CN102516497B - Fluorine-containing resin, preparation method thereof, conformal coating and printed circuit board - Google Patents
Fluorine-containing resin, preparation method thereof, conformal coating and printed circuit board Download PDFInfo
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- CN102516497B CN102516497B CN 201110316774 CN201110316774A CN102516497B CN 102516497 B CN102516497 B CN 102516497B CN 201110316774 CN201110316774 CN 201110316774 CN 201110316774 A CN201110316774 A CN 201110316774A CN 102516497 B CN102516497 B CN 102516497B
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Abstract
The invention provides a fluorine-containing resin. The molecular structure of the fluorine-containing resin contains a plurality of carbon-carbon double bonds, a methylene group is between at least two carbon-carbon double bonds in all the carbon-carbon double bonds, and the fluorine-containing resin is a fluorine-containing epoxy resin. The invention also provides a preparation method of the fluorine-containing resin. According to the method, a fluorine atom-containing epoxy resin precursor and an unsaturated fatty acid with the molecular structure containing a plurality of the carbon-carbon double bonds and the methylene group between at least two carbon-carbon double bonds in all the carbon-carbon double bonds undergo a condensation reaction and/or a ring-opening addition reaction. The invention further provides a conformal coating containing the fluorine-containing resin of the invention, and a printed circuit board containing the fluorine-containing resin of the invention. The adhesion force of a coating layer formed after the curing of the conformal coating containing the fluorine-containing resin of the invention to the printed circuit board reaches 5B, the hardness reaches a B grade, the flexibility is 0.5mm, the surface energy is 16.56-17.51mJ/cm<2>, and the voltage resistance is higher than 10,000V; and no foaming appears after fifty cycles when the printed circuit board which is sprayed with the conformal coating of the invention and is completely cured is immersed in 50DEG C water.
Description
The application is that the application number that proposed on December 19th, 2008 is 200810186468.9, name is called dividing an application of " fluorine resin and preparation method thereof and conformal coating and printed-wiring board (PWB) ".
Technical field
The conformal coating and the printed-wiring board (PWB) that the invention relates to a kind of fluorine resin and preparation method thereof and contain this fluorine resin.
Background technology
Conformal coating is one deck protecting materials that is coated on the printed-wiring board (PWB) (PCB) that welds plug connector elements; after solidifying fully, dope layer can strengthen protection against the tide and the antifouling ability of electronic circuit and components and parts; prevent that solder joint and conductor from suffering erosion; also can play shielding and eliminate electromagnetic interference and prevent the effect of line short, improve the insulating property of wiring board.In addition, the dope layer protective membrane also is conducive to improve rub resistance and the solvent resistance of circuit and components and parts, and can release temperature the pressure that causes of periodical change, improve the stability of electronic product, prolong the work-ing life of electronic product.According to the difference of curing mode, conformal coating can be divided into single curing, for example: and ultraviolet light polymerization, thermofixation, moisture solidification, electricity curing and air curing etc., and two curing, for example: light-moisture solidification, light-thermofixation and light-chemosetting etc.; According to the difference of using resin system, conformal coating can be divided into epoxy type, acrylic type, polyurethane-type or terephthalylidene type etc.The concrete coating of which kind of curing mode that adopts needs to decide according to the Working environment of execution conditions, coating cost and pcb board.
For example, US4451523 discloses a kind of not solvent-laden coating, and described coating contains at least a carbamate-acrylate or carbamate-methacrylate compound, contain allylic carbamate or contain allylic methacrylate compound, do not contain allylic acrylate or methacrylate compound, light trigger and metal siccative as thinner.Above-mentioned coating adopts the two methods of solidifying of light-chemosetting to realize the curing fully of dope layer, there be not the dark areas of irradiate light, need impel allyl group to be cured reaction as catalyzer by the metal-salt more than the divalence and unsaturated organic acid, obtain the dope layer of completion of cure.
Though the conformal coating of above-mentioned various resin systems can both satisfy the requirement of general electronic devices and components, and have certain moistureproofness, water tolerance and a withstand voltage properties, but can only be used for humidity resistance and the less demanding PCB of withstand voltage properties, occasion for the condition harshness is just no longer suitable, in the time of need being in hot and humid environment for a long time even needing not timing to be immersed in the water as wiring board, distance is very near and when having high voltage between the wiring board stitch, more than the coating of several systems all can not meet the demands.And the curing speed of the disclosed coating of US4451523 is slow, and therefore, the conformal coating of development of new is very urgent with the service requirements of satisfying severe rugged environment.
Summary of the invention
The water tolerance, moistureproofness and the proof voltage that the objective of the invention is to overcome existing conformal coating can not satisfy service requirements and the slow shortcoming of curing speed of severe rugged environment, the ambient cure of a kind of energy is provided, and solidify the back dope layer and have excellent hydrophobic property and withstand voltage properties, and wiring board is had the fluorine resin of good adhesion property; The present invention also provides the preparation method of this fluorine resin; The present invention also further provides conformal coating and the printed-wiring board (PWB) that comprises described fluorine resin.
The invention provides a kind of fluorine resin, contain a plurality of carbon-carbon double bonds in the described fluorine resin molecular structure, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; Described fluorine resin is fluorine-containing epoxy resin.
The present invention also provides the preparation method of described fluorine resin, this method comprises that resin precursor and the unsaturated fatty acids that will contain fluorine atom carry out condensation reaction and/or opening under catalyst action, wherein, contain a plurality of carbon-carbon double bonds in the described monounsaturated fatty acid molecule structure, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; The described resin precursor that contains fluorine atom is the Resins, epoxy precursor that contains fluorine atom, and the carbonatoms of described unsaturated fatty acids is 8-36.
The present invention also provides a kind of conformal coating, and described conformal coating comprises matrix resin and siccative, and wherein, described matrix resin is by fluorine resin provided by the invention.
The present invention also further provides a kind of printed-wiring board (PWB), and described printed-wiring board (PWB) comprises wiring board and conformal coating layer, wherein, and the layer of described conformal coating layer for being solidify to form by conformal coating provided by the invention.
