CN102282188A - Novolac resin and method for producing same - Google Patents
Novolac resin and method for producing same Download PDFInfo
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- CN102282188A CN102282188A CN2009801541420A CN200980154142A CN102282188A CN 102282188 A CN102282188 A CN 102282188A CN 2009801541420 A CN2009801541420 A CN 2009801541420A CN 200980154142 A CN200980154142 A CN 200980154142A CN 102282188 A CN102282188 A CN 102282188A
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- novolac resin
- resin
- acid
- phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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- 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
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- Chemical & Material Sciences (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
Disclosed is a method for producing a novolac resin, wherein a phenol and an aldehyde are reacted with each other in the presence of a catalyst that contains calcium chloride and an acid. The method is characterized in that a novolac resin having a low molecular weight and a low melt viscosity is efficiently produced by reacting a phenol and an aldehyde with each other under mild conditions.
Description
Technical field
The present invention relates to obtain with high yield the manufacture method of the low and low-molecular-weight novolac resin of melt viscosity.
Background technology
Phenol resins has thermotolerance, can use in various fields.
For example, under situation about using as curing agent for epoxy resin, thermotolerance, adhesivity, electrical insulating property etc. are all excellent, thus can printed base plate with resin combination, printed base plate and adhere to the interlayer dielectic that uses in the Copper Foil of resin with the sealing material use resin combination of resin combination, electronic unit, etching resisting ink, conducting paste, coating, binding agent, matrix material etc. in use.
Along with technical renovation in recent years, the thermotolerance of the further raising of requirement composition epoxy resin, moistureproofness, flame retardant resistance etc.
As one of its solution, be the usage quantity that increases weighting agent.
By increasing filling dose, the linear expansivity of moulding product be can reduce and/or rate of moisture absorption, raising flame retardant resistance reduced, but then, the flowability that can produce title complex reduces because loading level increases, the such problem of formability variation, thereby needs to reduce the melt viscosity of resinous principle.
Novolac resin makes phenols and aldehydes carry out addition condensation in the presence of an acidic catalyst and makes.
Usually, aldehydes uses 0.3～0.9 mole scope with respect to the mol ratio of phenols, recently controls the molecular weight of gained resin by adjusting mole.
In order to reduce the melt viscosity of resin, high molecular weight components need be reduced as far as possible, but, the mol ratio of aldehydes must be reduced with respect to phenols in order to obtain the low novolac resin of molecular weight, unreacted phenol monomer is remaining in a large number under this situation.
Can be by under reduced pressure distilling the unreacted phenolic monomers that reduces in the resin, but since the mol ratio of resin low more then needs more remove a large amount of phenolic monomers by distillation, so yield to reduce be inevitable.
On the other hand, in resin, under the situation of remaining phenolic monomers, can cause that the dimensional stability of forming composition reduces, produce space etc., so the phenolic monomers in the preferred resin is few as far as possible.
Based on such background, studied the high yieldization (with reference to patent documentation 1 and 2) of novolac resin.
In patent documentation 1, disclose and make phenols and paraformaldehyde in the presence of phosphoric acid catalyst, carry out the method for inhomogeneous reaction.
Though adopt this method to improve the reactivity of phenols, but catalyzer is restricted to phosphoric acid, therefore under the situation that the aromatic aldehydes such as fatty aldehyde such as aldehyde, for example acetaldehyde and/or butyraldehyde, phenyl aldehyde and/or salicylic aldehyde that make reactivity be lower than paraformaldehyde react, can not get sufficient reactivity.
In patent documentation 2, the method that phenols and aldehydes are reacted in the presence of organic phospho acid catalyzer and water-soluble neutral salt is disclosed, exist the water of catalyzer and the easy dissolved organic phase of resin to improve the monomer reaction rate by formation.
Therefore yet catalyzer also is restricted to organic phospho acid in the method, being lower than under the situation of aldehyde reaction of formaldehyde with above-mentioned reactivity, can not get sufficient reactivity.
In addition, in order to improve catalyst efficiency, need the temperature more than 110 ℃, so the generation of high molecular body being inevitably, is being not preferred obtaining aspect the low-molecular-weight novolac resin.
In addition, in patent documentation 2, neutral salt for the ionic concn that improves water more clearly to separate organic phase and water uses.
Therefore, as neutral salt, be important to the solvability height of water, it constitutes element is not particularly important.
