulation employing lead frame in the past, the single facer encapsulation such as the ball grid array (hereinafter referred to as BGA) connected by projection are developed, further by the three-dimension packaging of its lamination.On the other hand, encapsulating semiconductor material has also carried out the cooperation research of the compositions of thermosetting resin being suitable for various encapsulation, the improvement of forming method.The face of such as carrying out sealing in single facer encapsulation is only one side, and the warpage occurred due to substrate-side and the difference of the shrinking percentage of sealing material side time therefore shaping becomes problem, requires the compositions of thermosetting resin of this warpage of suppression.
For such requirement, have studied various solution.As one of this solution, such as, known following means.Compositions of thermosetting resin generally contains various weighting agent, the known method suppressing warpage by increasing weighting agent usage quantity.
In addition known, the method for cross-linking density is improved by the functional group number increasing the resinous principle in compositions of thermosetting resin.Such as, have studied and there is the epoxy resin of triphenylmethane structure or phenol resins by using or use the epoxy resin with four phenol ethane structures or phenol resins to suppress the method for warpage.
As the document that such means are shown, such as, the warpage by coordinating inorganic filler 85 ~ 95 % by weight to reduce encapsulation is described in patent documentation 1.
In addition, such as, describe in patent documentation 2, after shaping by the sealing material low with second-order transition temperature, be coated to by the sealing material that second-order transition temperature is high and suppress warpage.
On the other hand; describe in patent documentation 3; by make to have coordinated in molecule in (methyl) polyacryl novolac resin have the compound of more than 2 epoxy group(ing), the curable resin composition of aliphatic tertiary amine more than 50 DEG C less than 100 DEG C carry out mixing and carry out thickening; the feature of described (methyl) polyacryl novolac resin is; by making the phenolic hydroxyl group of novolac resin and carrying out reacting obtaining relative to (methyl) glycidyl acrylate that this phenolic hydroxyl group is below equivalent, and in molecule, there is phenolic hydroxyl group.
In addition, describe except the miniaturization except single facer type encapsulates, slimming in patent documentation 4, the proprietary area of semi-conductor chip increases, thus improves for the demand of the problem of the convexity warp solved under opposite normal temperature.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-1541 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-112515 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2000-198832 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2012-72209 publication
Summary of the invention
Invent problem to be solved
In order to reduce warpage, have the shrinking percentage during solidification making compositions of thermosetting resin as far as possible little, or the rigidity improving compositions of thermosetting resin resist the method for warpage etc. itself.
Under these circumstances, as shown in patent documentation 1 and 2, have studied and increase the use level of inorganic filler to improve Young's modulus, or in order to make the cured article of compositions of thermosetting resin until as far as possible high temperature all improves the method for the second-order transition temperature of cured article in the state of the little glassy zone of linear expansivity.
But method such shown in patent documentation 1 and 2, the warpage for the recessed direction of chip mounting face is effective, but has the opposite effect for the warpage of the convex direction occurred in thin encapsulation.Namely for the warpage of convex direction, in order to the warpage of offset substrate, the shrinking percentage increasing compositions of thermosetting resin is needed.
In addition, though described in patent documentation 3 by making the compositions of thermosetting resin of specific formation carry out thickening in specific range of temperatures mixing, for the warpage of convex direction, be still difficult to suppress the warpage of substrate.
The object of the present invention is to provide the compositions of thermosetting resin of the cured article that shrinking percentage when can obtain solidification is high, solidified and the manufacture method of the cured article obtained and modified phenolic resin.
For solving the method for problem
That is, the present invention is formed as follows.
(1) a kind of compositions of thermosetting resin, it is characterized in that, comprise the modified phenolic resin (A) shown in general formula (I) and epoxy resin (B), basic metal in above-mentioned modified phenolic resin (A), the total content of alkaline-earth metal are below 0.1 quality % relative to the total amount of above-mentioned phenol resins (A), further, the content of the amine compound in above-mentioned modified phenolic resin (A) is below 0.1 quality % relative to the total amount of above-mentioned phenol resins (A).
(in formula, R
1for the group shown in hydrogen atom or following formula (II), and whole R
1middle R
1for the ratio of hydrogen atom is more than 20% and is less than 80%.R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another.N represents the integer of 0 ~ 40.)
(in formula, R
4for hydrogen atom or methyl.)
(2) compositions of thermosetting resin Gen Ju (1), the total content of the basic metal in above-mentioned compositions of thermosetting resin, alkaline-earth metal is below 0.05 quality %, further, the content of the amine compound in above-mentioned compositions of thermosetting resin is below 0.05 quality %.
(3) according to (1) or the compositions of thermosetting resin described in (2), the weight-average molecular weight of above-mentioned modified phenolic resin (A) is 250 ~ 5000.
(4) according to the compositions of thermosetting resin described in any one of (1) ~ (3), relative to epoxy group(ing) 1.0 equivalent in above-mentioned epoxy resin (B), the hydroxyl of above-mentioned modified phenolic resin (A) is the scope of 0.6 equivalent ~ 1.2 equivalent.
(5) according to the compositions of thermosetting resin described in any one of (1) ~ (4), the weight-average molecular weight of above-mentioned epoxy resin (B) is 300 ~ 5000.