Contain a plurality of carbon-carbon double bonds in the fluorine resin molecular structure of the present invention, and the methylene radical of being separated by between at least two in a plurality of carbon-carbon double bonds, described methylene radical activity is higher, in the presence of suitable catalyzer, do not use uv equipment, can be generated free radical by the oxidation of airborne oxygen institute under the normal temperature, thereby initiation curing reaction, and the speed of curing reaction is fast, the state of cure height of dope layer, can access the dope layer of completion of cure, described dope layer has good mechanical performance and thermal characteristics; And also contain a large amount of fluorine atoms in the above-mentioned fluorine resin molecular structure, thereby make dope layer have excellent in water resistance, moistureproofness and withstand voltage properties.Therefore, be not clamminess and the hardness height, have good mechanical performance, excellent in water resistance, moistureproofness and withstand voltage properties in the surface that sprays to the dope layer that forms after solidifying on the printed-wiring board (PWB) as the conformal coating of matrix resin preparation with fluorine resin of the present invention.
Concrete, the conformal coating that contains fluorine resin of the present invention solidifies dope layer that the back forms the sticking power of printed-wiring board (PWB) is reached 5B, and hardness reaches the B level, and snappiness is 0.5mm, and surface energy is at 16.56-17.51mJ/cm
2Between, proof voltage is higher than 10000 volts; Sprayed conformal coating of the present invention and dope layer and solidified complete printed-wiring board (PWB) and also have good water tolerance, be immersed in 50 ℃ the water, 50 circulations are non-foaming.
Embodiment
The invention provides a kind of fluorine resin, contain a plurality of carbon-carbon double bonds in the described fluorine resin molecular structure, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two.
The existence of fluorine atom can reduce the surface energy of resin, thereby greatly improves water tolerance and the moistureproofness of resin, and also helpful for the withstand voltage properties that improves resin.
The introducing of the methylene radical between two carbon-carbon double bonds can make resin realize ambient cure, reaches the purpose of the mechanical property that improves resin.
Because as long as contain fluorine atom in the molecular structure of resin and the methylene radical between two carbon-carbon double bonds can be realized purpose of the present invention, therefore, fluorine resin of the present invention can be for containing fluorine atom and a plurality of carbon-carbon double bond simultaneously in the molecular structure, and any one resin of the methylene radical of being separated by between at least two carbon-carbon double bonds.For example: contain fluorine atom and a plurality of carbon-carbon double bond in the molecular structure simultaneously, and in epoxy resin, polyurethane-type resin, polyether-ether-ketone type resin, polyethersulfone type resin, polyimide type resin, polycarbonate type resin and the polyamides amine type resin of the methylene radical of being separated by between at least two carbon-carbon double bonds one or more.When fluorine resin of the present invention is used as the matrix resin of conformal coating, described fluorine resin is preferably and contains fluorine atom and a plurality of carbon-carbon double bond in the molecular structure simultaneously, and epoxy resin and/or the polyurethane-type resin of the methylene radical of being separated by between at least two carbon-carbon double bonds.
Because extensive, the cheap while synthesis technique of raw material sources of Resins, epoxy is simple, therefore, fluorine resin of the present invention is preferably and contains fluorine atom and a plurality of carbon-carbon double bond in the molecular structure simultaneously, and the epoxy resin of the methylene radical of being separated by between at least two carbon-carbon double bonds.Contain fluorine atom and a plurality of carbon-carbon double bond in the molecular structure of the present invention simultaneously, and the epoxy resin of the methylene radical of being separated by between at least two carbon-carbon double bonds is preferably the fluorine-containing epoxy resin shown in the formula 1.
Formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Can be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one can be F or CF
3R can be for containing the alkyl of a plurality of carbon-carbon double bonds, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; N can be the integer of 0-10.
Described fluorine-containing epoxy resin is the structure shown in the formula 2 more preferably:
Formula 2:
Wherein, R can be the alkyl of 7-35 for carbonatoms.
The molecular weight of resin and the intensity of resin and processing characteristics are closely related, and therefore, the molecular weight of resin is to synthesize, need in processing and the application process important indicator considered.In order further to improve the processibility of resin, n can be the integer of 0-10 in the above-mentioned fluorine-containing epoxy resin, is preferably the integer of 0-5, more preferably 0.
Contain fluorine atom and a plurality of carbon-carbon double bond in the described molecular structure simultaneously, and the structure optimization of the polyurethane-type resin of the methylene radical of being separated by between at least two carbon-carbon double bonds is for as shown in the formula shown in 3:
Formula 3:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Can be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one can be F or CF
3R can be for containing the alkyl of a plurality of carbon-carbon double bonds, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; P can be the integer of 5-8, and m can be the integer of 4-10.
The structure of above-mentioned fluorochemical urethane type resin is more preferably as shown in the formula shown in 4:
Formula 4:
Wherein, R can be the alkyl of 7-35 for carbonatoms.
R in the molecular structure of the fluorochemical urethane type resin shown in the fluorine-containing epoxy resin shown in above-mentioned formula 1 and the formula 2 and formula 3 and the formula 4 is the alkyl that contains a plurality of carbon-carbon double bonds, and the methylene radical of being separated by between at least two carbon-carbon double bonds.In order further to improve processibility and the thermostability of resin, above-mentioned formula 1 is that carbonatoms is the straight-chain alkyl of 7-35 to the R of the fluorine resin shown in the formula 4, and under the preferable case, R can be the straight-chain alkyl of the integer of 7-30 for carbonatoms.Described R more preferably
-(CH
2)
xCH=CH-CH
2-CH=CH (CH
2)
yCH
3, wherein, x is the integer of 1-24, y is the integer of 0-23, and x+y is the integer of 1-24; And/or
-(CH
2)
eCH=CH-CH
2-CH=CH-CH
2-CH=CH (CH
2)
fCH
3, wherein, e is the integer of 1-21, f is the integer of 0-20, and e+f is the integer of 1-21.