When making the reaction of aromatic aldehyde such as fatty aldehyde such as acetaldehyde and/or butyraldehyde, phenyl aldehyde and/or salicylic aldehyde and phenols, use hydrogen halide and/or sulfonic acid based compound geometric ratio phosphoric acid and/or the stronger acid of organic phospho acid in a large number, and need high reaction temperature.
Under such condition, generate high molecular weight components easily, therefore be difficult to obtain low-molecular-weight novolac resin.
Like this, if the aldehydes of wanting to use reactivity to be lower than formaldehyde and/or paraformaldehyde obtains low-molecular-weight novolac resin with high yield, then also there is not effective manufacture method up to now.
Patent documentation 1: TOHKEMY 2004-339257 communique
Patent documentation 2: TOHKEMY 2002-128849 communique
Summary of the invention
The problem that invention will solve
The present invention is based on the above fact and proposes, its purpose is, providing and making phenols and aldehydes, particularly carbonatoms is that fatty aldehyde and aromatic aldehyde more than 2 reacts under the condition of gentleness, makes the method for the low and low-molecular-weight novolac resin of melt viscosity effectively.
Be used to solve the method for problem
Present inventors find, can solve above-mentioned problem by using the normally used catalyzer that comprises acid and calcium chloride, thereby finish the present invention.
That is, main points of the present invention are as follows.
1. the manufacture method of a novolac resin is characterized in that, in the presence of the catalyzer that comprises calcium chloride and acid, makes the reaction of phenols and aldehydes.
2. according to the manufacture method of above-mentioned 1 described novolac resin, wherein, acid is oxalic acid or phosphoric acid.
3. according to above-mentioned 1 or the manufacture method of 2 described novolac resins, it obtains dispersity is that weight-average molecular weight/number-average molecular weight is 1.3 below and the melt viscosity under 150 ℃ is a novolac resin below the 300mPas.
The effect of invention
According to the present invention, can obtain the low novolac resin of lower molecular weight and melt viscosity effectively by in the presence of the catalyzer that comprises calcium chloride and acid, making phenols and aldehydes reaction.
Description of drawings
Fig. 1 is the GPC figure of the novolac resin among the embodiment 1.
Fig. 2 is the GPC figure of the novolac resin in the comparative example 3.
Embodiment
Below, specifically describe the present invention.
The manufacture method of novolac resin of the present invention is the method that makes phenols and aldehydes reaction in the presence of the catalyzer that comprises calcium chloride and acid.
As the phenols that uses among the present invention, so long as the phenols that generally uses in the manufacturing of phenol resins get final product, can use separately or mix the following phenols of use more than 2 kinds: for example phenol, various cresols, various ethylphenol, various xylenol, various ethylphenol, various butylphenol, various octyl phenol, various nonylphenol, various phenylphenol, various cyclohexylphenol, various pseudocuminol, dihydroxyphenyl propane, catechol, Resorcinol, quinhydrones, various naphthols, pyrogallol etc.
Wherein, phenol and various cresols are preferred in practicality.
On the other hand, as with the aldehydes of phenols reaction, so long as the aldehydes that can use in the manufacturing of phenol resins gets final product.
Can use or mix use more than 2 kinds following aldehydes separately: for example, formaldehyde, acetaldehyde, paraformaldehyde, various propionic aldehyde, various butyraldehyde, various valeral, various hexanal, oxalic dialdehyde, crotonic aldehyde, glutaraldehyde, phenyl aldehyde, various hydroxy benzaldehyde, various Dihydroxy benzaldehyde, various methylol phenyl aldehydes etc.
The usage quantity of preferred above-mentioned aldehydes is 0.3～1.0 mole for 1 mole with respect to the total amount of phenols, preferably uses with 0.4～0.9 mole ratio.
If the usage quantity of aldehydes is less than 0.3 mole, then remaining phenolic monomers increases, so efficient is lower.
On the other hand, if the usage quantity of aldehydes greater than 1.0 moles, then the molecular weight of gained resin improves, and is therefore not preferred.
As the acid of using in the inventive method, so long as generally the acid of using in the manufacturing of novolac resin gets final product, for example can enumerate, oxalic acid, phosphoric acid, tosic acid and hydrochloric acid etc., they can use separately or mix more than 2 kinds and use.
If consider the corrosion of conversion unit etc., then preferred oxalic acid or phosphoric acid.
The usage quantity of preferred acid is 0.1～20 mass parts with respect to phenols 100 mass parts, preferably with 0.1～10 weight part, more preferably use with the ratio of 0.2～5 weight part.
In the present invention, also use calcium chloride as catalyst component.