(6) according to the compositions of thermosetting resin described in any one of (1) ~ (5), weighting agent is comprised.
(7) cured article is obtained the compositions of thermosetting resin solidification described in any one of (1) ~ (6).
(8) cured article Gen Ju (7), shrinking percentage is 0.15% ~ 0.40%.
(9) a kind of manufacture method of modified phenolic resin, it is characterized in that, phenol resins and (methyl) glycidyl acrylate are reacted under the existence of organophosphorus based compound, obtains the modified phenolic resin (A) shown in general formula (I).
(in formula, R
1for the group shown in hydrogen atom or following formula (II), and whole R
1middle R
1for the ratio of hydrogen atom is more than 20% and is less than 80%.R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another.N represents the integer of 0 ~ 40.)
(in formula, R
4for hydrogen atom or methyl.)
The manufacture method of the modified phenolic resin (10) Gen Ju (9), the usage quantity of organophosphorus based compound is below more than 0.001 mass parts 10 mass parts relative to phenol resins 100 mass parts.
The effect of invention
According to the present invention, provide the manufacture method of the compositions of thermosetting resin of the cured article that shrinking percentage when can obtain solidification is high, cured article and compositions of thermosetting resin.
Embodiment
< compositions of thermosetting resin >
Compositions of thermosetting resin of the present invention comprises modified phenolic resin (A) and epoxy resin (B).
Compositions of thermosetting resin of the present invention, in the limit not damaging effect of the present invention, can also comprise weighting agent, Synergist S-421 95 etc.
Below, compositions of thermosetting resin of the present invention is explained.
In addition, " ~ " numerical range of illustrating is used to represent numerical value described in the front and back comprising " ~ " scope respectively as minimum value and maximum value in this specification sheets.
(modified phenolic resin (A))
Modified phenolic resin (A) is applicable to by making phenol resins and (methyl) glycidyl acrylate carry out reacting obtaining under the existence of organophosphorus based compound.
(phenol resins)
As phenol resins used in the present invention, be not particularly limited, phenols and aldehydes can be used to carry out in the presence of acidic reacting and the known novolak type phenol resin obtained.
As the concrete example of phenols, can enumerate such as, phenol, cresols, ethylphenol, xylenol, butylphenol, octyl phenol, nonylphenol, phenylphenol, cyclohexylphenol, pseudocuminol, dihydroxyphenyl propane, catechol, Resorcinol, quinhydrones, naphthols, pyrogallol etc., from the view point of the shrinking percentage of the thermosetting resin of gained, be preferably phenol, cresols, as cresols, be preferably ortho-cresol.
As the concrete example of aldehydes, can enumerate formaldehyde, acetaldehyde, paraformaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, phenyl aldehyde, hydroxy benzaldehyde, Dihydroxy benzaldehyde, hydroxymethylbenzaldehyde, oxalic dialdehyde, crotonic aldehyde, glutaraldehyde etc., from the view point of the shrinking percentage of the thermosetting resin of gained, be preferably formaldehyde, phenyl aldehyde.
As phenol resins, can use such as, phenol resol resins, as phenol resol resins, trade(brand)name " シ ョ ウ ノ ー Le BRG-558 " (phenol novolacs can be enumerated, Showa Denko K. K's system, hydroxyl equivalent 104g/eq., the trade mark that " シ ョ ウ ノ ー Le " is Showa Denko K. K), trade(brand)name " シ ョ ウ ノ ー Le CRG-951 " (o-cresol novolak, Showa Denko K. K's system, hydroxyl equivalent 118g/eq., the trade mark that " シ ョ ウ ノ ー Le " is Showa Denko K. K).
(manufacture method of modified phenolic resin (A))
The manufacture method of modified phenolic resin of the present invention is reacted under the existence of organophosphorus based compound for making phenol resins and (methyl) glycidyl acrylate, obtains the method for the modified phenolic resin (A) shown in general formula (I).
In formula, R
1for the group shown in hydrogen atom or following formula (II), and whole R
1middle R
1for the ratio of hydrogen atom is more than 20% and is less than 80%.R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another.N represents the integer of 0 ~ 40.
(in formula, R
4for hydrogen atom or methyl.)
N+2 in the general formula of modified phenolic resin (A) whole R
1in R
1for the ratio of hydrogen atom is more than 20% and is less than 80%, be preferably 30 ~ 70%, be more preferably 40 ~ 60%.
By making the R in the general formula of modified phenolic resin (A)
1the ratio of hydrogen atom be more than 20% and be less than 80%, thus shrinking percentage when comprising the solidification of the compositions of thermosetting resin of modified phenolic resin (A) and epoxy resin described later (B) increases.
In above-mentioned formula (I), R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another.
As the aliphatic alkyl of carbonatoms 1 ~ 20, the saturated alkyl on chain or side chain or unsaturated alkyl can be enumerated, be preferably carbonatoms 1 ~ 12, be more preferably carbonatoms 1 ~ 6.Specifically, methyl, ethyl, sec.-propyl, n-octyl, vinyl, butenyl etc. can be enumerated, but be not limited to this.From the view point of versatility, reaction easiness, be preferably methyl, ethyl.
As the aromatic hydrocarbyl of carbonatoms 1 ~ 20, phenyl, naphthyl etc. can be enumerated.