Concrete, described R can for
-(CH
2)
7CH=CH-CH
2-CH=CH (CH
2)
4CH
3And/or
-(CH
2)
7CH＝CH-CH
2-CH＝CH-CH
2-CH＝CHCH
2CH
3。
The present invention also provides the preparation method of above-mentioned fluorine resin, this method comprises that resin precursor and the unsaturated fatty acids that will contain fluorine atom carry out condensation reaction and/or opening under catalyst action, wherein, contain a plurality of carbon-carbon double bonds in the described monounsaturated fatty acid molecule structure, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two.
The present invention carries out condensation reaction and/or opening by making the resin precursor and the unsaturated fatty acids that contain fluorine atom under catalyst action, make to form chemical bond between the resin precursor contain fluorine atom and the unsaturated fatty acids, thereby obtain fluorine resin of the present invention.Therefore, should contain the group that can carry out condensation reaction and/or opening with the carboxyl of unsaturated fatty acids in the described resin precursor molecular structure that contains fluorine atom, for example: one or more in hydroxyl, amido and the epoxy group(ing), but be not limited to this.
The described resin precursor that contains fluorine atom can for contain in the molecular structure fluorine atom and can with any one resin of the group of the carboxyl generation condensation reaction of unsaturated fatty acids and/or opening.For example: contain the polyimide resin of the Resins, epoxy of fluorine atom, hydroxy-end capped urethane resin, hydroxy-end capped polyether-ether-ketone resin, hydroxy-end capped polyethersulfone resin, amido end-blocking, hydroxy-end capped polycarbonate resin and polyamide resin of amido end-blocking etc. in the molecular structure.When fluorine resin of the present invention during as the matrix resin of conformal coating, the described resin precursor that contains fluorine atom is preferably the Resins, epoxy precursor that contains fluorine atom and contains fluorine atom and with hydroxy-end capped urethane resin precursor.
The described Resins, epoxy precursor that contains fluorine atom is preferably the Resins, epoxy precursor shown in the formula 5.
Formula 5:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Can be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one can be F or CF
3N can be the integer of 0-10.
Concrete, the described Resins, epoxy precursor that contains fluorine atom can be the structure shown in the formula 6.
Formula 6:
The described structure optimization that contains the hydroxy-end capped urethane resin precursor of fluorine atom is as shown in the formula the structure shown in 7.
Formula 7:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Can be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one can be F or CF
3R can be for containing the alkyl of a plurality of carbon-carbon double bonds, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; P can be the integer of 5-8, and m can be the integer of 4-10.
Concrete, the described hydroxy-end capped urethane resin precursor that contains fluorine atom can be the structure shown in the formula 8:
Formula 8:
The Resins, epoxy precursor that contains fluorine atom shown in the formula 6 can make by making hexafluoro bisphenol-a and epoxy chloropropane carry out polycondensation under the basic catalyst effect.Concrete, described hexafluoro bisphenol-a and epoxy chloropropane adopt the raw material that is purchased to get final product, for example the hexafluoro bisphenol-a of sea, Shanghai Qu Huagong company limited, German Honeywell or E.I.Du Pont Company's production; The epoxy chloropropane that Dow Chemical, Solvay, Spolek, Zachem, Asahi Glass, Sumitomo Chemical or South Asia company produce.The hexafluoro bisphenol-a that uses in the embodiment of the invention is that epoxy chloropropane is available from Dow Chemical available from sea, Shanghai Qu Huagong company limited.Described polycondensation comprises two reactions in fact, i.e. coupled reaction and the reaction of deviating from hydrogenchloride.Described first reaction, it is coupled reaction, can adopt this area coupling type basic catalyst commonly used, quaternary ammonium salt for example, quaternary ammonium salt commonly used comprises tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide or Tetrabutyl amonium bromide.Since the alkalescence of coupling type basic catalyst a little less than, deficiency so that hydrogenchloride deviate from, therefore, after coupled reaction is finished, also need to replenish the alkali-metal oxyhydroxide of adding in the reaction mixture that obtains, for example: sodium hydroxide or potassium hydroxide make the reaction of hydrogenchloride to be finished smoothly.In the described coupled reaction, the mol ratio of hexafluoro bisphenol-a, epoxy chloropropane and coupling type basic catalyst is 1: 1.4-10: 0.1-0.2, and temperature of reaction is 50-60 ℃, the reaction times is 2-4 hour; After coupled reaction is finished, in the reaction mixture that obtains, add potassium hydroxide and/or sodium hydroxide, namely enter the reaction of hydrogenchloride, wherein, the mol ratio of hexafluoro bisphenol-a and sodium hydroxide and/or potassium hydroxide can be 1: 0.9-1.0, temperature of reaction can be 65-75 ℃, and the reaction times can be 3-5 hour.Adjust the mol ratio between hexafluoro bisphenol-a and the epoxy chloropropane, and the temperature of reaction of control polycondensation and reaction times can be regulated and control to the number-average molecular weight of the Resins, epoxy precursor that contains fluorine atom.
The method of the Resins, epoxy precursor that contains fluorine atom shown in the above-mentioned preparation formula 6 and reaction conditions also are applicable to the Resins, epoxy precursor that contains fluorine atom shown in the preparation formula 5, and different is to adopt the different biphenol monomer that contains fluorine atom of molecular structure to replace hexafluoro bisphenol-a and epoxy chloropropane to carry out polycondensation.
The hydroxy-end capped urethane resin precursor that contains fluorine atom shown in the formula 8 can be by the polycondensation between hexafluoro bisphenol-a and the hexamethylene diisocyanate, and adopts this area method for preparing urethane resin commonly used to make.Adjust the mol ratio between hexafluoro bisphenol-a and the hexamethylene diisocyanate and make hexafluoro bisphenol-a and the mol ratio of hexamethylene diisocyanate greater than 1, can obtain hydroxy-end capped and polymkeric substance that have different number-average molecular weights, be not described in detail here.Adopt the different biphenol monomer that contains fluorine atom of molecular structure to replace hexafluoro bisphenol-a can obtain the hydroxy-end capped urethane resin precursor that contains fluorine atom shown in the formula 7.