Calcium chloride has calcium chloride and the anhydride that contains crystal water, preferred anhydride.
The usage quantity of preferably calcium chloride is 1～20 mass parts with respect to phenols 100 mass parts, preferably uses with the ratio of 2～10 weight parts.
If the usage quantity of calcium chloride is less than 1 mass parts, then the reactivity of phenols and aldehydes is low, and is therefore not preferred, if greater than 20 mass parts, then the effect of reactivity raising almost disappears, and is therefore impracticable.
The number-average molecular weight of the novolac resin that adopts manufacture method of the present invention and obtain is 200～500, is preferably 250～400, more preferably 250～350.
If number-average molecular weight in above-mentioned scope, then can reduce the melt viscosity of novolac resin, and give full play to effect as curing agent for epoxy resin.
In addition, dispersity is that weight-average molecular weight/number-average molecular weight is below 1.3, to be preferably below 1.2.
Dispersity is to mean below 1.3 that the polykaryon in the novolac resin is few.In order to reduce the melt viscosity of novolac resin, coenocytic content is reduced as far as possible.
In addition, the melt viscosity under 150 ℃ is below the 300mPas, to be preferably below the 250mPas.
If melt viscosity is below the 300mPas, then when using,, therefore can obtain the title complex of formability excellence because the flowability of title complex improves as curing agent for epoxy resin.
The method that makes the reaction of phenols and aldehydes is had no particular limits, for example can enumerate: add the method that phenols, aldehydes, calcium chloride and acid make its reaction in the lump; Or adding phenols, calcium chloride and acid, the method for under the temperature of reaction of regulation, adding aldehydes again.
This moment, temperature of reaction was preferably 30～120 ℃ scope.
If temperature is lower than 30 ℃, then Fan Ying carrying out is slower, and remaining unreacted phenols, and be therefore not preferred, in addition, if temperature greater than 120 ℃, then promotes the generation of high molecular weight components, therefore not preferred.
Reaction times is not particularly limited, as long as adjust according to amount, the temperature of reaction of aldehydes, calcium chloride and acid.
During reaction, certainly with an organic solvent.
As organic solvent, can use separately or merge more than 2 kinds and use following organic solvent: alcohols such as propyl alcohol, butanols, glycols such as ethylene glycol, propylene glycol, glycol ethers such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, butyleneglycol monomethyl ether, butyleneglycol list ethyl ether, butyleneglycol list propyl ether, ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ester classes such as propyl acetate, butylacetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,4-two
Ethers such as alkane etc.
Above-mentioned organic solvent can be according to being 0～1,000 mass parts with respect to phenols 100 mass parts, being preferably about 10～100 mass parts and using like that.
Yet,, preferably do not make water as solvent.
Because the water-soluble height of calcium chloride if therefore have water in the system, will dissolve immediately, in case calcium chloride forms the aqueous solution, reaction efficiency will descend, and is therefore not preferred.
In addition, because the reaction of phenols and aldehydes can generate condensation water, therefore along with the carrying out of reaction, calcium chloride is planar water and become dissolved state gradually, but does not just have special problem so long as not complete transparent state.
Yet,, can also use siccative such as calcium sulfate, silica gel, molecular sieve in order to prevent the calcium chloride adsorption moisture.
Above-mentioned siccative can be according to being about 0～20 mass parts with respect to phenolic compound 100 mass parts, being preferably about 0～10 mass parts and using like that.
After reaction finishes, can remove condensation water, can also wash as required in addition and remove calcium chloride and acid by distillation.
In addition, preferably remove unreacted phenols and/or unreacted aldehydes by carrying out underpressure distillation or wet distillation.
Embodiment
The embodiment and the comparative example that utilize manufacture method of the present invention to make novolac resin below are shown, are described more specifically the present invention, but the invention is not restricted to following examples.
Embodiment 1
In the flask that possesses cooling tube, stirrer, add phenol 100g, phenyl aldehyde 56g, calcium chloride 5g and oxalic acid 1g, it was reacted 3 hours down at 50 ℃.
Next, with pure water 100g washing 3 times, remove calcium chloride and oxalic acid.
Next, under 180 ℃, the decompression of 50mmHg, remove and distillate branch, thereby obtained novolac resin A 98g.
Fig. 1 shows gel permeation chromatography (GPC) figure of Resin A.Wherein, transverse axis represent dissolution time (minute).In Resin A, low-molecular-weight 2 nucleomes are principal products as shown in Figure 1.
Embodiment 2
Except using phosphatase 11 g replacement oxalic acid, react similarly to Example 1, thereby obtained novolac resin B 98g.