From the view point of versatility, reaction easiness, preferred R
2and R
3be methyl, ethyl independently of one another.
In above-mentioned formula (I), n represents the integer of 0 ~ 40, is preferably 0 ~ 30, is more preferably 0 ~ 20.If the n in above-mentioned formula (I) is the integer of 0 ~ 40, then can control in specified range by the weight-average molecular weight of modified phenolic resin (A), be applicable from the viewpoint of mobility.
Here, modified phenolic resin (A) can carry out reacting obtaining by making phenol resins and (methyl) glycidyl acrylate under basic catalyst.
The usage quantity of (methyl) glycidyl acrylate, relative to the mole number of the hydroxyl in phenol resins, is preferably 20 ~ 90 % by mole, is more preferably 30 ~ 80 % by mole.By making the usage quantity of (methyl) glycidyl acrylate be more than 20 % by mole less than 90 % by mole, then can by the R in the general formula of modified phenolic resin (A)
1the ratio of hydrogen atom be adjusted to specified amount.
As basic catalyst, can enumerate such as, the oxyhydroxide of alkali (soil) metal, organophosphorus based compound.
But, when employing the oxyhydroxide of alkali (soil) metal, remaining metal ion in modified phenolic resin.In such as electronic material purposes, there is the possibility that undesirable condition occurs due to being mixed into of metal ion, therefore need the removal step of catalyzer.Catalyzer removal step is such as the washing of modified phenolic resin carried out repeatedly, or to be washed with water by the salt of generation with acid neutralization and remove.Such operation produces a large amount of waste water and activity time is elongated, therefore not preferred.
If use amine compound as basic catalyst, then remaining amine compound in modified phenolic resin.Amine compound works as the solidifying agent of epoxy resin, and generally speaking its temperature of reaction is lower than the temperature of reaction of phenol resins and epoxy resin.Modified phenolic resin (A) in rear operation collapses with the molecular balance of epoxy resin (B), therefore not preferred.Such as when using vulkacit H as amine compound, modified phenolic resin is had to combine the effect carrying out being cross-linked each other with methylene radical, therefore modified phenolic resin (A) becomes insufficient with the reaction of epoxy resin (B), therefore not preferred.
(organophosphorus based compound)
Therefore, use organophosphorus based compound as basic catalyst in the present invention.
As organophosphorus based compound, ethyl phosphine, propyl group phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenylborane coordination compound, tetraphenyl boron tetraphenyl can be enumerated
deng.They can be used alone, also can more than two kinds and use, if be considered as the characteristic of compositions of thermosetting resin, are then preferably triphenylphosphine.
The usage quantity of organophosphorus based compound, relative to phenol resins 100 mass parts, is preferably 0.001 mass parts ~ 10 mass parts, is more preferably 0.01 mass parts ~ 8 mass parts, more preferably 0.1 mass parts ~ 5 mass parts.
If the usage quantity of organophosphorus based compound is more than 0.001 mass parts relative to phenol resins 100 mass parts, then the reaction times being used for obtaining modified phenolic resin (A) can be foreshortened to usage range.In addition, if the usage quantity of organophosphorus based compound is below 10 mass parts relative to phenol resins 100 mass parts, then the control of the speed of response of compositions of thermosetting resin becomes easy.
(other additive)
As required, from the view point of the storage stability of composition, stopper can be added.As stopper, quinhydrones, toluhydroquinone etc. can be enumerated.
The method of reacting is carried out for making phenol resins and (methyl) glycidyl acrylate, be not particularly limited, can enumerate such as, make phenol resins add the method for carrying out reacting in the lump with (methyl) glycidyl acrylate and basic catalyst; Or add phenol resins and basic catalyst, under the temperature of reaction of regulation, add the method for (methyl) glycidyl acrylate.
Now, temperature of reaction is preferably carried out the scope of 30 DEG C ~ 120 DEG C, more preferably carries out the scope of 60 DEG C ~ 110 DEG C.
By making temperature of reaction be more than 30 DEG C, thus it is slow that the carrying out of reaction can be made to be difficult to.In addition, by making temperature of reaction be less than 120 DEG C, thus the radical polymerization of (methyl) glycidyl acrylate can be suppressed.
Reaction times is not particularly limited, as long as according to amount, the temperature of reaction of (methyl) glycidyl acrylate and catalyzer, suitably adjust.
During reaction, can be with an organic solvent.
(organic solvent)
As such organic solvent, ester class, the Isosorbide-5-Nitraes-two such as the ketones such as glycol ethers, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) such as the glycolss such as alcohols, ethylene glycol, propylene glycol such as methylol, ethyl alcohol, propyl group alcohol, butanols, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, butyleneglycol monomethyl ether, butyleneglycol list ethyl ether, butyleneglycol list propyl ether, ethyl acetate, propyl acetate, butylacetate, ethyl lactate, ethylene glycol monomethyl ether acetic acid ester, propylene glycol monomethyl ether
the ethers etc. such as alkane can be used alone, or can more than two kinds and use.
Above-mentioned organic solvent can be preferably 0 mass parts ~ 1 relative to phenol resins 100 mass parts, and 000 mass parts, the mode be more preferably about 10 mass parts ~ 100 mass parts, more preferably 10 mass parts ~ 50 mass parts use.