The R of unsaturated fatty acids RCOOH is the alkyl that contains a plurality of carbon-carbon double bonds described in the method for preparing fluorine resin of the present invention, and the methylene radical of being separated by between two carbon-carbon double bonds.The R of described unsaturated fatty acids can for contain a plurality of carbon-carbon double bonds simultaneously carbonatomss be the alkyl of 7-35, and the methylene radical of being separated by between at least two carbon-carbon double bonds.In order further to improve the thermotolerance of fluorine resin of the present invention, described unsaturated fatty acids is preferably:
CH
3(CH
2)
yCH=CH-CH
2-CH=CH (CH
2)
x-COOH, wherein, x is the integer of 1-24, y is the integer of 0-23, and x+y is the integer of 1-24; And/or
CH
3(CH
2)
fCH=CH-CH
2-CH=CH-CH
2-CH=CH (CH
2)
e-COOH, wherein, e is the integer of 1-21, f is the integer of 0-20, and e+f is the integer of 1-21.
Unsaturated fatty acids of the present invention can be the unsaturated organic acid of originating arbitrarily, both can adopt and synthesize for chemical process well known to those skilled in the art, also can utilize the unsaturated organic acid that refines from the material that nature exists.From being easy to get property of raw material and point of view of environment protection, the preferred described unsaturated organic acid of the present invention is linolenic acid and/or linolic acid.The structure of above-mentioned linolenic and linoleic respectively as shown in the formula 9 and formula 10 shown in:
Formula 9:
CH
3(CH
2)
4CH＝CH-CH
2-CH＝CH(CH
2)
7-COOH；
Formula 10:
CH
3CH
2CH＝CH-CH
2-CH＝CH-CH
2-CH＝CH(CH
2)
7-COOH。
According to the preparation method of fluorine resin of the present invention, describedly contain the resin precursor of fluorine atom and unsaturated fatty acids carries out condensation reaction under the effect of catalyzer and/or opening can obtain fluorine resin of the present invention.The catalyzer that uses in described condensation reaction and/or the opening can be basic catalyst or an acidic catalyst, and described basic catalyst and an acidic catalyst can carry out the catalyzer commonly used of condensation reaction and/or opening for this area is used for catalysis organic acid and hydroxyl, amido or epoxy group(ing).But, when the resin precursor that contains fluorine atom is when containing the Resins, epoxy of hydroxyl, adopted according to Liao Ming and Chen Ping writes " macromolecular material " (Chemical Industry Press, 2005) record in the 94-95 page or leaf, for make the organic acid carboxyl optionally with epoxy reaction, and not with or substantially not with hydroxyl reaction, described catalyzer adopts basic catalyst.Described basic catalyst is preferably one or more in the refined reagent of sodium alkyl, potassium alkyl, butyllithium and Gree, and described alkyl can be C
1-C
5Straight chained alkyl.The described mol ratio that contains Resins, epoxy precursor, unsaturated organic acid and the basic catalyst of fluorine atom can be 1: 1.2-2: 0.2-0.5, and temperature of reaction can be 100-125 ℃, the reaction times can be 4-6 hour.
The resin precursor that contains fluorine atom of the present invention also is preferably the hydroxy-end capped urethane resin precursor that contains fluorine atom, and fluorine resin is to make by the condensation reaction between the carboxyl of the hydroxyl of the urethane resin precursor that contains fluorine atom and unsaturated fatty acids.Condensation reaction between described hydroxyl and the carboxyl can adopt this area reaction conditions commonly used to carry out, and repeats no more here.
The present invention also provides a kind of conformal coating, and described conformal coating contains matrix resin and siccative, and wherein, described matrix resin is according to fluorine resin of the present invention.
Contain a plurality of carbon-carbon double bonds in the molecular structure according to the matrix resin of conformal coating of the present invention, and the methylene radical of being separated by between at least two carbon-carbon double bonds in a plurality of carbon-carbon double bond.Described methylene radical between two carbon-carbon double bonds has very high reactive behavior under the situation that suitable siccative exists, can generate free radical under the effect of oxygen in air, thereby causes curing reaction.Therefore, need not to react at normal temperatures by external energies such as light, heat as the conformal coating of matrix resin with fluorine resin of the present invention and be cured, obtain the dope layer of completion of cure; And contain the surface property that a large amount of fluorine atoms can improve coating in the fluorine resin molecular structure of the present invention, and improve water tolerance, moistureproofness and the withstand voltage properties of coating.Therefore, fluorine resin of the present invention is suitable as the matrix resin of conformal coating.
Described siccative is the main auxiliary agent of conformal coating of the present invention, and its effect is oxidation, polymerization and the drying of accelerating dope layer, reaches the purpose of quick-drying.Siccative of the present invention can be in molysite, zirconates or the rare earth metal salt one or more.Described molysite, zirconates or rare earth metal salt can be naphthenate, isocaprylic acid hydrochlorate, neodecanoate or Semen Lini oil soap.Siccative of the present invention also can be used for two or more siccative, with cobalt salt, manganese salt or lead salt as main siccative, one or more in cobalt naphthenate, cobalt iso-octoate, manganese iso-octoate, isocaprylic acid lead, manganese naphthenate and the lead naphthenate for example, with zinc salt and/or calcium salt as auxiliary siccative, one or more in isocaprylic acid zinc, calcium iso-octoate, zinc naphthenate and the calcium naphthenate for example; The weight ratio of described main siccative and auxiliary siccative can be 1: 0.5-1.In order further to reduce the cost of conformal coating, under the prerequisite of guaranteeing the conformal coating performance, can reduce the consumption of siccative as far as possible.Total amount with matrix resin in the conformal coating is benchmark, and the consumption of siccative of the present invention can be 0.01-5 weight %, is preferably 0.03-2 weight %.