Embodiment 3
Except using isobutyric aldehyde 38g, react similarly to Example 1, thereby obtained novolac resin C 90g as the aldehydes.
Embodiment 4
Except use ortho-cresol 100g as phenols, use isobutyric aldehyde 33g as the aldehydes, react similarly to Example 1, thereby obtained novolac resin D 89g.
Comparative example 1
Add ortho-cresol 100g, phenyl aldehyde 49g and oxalic acid 1g in the flask that possesses cooling tube, stirrer, it was reacted 8 hours down at 100 ℃, bearing reaction does not carry out, can not get resin.
Comparative example 2
Add ortho-cresol 100g, phenyl aldehyde 49g, sodium-chlor 5g and oxalic acid 1g in the flask that possesses cooling tube, stirrer, it was reacted 8 hours down at 100 ℃, bearing reaction does not carry out, can not get resin.
Comparative example 3
In the flask that possesses cooling tube, stirrer, add phenol 100g, phenyl aldehyde 56g and tosic acid 10g, it was reacted 8 hours down at 100 ℃.
Next, neutralize, with pure water 100g washing 5 times, remove generation salt then with aqueous sodium hydroxide solution.
Next, under 180 ℃, the decompression of 50mmHg, remove and distillate branch, thereby obtained novolac resin E 83g.
Fig. 2 shows gel permeation chromatography (GPC) figure of resin E.Wherein, transverse axis represent dissolution time (minute).
As shown in Figure 2, in resin E, except generating 2 nucleomes, also generated the polykaryon of a great deal of.
Comparative example 4
Except using ortho-cresol, similarly react with comparative example 3, thereby obtained novolac resin F 77g as the phenols.
For the novolac resin that obtains in the novolac resin that obtains among the embodiment 1～3, the comparative example 3 and 4, adopt the following analysis method to measure, the value of gained is shown in table 1.
The analytical procedure of resin is as follows.
(1) number-average molecular weight, weight-average molecular weight, dispersity
(GPC) measures by gel permeation chromatography.
Post constitutes 2 KF-804 clear and electrician's (strain) makes of use, uses tetrahydrofuran (THF) as solvent, measures under flow 1ml/ minute.
Molecular weight calculates with polystyrene conversion, and content calculates with the percentage ratio in total peak area.
Dispersity calculates with weight-average molecular weight/number-average molecular weight.
(2) softening temperature (℃)
Using the エ レ Star Network ス length of schooling gas phase softening point measurement device EX-719PD of section is to measure under 2.5 ℃/minute at heat-up rate.
(3) melt viscosity (mPas)
Use リ サ one チ イ Network ウ イ Star プ society system ICI viscometer under 150 ℃, to measure.
Table 1
| Resin A | Resin B | Resin C | Resin D | Resin E | Resin F | |
| Number-average molecular weight | 310 | 300 | 290 | 290 | 670 | 610 |
| Weight-average molecular weight | 370 | 360 | 340 | 320 | 1700 | 1300 |
| Dispersity | 1.2 | 1.2 | 1.2 | 1.1 | 2.5 | 2.1 |
| Receipts amount (g) | 98 | 98 | 90 | 89 | 83 | 77 |
| Melt viscosity (mPas) | 225 | 210 | 31 | 34 | 2000 | 1000 |
| Softening temperature (℃) | 96 | 94 | 68 | 71 | 119 | 117 |
The industry utilizability
Novolac resin of the present invention because melt viscosity is low, thereby mobile high, uses it to significantly improve as the compositions of thermosetting resin of curing agent for epoxy resin flowability when the moulding.
Using under the situation of novolac resin of the present invention as semiconductor sealing material use, can to reduce the linear expansivity of moulding product low and/or reduce rate of moisture absorption, raising flame retardant resistance by increasing filling dose.
In addition, the cured article of novolac resin of the present invention has good thermotolerance, moistureproofness, mechanical characteristics, electrical insulating property, with the cohesiveness of metal etc., is very effective in needing the electronic material purposes of high reliability therefore.
Particularly, can be at the sealing material use resin combination of electronic unit, printed base plate with resin combination, printed base plate with adhere to the interlayer dielectic that uses in the Copper Foil of resin with using in resin combination, etching resisting ink, conducting paste (containing the electroconductibility weighting agent), coating, binding agent, the matrix material etc.
Claims (3)
1. the manufacture method of a novolac resin is characterized in that, in the presence of the catalyzer that comprises calcium chloride and acid, makes the reaction of phenols and aldehydes.