The modification phenol obtained by reacting can remove organic solvent by distillation after the reaction, can carry out washing as required to remove catalyzer in addition.
In addition, underpressure distillation or wet distillation can be carried out to remove unreacted phenols.
The content of the basic metal in modified phenolic resin (A), the total content of alkaline-earth metal or amine compound is below 0.1 quality % relative to the total amount of above-mentioned phenol resins (A), be preferably below 0.05 quality %, be more preferably below 0.01 quality %.As amine compound, be not particularly limited, the amine compound etc. of the basic catalyst derived from when obtaining modified phenolic resin (A) can be enumerated, can enumerate such as, the aromatic amines such as fatty amine, m-xylene diamine such as vulkacit H.
By making the total amount relative to above-mentioned phenol resins (A), the total content of basic metal, alkaline-earth metal or the content of amine compound are below 0.1 quality %, thus the washing times of the modified phenolic resin of gained can be reduced, consequently shorten manufacturing process's time, in addition, the modified phenolic resin (A) after suppressing in operation collapses with the balance of the reaction of epoxy resin (B).
In addition, as the total content of the basic metal in compositions of thermosetting resin, alkaline-earth metal or the content of amine compound, be below 0.05 quality % relative to the total amount of above-mentioned compositions of thermosetting resin.Now, when compositions of thermosetting resin comprises weighting agent, because it does not participate in curing reaction, therefore consider relative to remove from the total amount of compositions of thermosetting resin the amount after weighting agent, the total content of basic metal, alkaline-earth metal or the content of amine compound.
Basic metal in modified phenolic resin (A), alkaline-earth metal use atomic absorption spectrophotometer (AAS) to carry out quantitative assay.In addition, the amine compound in modified phenolic resin (A) uses gas chromatographic analysis device (GC) to carry out quantitative analysis.Analysis conditions etc. describe in detail in an embodiment.
About the weight-average molecular weight of modified phenolic resin (A), if consider the mobility of compositions of thermosetting resin, be then preferably 250 ~ 5000, be more preferably 300 ~ 4000, more preferably 400 ~ 3000.
The weight-average molecular weight of resin such as can be passed through gel permeation chromatography (GPC) and measure.As the concrete condition determination of GPC, can enumerate such as,
Post: trade(brand)name " KF-801 ", " KF-802 ", " KF-802 " and " KF-803 " (Showa Denko K. K's system, Shodex (trade mark) series) are connected use.
Detector: trade(brand)name " RI-71 " (Showa Denko K. K's system, differential refractometer " Shodex " (trade mark))
Solvent: tetrahydrofuran (THF)
Flow: 1ml/ minute
Deng.
(epoxy resin (B))
As epoxy resin used in the present invention, be not particularly limited, known epoxy resin can be used.As the concrete example of epoxy resin, bisphenol A type epoxy resin can be enumerated, bisphenol f type epoxy resin, bisphenol-s epoxy resin, dihydroxyphenyl propane D type epoxy resin, Resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol-type epoxy resin, dihydroxy naphthlene type epoxy resin, biphenyl type epoxy resin, the epoxy resin that tetramethyl biphenyl type epoxy resin etc. is derived by divalence phenols, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, Dicycldpentadiene-phenol modified version epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol novolac type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-cresols cocondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbons formaldehyde resin modified phenolic resin type epoxy resin, the epoxy resin that biphenyl modified novolac type epoxy resin etc. are derived by the above phenols of trivalent, epoxy resin etc. by the modification of organophosphorus based compound.Wherein be preferably triphenylmethane type epoxy resin.In addition these epoxy resin can be used alone, also can more than two kinds and use.Wherein, be preferably bisphenol-type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, biphenyl aralkyl-type epoxy resin, be more preferably biphenyl aralkyl-type epoxy resin.
About the weight-average molecular weight of epoxy resin (B), from the view point of the mobility of compositions of thermosetting resin and the balance of thermotolerance, be preferably 300 ~ 5000, be more preferably 400 ~ 3500, more preferably 400 ~ 3000.
Epoxy resin (B) with the blending ratio of phenol resins (A) is, relative to epoxy group(ing) 1.0 equivalent in epoxy resin (B), hydroxyl in phenol resins (A) is preferably the scope of 0.5 equivalent ~ 1.3 equivalent, be more preferably the scope of 0.6 equivalent ~ 1.2 equivalent, more preferably the scope of 0.7 equivalent ~ 1.1 equivalent.
In compositions of thermosetting resin, to promote for the purpose of curing reaction, also can be suitable for using curing catalyst.
As curing catalyst, can enumerate such as, imidazole compound, organophosphorus based compound, Lewis acid etc.They can be used alone, also can more than two kinds and use.
As imidazole compound, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazole, 4 can be enumerated, 5-diphenyl-imidazole, glyoxal ethyline quinoline, 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2-heptadecyl imidazole quinoline, 2 isopropyl imidazole, 2,4-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline, 2,4-methylimidazole quinolines, 2-phenyl-4-methylimidazole quinoline etc.
Imidazole compound can be masked by sequestering agent.
As sequestering agent, vinyl cyanide, phenylene diisocyanate, toluidine isocyanate (ト Le イ ジ Application イ ソ シ ア ネ ー ト), naphthalene diisocyanate, Methylene bis phenyl isocyanic ester, melamine acrylate etc. can be enumerated.