Under the preferable case, described conformal coating also contains one or more in flow agent, defoamer and the fluorescent material, and is benchmark with the total amount of described conformal coating, and the total amount of described flow agent, defoamer and fluorescent material can be 0-6 weight %.
Concrete, in order to improve the surface effect of conformal coating, can contain flow agent in the conformal coating of the present invention.The present invention can be this area flow agent commonly used to kind and the consumption and without particular limitation of flow agent, and for example: the trade mark is the flow agent of BYK333, BYK331, AFCONA3034 or AFCONA3770.The present invention also has no particular limits the consumption of flow agent, as long as can guarantee that the surfacing of shape dope layer is bright and clean, total amount with conformal coating is benchmark, and the consumption of flow agent can be 0-2 weight % in the conformal coating of the present invention, is preferably 0.5-1.5 weight %.
For the dope layer that makes preparation has detectability, can also comprise fluorescent material in the conformal coating of the present invention.The present invention has no particular limits the kind of fluorescent material, uses this area fluorescent material commonly used to get final product, for example: the blue colour fluorescent powder of the grand company of blue colour fluorescent powder or Taiwan of the rich company of Guangzhou name.The present invention also has no particular limits consumption and the glow color under UV-light of fluorescent material, as long as the add-on of fluorescent material can make the color that dope layer can be luminous and luminous under the irradiation of UV-light can be by the visual inspection defective.But from the angle of controlling cost, be benchmark with the total amount of conformal coating, the consumption of the fluorescent material in the conformal coating of the present invention can be 0-2 weight %, is preferably 0.01-1.5 weight %.
Can also contain defoamer in the conformal coating of the present invention.Defoamer can reduce the surface tension of conformal coating glue, prevents that foam from forming or reducing original foam.Defoamer of the present invention can be this area defoamer commonly used, for example saturated alcohol, lipid acid and ester class thereof, higher fatty acid metallic soap class, sulphonated oil and organic silicone oil.The preferred defoamer of the present invention can be the defoamer of AFCONA2045, AFCONA2022, BYK052 or BYK065 for the trade mark.Total amount with conformal coating is benchmark, and the consumption of the defoamer in the conformal coating of the present invention can be 0-2 weight %, is preferably 0.5-1.5 weight %.
The present invention is also without particular limitation for the preparation method of conformal coating, with matrix resin, siccative and other filler, for example: flow agent, fluorescent material and defoamer, mix, the pack sealing gets final product.In order to prolong the storage period of described conformal coating, charge into for example nitrogen of rare gas element before can after pack, sealing.For each component that further makes conformal coating mixes, obtain the conformal coating of stable homogeneous, conformal coating of the present invention can achieve the above object by adding thinner.Conformal coating in the embodiment of the invention adopts has the method for the solution blending under the thinner existence to make.Because the evaporation rate by the control thinner can also be regulated and control the solidification rate of conformal coating, therefore, thinner of the present invention can be the thinner of quick-dry type, the boiling point of described quick-dry type thinner is less than 100 ℃, for example one or more in ethyl acetate, acetone, tetrahydrofuran (THF) and the butanone; Conformal coating of the present invention also can be middle dry type thinner, described in the boiling point of dry type thinner between 110-145 ℃, one or more in toluene, dimethylbenzene, N-BUTYL ACETATE and the butanols for example; Conformal coating of the present invention can also be slow curing type thinner, and the boiling point of described slow curing type thinner is between 145-170 ℃, for example: one or more in ethylene glycol n-butyl ether, ethylene glycol ethyl isobutyl ether and the ethyl cellosolve acetate.Above-mentioned quick-dry type, middle dry type and slow curing type thinner can use separately, also can use the mixture of above-mentioned three class thinners.Conformal coating of the present invention is also without particular limitation to the consumption of thinner, applies operational requirement as long as each component of conformal coating is mixed and satisfy.But from reducing cost and point of view of environment protection, be benchmark with the total amount of conformal coating, the consumption of thinner of the present invention can be 15-60 weight %, is preferably 40-60 weight %.
The present invention also further provides the printed-wiring board (PWB) that comprises above-mentioned conformal coating, and described printed-wiring board (PWB) comprises wiring board and conformal coating layer.
Because containing fluorine resin of the present invention by interpolation in conformal coating, the present invention make printed-wiring board (PWB) have excellent water tolerance, moistureproofness and dielectric properties, therefore, the present invention is for structure and the not special restriction of formation method of printed-wiring board (PWB), and described wiring board adopts the printed-wiring board (PWB) that is purchased to get final product.
The curing that contains the printed-wiring board (PWB) of conformal coating of the present invention needs only can be carried out in the presence of oxygen or air, and described curing both can be carried out at normal temperatures, also can carry out under the condition of heating.Described normal temperature is that temperature is generally 15-35 ℃, and be 2-5 hour set time; The described temperature that is heating and curing is generally 50-100 ℃, and be 2-4 hour set time.Be cured as ambient cure in the embodiment of the invention, be about to wiring board of the present invention and place drying, clean environment, under 15-40 ℃, solidified 2-5 hour.The present invention also has no particular limits for the thickness of the dope layer that conformal coating forms, and the thickness of the conformal coating layer that employing those skilled in the art use always gets final product, for example 20-60 μ m.Conformal coating of the present invention has excellent performance, and from the angle of controlling cost, the thickness of the dope layer that conformal coating of the present invention solidify to form is preferably 30-45 μ m.
The present invention introduces the alkyl that contains a plurality of carbon-carbon double bonds by chemical reaction in the fluorine resin molecular structure, and the methylene radical of being separated by between at least two carbon-carbon double bonds.Described methylene radical has very high reactive behavior under the effect of suitable siccative, just can form complete conformal coating layer by fast setting under the normal temperature.Therefore, use the conformal coating of fluorine resin of the present invention preparation to use up, to be cured under the condition of external energy such as heat not making, give the mechanical property of dope layer excellence, and the degree of curing reaction is not subjected to the restriction of the structure of printed-wiring board (PWB), can access the conformal coating layer of completion of cure, have very high production efficiency.Owing to contain a large amount of fluorine atoms in the molecular structure of fluorine resin of the present invention, therefore conformal coating of the present invention not only can be given the good water tolerance of printed-wiring board (PWB) and humidity resistance, can also further improve thermostability and the elctrical stability of printed-wiring board (PWB).