2. the manufacture method of novolac resin according to claim 1, wherein, acid is oxalic acid or phosphoric acid.
3. the manufacture method of novolac resin according to claim 1 and 2, it obtains, and number-average molecular weight is 200～500, dispersity is that weight-average molecular weight/number-average molecular weight is 1.3 below and the melt viscosity under 150 ℃ is a novolac resin below the 300mPas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009003353A JP5513747B2 (en) | 2009-01-09 | 2009-01-09 | NOVOLAC RESIN AND PROCESS FOR PRODUCING THE SAME |
| JP2009-003353 | 2009-02-19 | ||
| PCT/JP2009/070880 WO2010079673A1 (en) | 2009-01-09 | 2009-12-15 | Novolac resin and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102282188A true CN102282188A (en) | 2011-12-14 |
Family
ID=42316443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801541420A Pending CN102282188A (en) | 2009-01-09 | 2009-12-15 | Novolac resin and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5513747B2 (en) |
| KR (1) | KR101348994B1 (en) |
| CN (1) | CN102282188A (en) |
| TW (1) | TWI465488B (en) |
| WO (1) | WO2010079673A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119500A (en) * | 2013-04-23 | 2014-10-29 | 宝山钢铁股份有限公司 | Epoxy-resin curing agent and preparation method thereof |
| CN106068292A (en) * | 2014-03-20 | 2016-11-02 | Dic株式会社 | Phenolic varnish type phenolic hydroxy group resin, its manufacture method, solidification compound, protective agent compositions and colourama resist |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101869929B1 (en) * | 2011-06-03 | 2018-06-21 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Phenolic resin and material for forming underlayer film for lithography |
| WO2014178348A1 (en) * | 2013-04-30 | 2014-11-06 | 明和化成株式会社 | Phenolic resin, epoxy resin composition and cured product using same, copper-clad laminate, and semiconductor sealing material |
| WO2017069063A1 (en) * | 2015-10-19 | 2017-04-27 | 日産化学工業株式会社 | Resist underlayer film-forming composition containing long-chain alkyl group-containing novolac |
| WO2023068089A1 (en) * | 2021-10-22 | 2023-04-27 | 日本化薬株式会社 | Phenolic resin, epoxy resin, curable resin composition, and cured product thereof |
| JP7251006B1 (en) * | 2021-10-22 | 2023-04-03 | 日本化薬株式会社 | Phenolic resins, epoxy resins, curable resin compositions, and cured products thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2954398B2 (en) * | 1991-07-22 | 1999-09-27 | 花王株式会社 | Resin composition for producing ester-curable mold and method for producing mold |
| JP2002128849A (en) * | 2000-10-26 | 2002-05-09 | Sumitomo Bakelite Co Ltd | Method of manufacturing phenol resin |
| JP4855641B2 (en) * | 2003-05-13 | 2012-01-18 | 旭有機材工業株式会社 | Method for producing novolac type phenolic resin |
| JP2007297574A (en) * | 2006-04-27 | 2007-11-15 | Toshio Honda | New method for producing resorcinol resin containing unreacted resorcinol in reduced amount |
-
2009
- 2009-01-09 JP JP2009003353A patent/JP5513747B2/en not_active Expired - Fee Related
- 2009-12-15 CN CN2009801541420A patent/CN102282188A/en active Pending
- 2009-12-15 WO PCT/JP2009/070880 patent/WO2010079673A1/en active Application Filing
- 2009-12-15 KR KR1020117015548A patent/KR101348994B1/en not_active IP Right Cessation
-
2010
- 2010-01-06 TW TW099100138A patent/TWI465488B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119500A (en) * | 2013-04-23 | 2014-10-29 | 宝山钢铁股份有限公司 | Epoxy-resin curing agent and preparation method thereof |
| CN106068292A (en) * | 2014-03-20 | 2016-11-02 | Dic株式会社 | Phenolic varnish type phenolic hydroxy group resin, its manufacture method, solidification compound, protective agent compositions and colourama resist |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
| CN111205799B (en) * | 2020-02-28 | 2021-01-19 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201033255A (en) | 2010-09-16 |
| WO2010079673A1 (en) | 2010-07-15 |
| KR101348994B1 (en) | 2014-01-09 |
| JP2010159362A (en) | 2010-07-22 |
| JP5513747B2 (en) | 2014-06-04 |
| KR20110102409A (en) | 2011-09-16 |
| TWI465488B (en) | 2014-12-21 |
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