As organophosphorus based compound, ethyl phosphine, propyl group phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenylborane coordination compound, tetraphenyl boron tetraphenyl can be enumerated
deng.
In these curing catalysts, be preferably triphenylphosphine.
(weighting agent)
In compositions of thermosetting resin of the present invention, for the purpose of flame retardant resistance imparting, thermal expansion suppression etc., preferably coordinate weighting agent.As concrete example, can enumerate such as, the inorganic fillers such as fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconium white, forsterite, steatite, spinel, titanium dioxide, aluminium hydroxide, magnesium hydroxide.
Fused silica can use broken shape, spherical any one, in order to improve the use level of fused silica, and being suppressed to the rising of the melt viscosity of shaped material, preferably mainly using spherical fused silica.In addition, in order to improve the use level of spherical silicon dioxide to compositions of thermosetting resin, preferably the size-grade distribution of spherical silicon dioxide is suitably adjusted.The fit rate of fused silica is suitable for purposes with desired characteristic and desired scope is different according to compositions of thermosetting resin.Such as, when compositions of thermosetting resin being used for encapsulating semiconductor material purposes, if in view of linear expansivity, the flame retardant resistance of the cured article of compositions of thermosetting resin, then the fit rate of preferred molten silicon-dioxide is high.Specifically, be preferably more than 50 quality % relative to compositions of thermosetting resin total amount, be more preferably more than 60 quality %, more preferably 70 quality % ~ 90 about quality %.
In addition, when compositions of thermosetting resin being used for the purposes such as conductive paste, conducting film, as weighting agent, the agent of the conductive filler such as silver powder, copper powder can be used.
In addition, compositions of thermosetting resin of the present invention can as required containing various Synergist S-421 95s such as the thermosetting resin used as properties-correcting agent and thermoplastic resin, pigment, silane coupling agent, releasing agents.
The thermosetting resin used as properties-correcting agent and thermoplastic resin can use known various material.
As thermosetting resin and thermoplastic resin, can use such as required in the scope not damaging effect of the present invention, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene oxide resin, polyphenylene sulfide vibrin, polystyrene resin, pet resin etc.
As silane coupling agent, the silane coupling agents such as aminosilane based compound, vinyl silanes based compound, polystyrene silane compound, methacrylic acyloxy silane based compound can be enumerated.
In addition, as releasing agent, stearic acid, Zinic stearas, calcium stearate, aluminum stearate, Magnesium Stearate and carnauba wax etc. can be enumerated.
The cured article that shrinking percentage when the compositions of thermosetting resin acquisition containing modified phenolic resin (A) and epoxy resin (B) of the present invention is solidified is high.
When the sealing material as electronic unit uses with resin combination, particularly from the view point of the convexity warp suppressing thin encapsulation, shrinking percentage when compositions of thermosetting resin is solidified is preferably 0.15% ~ 0.40%, be more preferably 0.20% ~ 0.40%, more preferably 0.25% ~ 0.40%.
Compositions of thermosetting resin of the present invention particularly can be suitable for interlayer dielectic resin combination that the sealing material resin combination of electronic unit, printed base plate resin combination, printed base plate and the Copper Foil with resin use, conductive paste, coating, caking agent and matrix material containing conductive filler agent.
< cured article >
Compositions of thermosetting resin solidification of the present invention obtains by cured article of the present invention.
The curing of compositions of thermosetting resin is not particularly limited, such as, as long as carried out heating by compositions of thermosetting resin under Heating temperature 170 DEG C ~ 250 DEG C, the condition of 60 minutes ~ 20 hours heat-up time.Heating temperature is more preferably 170 DEG C ~ 220 DEG C, more preferably 170 DEG C ~ 200 DEG C.Be more preferably 60 minutes ~ 10 hours heat-up time, more preferably 90 minutes ~ 8 hours.
In addition, preferably before the manufacture of cured article, compositions of thermosetting resin is carried out extrusion forming.Pressure during extrusion forming is preferably 2 ~ 20MPa, is more preferably 4 ~ 15MPa, more preferably 5 ~ 12MPa.In addition, temperature during extrusion forming is preferably 170 ~ 250 DEG C, is more preferably 170 ~ 220 DEG C, more preferably 170 ~ 200 DEG C.
Embodiment
Below, in further detail the present invention is described by embodiment, but the present invention is not limited to this, in embodiment and comparative example " part " is quality criteria with " % ".
Production Example 1 (synthesis of modified phenolic resin A)
In the flask possessing cooling tube and stirrer, add trade(brand)name " シ ョ ウ ノ ー Le (trade mark) BRG-558 " (the Showa Denko K. K's system as phenol resol resins, hydroxyl equivalent 104g/eq.) 104g, methyl ethyl ketone 50g, quinhydrones 0.04g and glycidyl methacrylate 43g, carry out mixing until become even at 60 DEG C.Be cooled to less than 40 DEG C, then add triphenylphosphine 2g.100 DEG C of reactions 5 hours, then at 120 DEG C, under the decompression of 50mmHg, from resultant, remove cut, obtain the modified phenolic resin A of the filbert bulk of 147g.The softening temperature of the modified phenolic resin A of gained is 83 DEG C, and weight-average molecular weight is 1900.