Describe the present invention in detail below in conjunction with embodiment.The resin precursor that contains fluorine atom that adopts among the embodiment of the invention 1-5 is the Resins, epoxy precursor that contains fluorine atom shown in the formula 6, and the resin precursor that contains fluorine atom that adopts among the embodiment 6 is the hydroxy-end capped urethane resin precursor that contains fluorine atom shown in the formula 8.Among following examples 1-6, the method for employing GPC is measured number-average molecular weight and the molecular weight distribution of the resin precursor and the fluorine resin that contain fluorine atom.Among the embodiment 1-5, the method that adopts GB4612-84 to stipulate is measured the epoxy equivalent (weight) of the Resins, epoxy precursor that contains fluorine atom, and the method that adopts HG/T 2709-95 to stipulate is measured the hydroxy radical content of fluorine-containing epoxy resin.The method that adopts GB6743-86 to stipulate among the embodiment 6 detects the NCO content of the urethane resin precursor that contains fluorine atom.
Embodiment 1
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
In the 500ml there-necked flask, add 36.6g hexafluoro bisphenol-a, 75.0g epoxy chloropropane and 150mlN-methyl-2-pyrrolidone as reaction solvent, treat that above-mentioned two kinds of reactants dissolve the tetrabutylammonium chloride that the back adds 2.75g fully, react 3 hours down at 55 ℃; Then, in reaction system, add 4g sodium hydroxide, reacted 4 hours down at 70 ℃.After reaction is finished, carry out purifying with the method for underpressure distillation and namely obtain the Resins, epoxy precursor that contains fluorine atom of the present invention.This epoxy equivalent (weight) that contains the Resins, epoxy precursor of fluorine atom is 410, and number-average molecular weight is 840, and molecular weight distribution is 1.05, corresponding to the Resins, epoxy precursor that contains fluorine atom of the n=1 in the structural formula 6.
The Resins, epoxy precursor 75g that contains fluorine atom that makes is placed the 500ml there-necked flask, add the 150ml N-Methyl pyrrolidone as reaction solvent, back adding 40g linolic acid stirs, use oil bath heating, make the temperature of reaction system be increased to 110 ℃, add butyllithium 2.35g, begin to carry out esterification, react after 4 hours, the pH value of reaction system remains unchanged substantially, shows to react to finish, and extracts with 100ml water then, and the collection organic phase, the organic phase that obtains carries out namely obtaining fluorine resin of the present invention after drying and underpressure distillation steam solvent.The hydroxy radical content of this fluorine resin is 3.61g/100g, and number-average molecular weight is 1400, and molecular weight distribution is 1.08, corresponding to the fluorine resin of n=1 in the structural formula 2.
Embodiment 2
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
In the 500ml there-necked flask, add 36.6g hexafluoro bisphenol-a, 19.3g epoxy chloropropane and 100mlN-methyl-2-pyrrolidone as reaction solvent, treat that above-mentioned two kinds of reactants dissolve the tetrabutylammonium chloride that the back adds 2.75g fully, react 4 hours down at 60 ℃; Then, in reaction system, add 4g sodium hydroxide, reacted 5 hours down at 70 ℃.After reaction is finished, carry out purifying with the method for underpressure distillation and namely obtain the Resins, epoxy precursor that contains fluorine atom of the present invention.This epoxy equivalent (weight) that contains the Resins, epoxy precursor of fluorine atom is 1215, number-average molecular weight 2400, and molecular weight distribution is respectively 1.09, corresponding to the Resins, epoxy precursor that contains fluorine atom of the n=5 in the structural formula 6.
The Resins, epoxy precursor 25g that contains fluorine atom that makes is placed the 100ml there-necked flask, add the 25ml N-Methyl pyrrolidone as reaction solvent, back adding 4g linolenic acid stirs, use oil bath heating, make the temperature of reaction system be increased to 110 ℃, add butyllithium 0.25g, begin to carry out esterification, react after 6 hours, the pH value of reaction system remains unchanged substantially, shows to react to finish, and extracts with 100ml water then, and the collection organic phase, the organic phase that obtains carries out namely obtaining fluorine resin of the present invention after drying and underpressure distillation steam solvent.The hydroxy radical content of this fluorine resin is 4.1g/100g, and number-average molecular weight is 3000, and molecular weight distribution is 1.1, corresponding to the fluorine resin of n=5 in the structural formula 2.
Embodiment 3
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
In the 500ml there-necked flask, add 36.6g hexafluoro bisphenol-a, 30g epoxy chloropropane and 100mlN-methyl-2-pyrrolidone as reaction solvent, treat that above-mentioned two kinds of reactants dissolve the tetrabutylammonium chloride that the back adds 2.75g fully, react 4 hours down at 50 ℃; Then, in reaction system, add 4g sodium hydroxide, reacted 3 hours down at 75 ℃.After reaction is finished, carry out purifying with the method for underpressure distillation and namely obtain the Resins, epoxy precursor that contains fluorine atom of the present invention.This epoxy equivalent (weight) that contains the Resins, epoxy precursor of fluorine atom is 600, and number-average molecular weight 1250, molecular weight distribution are 1.04, corresponding to the Resins, epoxy precursor that contains fluorine atom of n=2 in the structural formula 6.
The Resins, epoxy precursor 120g that contains fluorine atom that makes is placed the 500ml there-necked flask, add the 100ml N-Methyl pyrrolidone as reaction solvent, back adding 40g linolenic acid stirs, use oil bath heating, make the temperature of reaction system be increased to 110 ℃, add butyllithium 2.35g, begin to carry out esterification, react after 4 hours, the pH value of reaction system remains unchanged substantially, shows to react to finish, and extracts with 100ml water then, and the collection organic phase, the organic phase that obtains carries out namely obtaining fluorine resin of the present invention after drying and underpressure distillation steam solvent.The hydroxy radical content of this fluorine resin is 3.8g/100g, and number-average molecular weight is 1800, and molecular weight distribution is 1.05, corresponding to the fluorine resin of n=2 in the structural formula 2.