Production Example 2 ~ 3, compare Production Example 2 ~ 4
Use the composition of table 1, in addition, react in the same manner as Production Example 1, obtain modified phenolic resin B ~ C, the J ~ L shown in table 2,3.
Production Example 4
In the flask possessing cooling tube and stirrer, add Bisphenol F 200g, methyl ethyl ketone 100g makes them dissolve, then add quinhydrones 0.08g, glycidyl methacrylate 56g and carry out mixing until become even, then add triphenylphosphine 2g.100 DEG C of reactions 5 hours, then at 120 DEG C, under the decompression of 50mmHg, from resultant, remove cut, obtain modified phenolic resin D256g.
Production Example 5
In the flask possessing cooling tube, stirrer, add ortho-cresol 100g, phenyl aldehyde 49g, tosic acid 10g, 100 DEG C of reactions 8 hours.Then, with in aqueous sodium hydroxide solution and after, with pure water 100g carry out 5 times washing, except desalting.
Then at 180 DEG C, under the decompression of 50mmHg, remove cut, be then dissolved in methyl ethyl ketone 39g.Then add quinhydrones 0.04g, glycidyl methacrylate 19g, carry out mixing until become even, then add triphenylphosphine 2g.100 DEG C of reactions 5 hours, then at 120 DEG C, under the decompression of 50mmHg, remove cut, obtain 98g modified phenolic resin E.
Production Example 6
Use the composition of table 1, in addition, react in the same manner as Production Example 5, obtain resin F.
Production Example 7,8
Use the composition of table 1, in not carrying out after the reaction of first stage and operation, carry out 2 washings with pure water 100g, in addition, react in the same manner as Production Example 5, obtain resin G, H.
Relatively Production Example 1
Operate in the same manner as Production Example 5, implement the reaction of first stage, carry out the removing of salt, the removing of cut and obtain phenol resol resins, be set to resin I.That do not carry out subordinate phase with reaction that is glycidyl methacrylate.
[table 1]
BRG-558: phenol resol resins, trade(brand)name " シ ョ ウ ノ ー Le (trade mark) BRG-558 ", Showa Denko K. K's system, hydroxyl equivalent 104g/eq.
CRG-951: o-cresol novolak, trade(brand)name " シ ョ ウ ノ ー Le (trade mark) CRG-951 ", Showa Denko K. K's system, hydroxyl equivalent 118g/eq.
The analytical procedure of modified phenolic resin and phenol resins is as follows.
(1) softening temperature (DEG C)
Use エ レ ッ Network ス science society system, gas phase softening point measurement device EX-719PD measures.Heat-up rate is set to 2.5 DEG C/min.
(2) weight-average molecular weight
Measured by gel permeation chromatography (GPC).
Post is configured to make Showa electrician society system, and trade(brand)name " KF-801 ", " KF-802 ", " KF-802 " are connected with " KF-803 ", uses tetrahydrofuran (THF) as solvent, measures with flow 1ml/ minute.Detector commodity in use name " RI-71 " (Showa Denko K. K's system, differential refractometer " Shodex " (trade mark)).Molecular weight calculates with polystyrene conversion.
(3) R of the general formula of modified phenolic resin
1the ratio of hydrogen atom
Use nucleus magnetic resonance (NMR) device (BRUKER society system, goods name " AVANCE400 "), the NMR of phenol resins is before modified schemed the ratio of the chemical shift of the 8.0 ~ 10.0ppm deriving from phenolic hydroxyl group (chemical shift deriving from 6.5 ~ 7.5ppm of phenyl ring with) to scheme (the same) with the NMR of modified phenolic resin and compare, calculate the R of general formula (I)
1the ratio of hydrogen.
(4) basic metal in modified phenolic resin (A), alkaline-earth metal use atomic absorption spectrophotometer (AAS) (Thermo Scientrific society system, goods name " iCE3000 ") to carry out quantitative assay.
(5) amine compound in modified phenolic resin (A) uses gas phase chromatographic device (GC) (Shimadzu Scisakusho Ltd's system, goods name " GC-8APF "), carries out quantitative analysis under the following conditions.
＜GC＞
Post: Port ラ パ ッ Network Q post (80 ~ 100 order)
Carrier gas: nitrogen
Flow: 40ml/ minute
Column temperature: 230 DEG C
About each analytical results, be shown in table 2 and table 3.
Embodiment 1 ~ 15 and comparative example 1 ~ 6
(modulation of compositions of thermosetting resin)
About by Production Example 1 ~ 8 with compare each modified phenolic resin and phenol resins that Production Example 1 ~ 4 obtains, mix with the cooperation shown in table 2, table 3, under temperature 90 DEG C, the condition of 5 minutes time, carry out melting mixing, obtain the compositions of thermosetting resin of embodiment 1 ~ 15 and comparative example 1 ~ 6.
The cooperation of the composition shown in table 2, table 3 is carried out as follows.
For the amount shown in table 2, table 3 (such as, in embodiment 1 be 10 parts) epoxy resin (weight-average molecular weight 1000), the modified phenolic resin of the hydroxyl equivalent described in mixture table 2, table 3/epoxide equivalent ratio and phenol resins, add the triphenylphosphine (curing catalyst) of 0.1 part, thus obtain resinous principle.Next, be that fused silica (inorganic filler) is mixed in above-mentioned resinous principle by the mode of 80 quality % to make the containing ratio in composition, utilize two roller (マ シ ナ リ ー society of western village system, NS-155 (S) type), mixing 5 minutes at 100 DEG C, modulate compositions of thermosetting resin.
(manufacture of cured article)
The compositions of thermosetting resin of acquisition is utilized the mould (circle of diameter 90mm specified in JIS K-6911, thickness 5mm, and the scope that can be produced on diameter 76 ~ 80mm has the mould of sample of the protuberance of height 3mm), 150 DEG C, 40 minutes, carry out extrusion forming under the condition of pressure 10MPa.Then, 180 DEG C of heating 5 hours, compositions of thermosetting resin is cured, produces the testing plate of cured article.
About the testing plate obtained, evaluate shrinkage rate by the following method.
(6) shrinking percentage
The method specified in JIS K-6911 is adopted to evaluate.
The measurement result of the shrinking percentage of the testing plate made by embodiment 1 ~ 15 and comparative example 1 ~ 6 shown in table 3, table 2.
[table 2]
[table 3]
Confirmed by table 2, table 3, the cured article (testing plate) of compositions of thermosetting resin of the present invention shows high shrinkage.Namely known, excellent far away compared with the shrinking percentage of the testing plate of embodiment and use novolac resin in the past and the cured article that obtains.
Claims (10)
1. a compositions of thermosetting resin, is characterized in that, comprises the modified phenolic resin (A) shown in general formula (I) and epoxy resin (B),
Basic metal in described modified phenolic resin (A), the total content of alkaline-earth metal are below 0.1 quality % relative to the total amount of described phenol resins (A), and,
The content of the amine compound in described modified phenolic resin (A) is below 0.1 quality % relative to the total amount of described phenol resins (A),
In formula, R
1for the group shown in hydrogen atom or following formula (II), and whole R
1middle R
1for the ratio of hydrogen atom is more than 20% and is less than 80%, R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another, n represents the integer of 0 ~ 40,
In formula, R
4for hydrogen atom or methyl.
2. compositions of thermosetting resin according to claim 1, the total content of the basic metal in described compositions of thermosetting resin, alkaline-earth metal is below 0.05 quality %, and,
The content of the amine compound in described compositions of thermosetting resin is below 0.05 quality %.
3. compositions of thermosetting resin according to claim 1 and 2, the weight-average molecular weight of described modified phenolic resin (A) is 250 ~ 5000.
4. the compositions of thermosetting resin according to any one of claims 1 to 3, relative to epoxy group(ing) 1.0 equivalent in described epoxy resin (B), the hydroxyl of described modified phenolic resin (A) is the scope of 0.6 equivalent ~ 1.2 equivalent.
5. the compositions of thermosetting resin according to any one of Claims 1 to 4, the weight-average molecular weight of described epoxy resin (B) is 300 ~ 5000.
6. the compositions of thermosetting resin according to any one of Claims 1 to 5, comprises weighting agent.
7. a cured article is obtained the compositions of thermosetting resin solidification described in any one of claim 1 ~ 6.
8. cured article according to claim 7, shrinking percentage is 0.15% ~ 0.40%.
9. the manufacture method of a modified phenolic resin, it is characterized in that, phenol resins and (methyl) glycidyl acrylate are reacted under the existence of organophosphorus based compound, obtains the modified phenolic resin (A) shown in general formula (I)
In formula, R
1for the group shown in hydrogen atom or following formula (II), and whole R
1middle R
1for the ratio of hydrogen atom is more than 20% and is less than 80%, R
2and R
3represent aliphatics or the aromatic hydrocarbyl of hydrogen atom or carbonatoms 1 ~ 20 independently of one another, n represents the integer of 0 ~ 40,
In formula, R
4for hydrogen atom or methyl.