Embodiment 4
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
In the 500ml there-necked flask, add 36.6g hexafluoro bisphenol-a, 95.0g epoxy chloropropane and 150mlN-methyl-2-pyrrolidone as reaction solvent, treat that above-mentioned two kinds of reactants dissolve the tetrabutylammonium chloride that the back adds 2.75g fully, react 2 hours down at 60 ℃; Then, in reaction system, add 4g sodium hydroxide, reacted 5 hours down at 65 ℃.After reaction is finished, carry out purifying with the method for underpressure distillation and namely obtain the Resins, epoxy precursor that contains fluorine atom of the present invention.This epoxy equivalent (weight) that contains the Resins, epoxy precursor of fluorine atom is 220, and number-average molecular weight 448, molecular weight distribution are 1.02, corresponding to the Resins, epoxy precursor that contains fluorine atom of n=0 in the structural formula 6.
The Resins, epoxy precursor 50g that contains fluorine atom that makes is placed the 500ml there-necked flask, add the 100ml N-Methyl pyrrolidone as reaction solvent, back adding 40g linolenic acid stirs, use oil bath heating, make the temperature of reaction system be increased to 125 ℃, add butyllithium 2.35g, begin to carry out esterification, react after 4 hours, the pH value of reaction system remains unchanged substantially, shows to react to finish, and extracts with 100ml water then, and the collection organic phase, the organic phase that obtains carries out namely obtaining fluorine resin of the present invention after drying and underpressure distillation steam solvent.The hydroxy radical content of this fluorine resin is 3.36g/100g, and number-average molecular weight is 1000, and molecular weight distribution is 1.05, corresponding to the fluorine resin of the n=0 in the structural formula 2.
Embodiment 5
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
In the 500ml there-necked flask, add 36.6g hexafluoro bisphenol-a, 14.8g epoxy chloropropane and 100mlN-methyl-2-pyrrolidone as reaction solvent, treat that above-mentioned two kinds of reactants dissolve the tetrabutylammonium chloride that the back adds 2.75g fully, react 4 hours down at 60 ℃; Then, in reaction system, add 4g sodium hydroxide, reacted 5 hours down at 70 ℃.After reaction is finished, carry out purifying with the method for underpressure distillation and namely obtain the Resins, epoxy precursor that contains fluorine atom of the present invention.This epoxy equivalent (weight) that contains the Resins, epoxy precursor of fluorine atom is 2300, number-average molecular weight 4500, and molecular weight distribution is respectively 1.11, obtains the Resins, epoxy precursor that contains fluorine atom corresponding to n=10 in the structural formula 6.
The Resins, epoxy precursor 46g that contains fluorine atom that makes is placed the 250ml there-necked flask, add the 100ml N-Methyl pyrrolidone as reaction solvent, back adding 4g linolenic acid stirs, use oil bath heating, make the temperature of reaction system be increased to 100 ℃, add butyllithium 0.25g, begin to carry out esterification, react after 6 hours, the pH value of reaction system remains unchanged substantially, shows to react to finish, and extracts with 200ml water then, and the collection organic phase, the organic phase that obtains carries out namely obtaining fluorine resin of the present invention after drying and underpressure distillation steam solvent.The hydroxy radical content of this fluorine-containing epoxy resin is 4.2g/100g, and number-average molecular weight is 4900, and molecular weight distribution is 1.12, corresponding to the fluorine resin of n=10 in the structural formula 2.
Embodiment 6
Present embodiment is used for explanation according to fluorine resin of the present invention and preparation method thereof.
Add 22g hexafluoro bisphenol-a (sea, Shanghai Qu Huagong company limited) in the 250ml there-necked flask, 16.9g hexamethylene diisocyanate (Asahi Chemical Corp) and 100ml N-Methyl pyrrolidone are as reaction solvent.React 3h down at 50 ℃.The variation of NCO content in the detection architecture when the content of isocyano in the system is 12.8g/100g, reduces temperature to room temperature.Add the 40g linolic acid in system, use the oil bath heating, make the temperature of reaction system be increased to 60 ℃, behind the reaction 4h, the pH value of reaction system remains unchanged substantially, shows to react and finishes.Underpressure distillation namely obtains fluorine resin of the present invention after steaming solvent.It is 3000 that GPC detects synthetic molecular resin amount, and molecular weight distribution is 1.13, corresponding to p=6 in the structural formula 4, m=5 fluorine resin.
Embodiment 7
Present embodiment is used for illustrating conformal coating provided by the invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 8
Present embodiment is used for illustrating the conformal coating of basic invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 9
Present embodiment is used for illustrating the conformal coating of basic invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
The fluorine resin 50 weight % of embodiment 2 preparations
Siccative is cobalt naphthenate 0.5 weight %
Thinner is ethylene glycol n-butyl ether 49.5 weight %
Embodiment 10
Present embodiment is used for illustrating the conformal coating of basic invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 11
Present embodiment is used for illustrating the conformal coating of basic invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 12
Present embodiment is used for illustrating the conformal coating of basic invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 13
Present embodiment is used for illustrating conformal coating provided by the invention.
The method of employing solution blending mixes each component of conformal coating, obtains conformal coating of the present invention.The proportioning of conformal coating makes that the total amount with conformal coating is benchmark, the consisting of of this conformal coating:
Embodiment 14-20
Embodiment 14-20 is used for illustrating the printed-wiring board (PWB) that has sprayed conformal coating of the present invention.
The conformal coating of embodiment 7-13 preparation is sprayed to respectively on the wiring board that is purchased, the described wiring board that is purchased is the circuit card of F3-FLASHER-V0.3 for the model that is used on the BYD F3 vehicle, then printed-wiring board (PWB) is placed drying, clean environment, under 26 ℃ temperature, be 3 hours set time, and the thickness of the conformal coating layer on the printed-wiring board (PWB) of formation is 40 μ m.
Comparative Examples 1
Spray other kind conformal coatings according to the described method of embodiment 14-20 at same print circuit board surface, different is that described conformal coating is that the model that Robnor resins company produces is the acrylic-type conformal coating of MP400C.Solidification value is 60 ℃, and be 4 hours set time, obtain completion of cure, thickness is the printed-wiring board (PWB) of the conformal coating layer of 40 μ m.
Performance test:
Sticking power: the sticking power of measuring the conformal coating layer according to the method for GB9286 regulation.
Hardness: the pencil hardness of measuring the conformal coating layer according to the method for GB/T6739 regulation.
Snappiness: the snappiness of measuring the conformal coating layer according to the method for GB/T6742 regulation.
Surface energy: the surface energy of measuring the conformal coating layer at the OCA of Dataphysics company series contact angle measurement.
Proof voltage: the proof voltage of measuring the conformal coating layer according to the method for MIL-1-46058C regulation.
Water tolerance: the water tolerance of measuring the conformal coating layer according to the method for 4.1.10 regulation among the QC/T484.
Measure the performance by the conformal coating layer of embodiment 14-20 and Comparative Examples 1 preparation according to the method described above respectively, test result is as shown in table 1.
Table 1
Data show in the table 1, and surface energy, hardness, water tolerance, proof voltage and the conformal coating layer that comprises the printed-wiring board (PWB) of conformal coating of the present invention all obviously is better than the performance of the printed-wiring board (PWB) of the acrylic type conformal coating spraying that is purchased to the sticking power of wiring board.
Claims (9)
1. a fluorine resin is characterized in that, contains a plurality of carbon-carbon double bonds in the molecular structure of described fluorine resin, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; Described fluorine resin is fluorine-containing epoxy resin; The structural formula of described fluorine-containing epoxy resin is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one is F or CF
3R is the alkyl that contains a plurality of carbon-carbon double bonds, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; N is the integer of 0-10.
2. fluorine resin according to claim 1, wherein, the structural formula of described fluorine-containing epoxy resin is as follows:
Wherein, R is that carbonatoms is the alkyl of 7-35.
3. fluorine resin according to claim 1 and 2, wherein, R is:
-(CH
2)
xCH=CH-CH
2-CH=CH (CH
2)
yCH
3, wherein, x is the integer of 1-24, y is the integer of 0-23, and x+y is the integer of 1-24; And/or
-(CH
2)
eCH=CH-CH
2-CH=CH-CH
2-CH=CH (CH
2)
fCH
3, wherein, e is the integer of 1-21, f is the integer of 0-20, and e+f is the integer of 1-21.
4. fluorine resin according to claim 3, wherein, R is:
-(CH
2)
7CH=CH-CH
2-CH=CH (CH
2)
4CH
3And/or
-(CH
2)
7CH=CH-CH
2-CH=CH-CH
2-CH=CHCH
2CH
3。
5. method for preparing the described fluorine resin of claim 1, it is characterized in that, this method comprises that resin precursor and the unsaturated fatty acids that will contain fluorine atom carry out condensation reaction and/or opening under catalyst action, wherein, contain a plurality of carbon-carbon double bonds in the described monounsaturated fatty acid molecule structure, and the methylene radical of being separated by between in a plurality of carbon-carbon double bond at least two; The described resin precursor that contains fluorine atom is the Resins, epoxy precursor that contains fluorine atom, and the carbonatoms of described unsaturated fatty acids is 8-36.
6. the preparation method of fluorine resin according to claim 5, wherein, the structural formula of the described Resins, epoxy precursor that contains fluorine atom is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Be H, CH independently of one another
3, F or CF
3, and R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least one is F or CF
3, n is the integer of 0-10;
Described unsaturated fatty acids is:
CH
3(CH
2)
yCH=CH-CH
2-CH=CH (CH
2)
x-COOH, wherein, x is the integer of 1-24, y is the integer of 0-23, and x+y is the integer of 1-24; And/or
CH
3(CH
2)
fCH=CH-CH
2-CH=CH-CH
2-CH=CH (CH
2)
e-COOH, wherein, e is the integer of 1-21, f is the integer of 0-20, and e+f is the integer of 1-21.
7. the preparation method of fluorine resin according to claim 6, wherein, the structure of the described Resins, epoxy precursor that contains fluorine atom is as follows:
Described unsaturated fatty acids is linolenic acid and/or linolic acid.
8. conformal coating, described conformal coating contains matrix resin and siccative, it is characterized in that, and described matrix resin is any described fluorine resin among the claim 1-4.
9. printed-wiring board (PWB), described printed-wiring board (PWB) comprises wiring board and conformal coating layer, it is characterized in that, described conformal coating layer is that the conformal coating described in the claim 8 solidifies formed layer.
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| JP2005082700A (en) * | 2003-09-09 | 2005-03-31 | Shin Etsu Chem Co Ltd | Primer composition for thermosetting type fluorine-based elastomer and bonding method |
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| WO2007083690A1 (en) * | 2006-01-19 | 2007-07-26 | Nippon Kayaku Kabushiki Kaisha | Active energy ray-curable resin composition and use thereof |
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|---|---|---|---|---|
| CN1208388C (en) * | 2002-01-17 | 2005-06-29 | 佳能株式会社 | Epoxy resin composition, surface treatment method, liquid jetting record head and liquid jetting recorder |
| JP2005082700A (en) * | 2003-09-09 | 2005-03-31 | Shin Etsu Chem Co Ltd | Primer composition for thermosetting type fluorine-based elastomer and bonding method |
| CN1641449A (en) * | 2004-01-10 | 2005-07-20 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing liquid crystal vertical orented membrane |
| WO2007083690A1 (en) * | 2006-01-19 | 2007-07-26 | Nippon Kayaku Kabushiki Kaisha | Active energy ray-curable resin composition and use thereof |
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