10. the manufacture method of modified phenolic resin according to claim 9, the usage quantity of organophosphorus based compound is below more than 0.001 mass parts 10 mass parts relative to phenol resins 100 mass parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-041807 | 2014-03-04 | ||
| JP2014041807A JP6497639B2 (en) | 2014-03-04 | 2014-03-04 | Thermosetting resin composition, cured product and method for producing modified phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892905A true CN104892905A (en) | 2015-09-09 |
| CN104892905B CN104892905B (en) | 2018-09-11 |
Family
ID=54025902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510067709.8A Expired - Fee Related CN104892905B (en) | 2014-03-04 | 2015-02-09 | The manufacturing method of compositions of thermosetting resin, solidfied material and modified phenolic resin |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6497639B2 (en) |
| KR (1) | KR20150104026A (en) |
| CN (1) | CN104892905B (en) |
| TW (1) | TW201544538A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111971322A (en) * | 2018-04-13 | 2020-11-20 | 株式会社Moresco | Compound and use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200135696A (en) | 2019-05-25 | 2020-12-03 | 이한울 | Chair a bus equipped with the notifications |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045839A (en) * | 2007-04-10 | 2007-10-03 | 深圳市容大电子材料有限公司 | Liquid photosensitive ink and applied in printing circuit board |
| CN101220224A (en) * | 2008-01-23 | 2008-07-16 | 深圳市容大电子材料有限公司 | UV solidified alkali resistant etching ink composition and uses thereof |
| US20090156715A1 (en) * | 2007-12-14 | 2009-06-18 | Thomas Eugene Dueber | Epoxy compositions comprising at least one elastomer and methods relating thereto |
| KR101248008B1 (en) * | 2012-05-02 | 2013-03-27 | 주식회사 이녹스 | Adhesive film composition for semiconductor package |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551507A (en) * | 1991-08-26 | 1993-03-02 | Soken Kagaku Kk | Thermosetting acrylate composition |
| JPH10180403A (en) * | 1996-12-26 | 1998-07-07 | Sumitomo Bakelite Co Ltd | Resin composition, permanent resist resin composition, and hardened resin thereof |
| JP4244421B2 (en) * | 1999-01-06 | 2009-03-25 | 住友ベークライト株式会社 | Curable resin composition and thickening method thereof |
| JP4514011B2 (en) * | 2001-09-13 | 2010-07-28 | 日本化薬株式会社 | Resin composition, solder resist resin composition, and cured products thereof |
| JP2005082782A (en) * | 2003-09-11 | 2005-03-31 | Showa Highpolymer Co Ltd | Electroconductive curable resin composition |
-
2014
- 2014-03-04 JP JP2014041807A patent/JP6497639B2/en active Active
-
2015
- 2015-02-02 KR KR1020150016072A patent/KR20150104026A/en not_active Application Discontinuation
- 2015-02-09 CN CN201510067709.8A patent/CN104892905B/en not_active Expired - Fee Related
- 2015-02-13 TW TW104105044A patent/TW201544538A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045839A (en) * | 2007-04-10 | 2007-10-03 | 深圳市容大电子材料有限公司 | Liquid photosensitive ink and applied in printing circuit board |
| US20090156715A1 (en) * | 2007-12-14 | 2009-06-18 | Thomas Eugene Dueber | Epoxy compositions comprising at least one elastomer and methods relating thereto |
| CN101220224A (en) * | 2008-01-23 | 2008-07-16 | 深圳市容大电子材料有限公司 | UV solidified alkali resistant etching ink composition and uses thereof |
| KR101248008B1 (en) * | 2012-05-02 | 2013-03-27 | 주식회사 이녹스 | Adhesive film composition for semiconductor package |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111971322A (en) * | 2018-04-13 | 2020-11-20 | 株式会社Moresco | Compound and use thereof |
| CN111971322B (en) * | 2018-04-13 | 2023-08-08 | 株式会社Moresco | Compounds and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201544538A (en) | 2015-12-01 |
| JP6497639B2 (en) | 2019-04-10 |
| KR20150104026A (en) | 2015-09-14 |
| JP2015166437A (en) | 2015-09-24 |
| CN104892905B (en) | 2018-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5774021B2 (en) | Phenol oligomer and method for producing the same | |
| TWI465488B (en) | Novolac resin and method for producing the same | |
| TWI648317B (en) | Phenolic resin, phenol resin mixture, epoxy resin, epoxy resin composition and hardened materials | |
| TWI466965B (en) | Method for producing novolak resin and novolak resin | |
| TWI640569B (en) | Epoxy resin composition, encapsulating material, hardened material thereof and phenol resin | |
| JP5366263B2 (en) | Phenol aralkyl resin, epoxy resin composition and cured product thereof | |
| CN104892905A (en) | Thermosetting resin composition,condensate and manufactur method for modified urushiol resin | |
| JP5233858B2 (en) | Epoxy resin composition, cured product thereof, and semiconductor device | |
| JP5254590B2 (en) | Low molecular weight novolak resin, method for producing the same, and thermosetting resin composition using the same | |
| TWI522385B (en) | An epoxy resin, an epoxy resin composition, and a cured product thereof | |
| JP2000103941A (en) | Epoxy resin composition and semiconductor sealing material | |
| JP6232271B2 (en) | Phenol resin composition, thermosetting resin composition, and cured product | |
| JP4628621B2 (en) | Method for producing phenol aralkyl resin | |
| CN104513358A (en) | Thermosetting resin composition and cured product obtained from curing the same | |
| KR20160068728A (en) | Phenolic resin, epoxy resin, epoxy resin composition, prepreg and cured product of said epoxy resin composition or prepreg | |
| JP2004244526A (en) | Novel phenol resin, curing agent for epoxy resin, and epoxy resin composition | |
| JP2981759B2 (en) | Epoxy compound and epoxy resin composition | |
| JP6729863B2 (en) | Method for producing novolac type phenol resin, novolac type phenol resin, thermosetting resin composition and cured product | |
| JP6519917B2 (en) | Epoxy resin and thermosetting resin composition | |
| JPH0597972A (en) | Epoxy resin composition | |
| JP2002332325A (en) | Novel epoxy resin, curing agent and epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20151120 Address after: Gunma Applicant after: Agfa SDK phenol Co Ltd Address before: Tokyo, Japan, Japan Applicant before: Showa Denko K. K. |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190218 Address after: Aichi Patentee after: Eike Kogyo K. K. Address before: Gunma Patentee before: Agfa SDK phenol Co Ltd |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180911 Termination date: 20200209 |