CN101575489B - White adhesive for flexible printed circuit and preparation method thereof - Google Patents
White adhesive for flexible printed circuit and preparation method thereof Download PDFInfo
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- CN101575489B CN101575489B CN2009100402367A CN200910040236A CN101575489B CN 101575489 B CN101575489 B CN 101575489B CN 2009100402367 A CN2009100402367 A CN 2009100402367A CN 200910040236 A CN200910040236 A CN 200910040236A CN 101575489 B CN101575489 B CN 101575489B
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Abstract
The invention discloses a white adhesive for a flexible printed circuit and a preparation method thereof. The white adhesive comprises the following raw material compositions: thermosetting resin, filler, thermoplastic resin, rubber, a curing agent and a curing accelerator, wherein the weight ratio in portion of the various raw material compositions is as follows: 20 to 80 portions of the thermosetting resin, 45 to 150 portions of the filler, 0 to 60 portions of the thermoplastic resin, 0 to 40 portions of the rubber, 2 to 9 portions of the curing agent, 0.5 to 2 portions of the curing accelerator and 40 to 120 portions of organic solvent. The white adhesive has good opacity and reflection performance. The invention simultaneously discloses the method for preparing the white adhesive.
Description
Technical field
The present invention relates to white adhesive that a kind of flexible print circuit uses and preparation method thereof, contain laminate structure of this white adhesive and preparation method thereof.
Background technology
Along with the design of mobile phone and other electronic product is weeded out the old and bring forth the new, the special design requirements for flexible printed circuit board is arranged, and in recent years; LED Lighting Industry high speed development because the luminous power of LED own has it restricted, is therefore also updated in the hope of helping LED luminous (optically focused) effect in the encapsulation technology of LED; Backboard---the FPC that tradition LED uses, the printing ink that needs to apply white again is to improve light reflectance, and technology is loaded down with trivial details; Yield rate reduces, and cost rises.
Publication number is that the patent application document of CN1900157 discloses a kind of tackiness agent, and it comprises thermosetting resin, thermoplastic resin, solidifying agent and curing catalyst, wherein; Thermosetting resin uses bisphenol A epoxide resin; Novolac epoxy and phosphorous epoxy resin, thermoplastic resin uses acrylic rubber, and solidifying agent uses DDM or DDS; Curing catalyst uses imidazoles derivatization reaction thing, but does not add filler in this tackiness agent.
Publication number is that the patent application document of CN1670107 also discloses a kind of tackiness agent, and it comprises thermosetting resin, thermoplastic resin, rubber, solidifying agent, curing catalyst and filler, and thermosetting resin uses halogen-free epoxy resin; Thermoplastic resin uses carboxylic thermoplastic resin; Viton uses and contains carboxy nitrile rubber, and solidifying agent uses phthalic anhydride, four ethylidene tetramines etc., and curing catalyst uses 2-ethyl-4-methylimidazole etc.; Filler comprises phosphorous filler and mineral filler; Wherein phosphorous filler comprises phosphoric acid acyl amine compound and nitrogenous phosphate compounds, the umber of mineral filler 30～40 parts, or 160～400 parts between, mineral filler can be used MOX; Like white lake, Marinco H, silicon-dioxide and molybdenum oxide, zinc oxide etc.; Preferred white lake and Marinco H, these mineral fillers can be used separately, perhaps two kinds or more kinds of different compounds combination use.
The problem that the product of above-mentioned prescription exists is that opacifying property, the reflective of product itself is low, when these tackiness agent are used among the LED, needs to apply the printing ink of white again, to improve light reflectance.Therefore, along with the development of electronic industry, opacifying property is good, and the flexible printed circuit board material that reflecting rate is high will be favored.
Summary of the invention
One of the object of the invention provides the white adhesive that a kind of flexible print circuit is used, and this white adhesive has opacifying property and reflective function preferably.
This purpose of the present invention realizes through following technical scheme: the white adhesive that a kind of flexible print circuit is used; Its feed composition comprises thermosetting resin, filler, thermoplastic resin, rubber, solidifying agent and curing catalyst, and the weight part proportioning of each feed composition is following:
20～80 parts of thermosetting resins
45～150 parts of fillers
0～60 part of thermoplastic resin
0～40 part of rubber
2～9 parts in solidifying agent
0.5～2 part of curing catalyst
40～120 parts of organic solvents
Among the present invention, selecting thermosetting resin is in order to reach good thermotolerance, because thermosetting resin can provide outstanding thermotolerance.Said thermosetting resin can be one or more the arbitrary combination in epoxy resin, vinyl resin, the polyimide resin, wherein:
Epoxy resin according to the invention can be bisphenol A type epoxy resin E-44 or bisphenol A type epoxy resin E-20 or six glycidyl ether tripolyphosphazenes or novolac epoxy F-44 or multiple functionality epoxide resin AG-80; Said bisphenol A epoxide resin E-44 and bisphenol A type epoxy resin E-20 all can provide high cohesive strength; Six glycidyl ether tripolyphosphazenes can improve flame retardant properties; Multiple functionality epoxide resin AG-80 can increase cross-linking density, improves second-order transition temperature.
Among the present invention, said vinyl resin can be methylacrylic acid epoxy ester resin or ortho-cresol epoxy acrylic resin; The vinyl resin solvent resistance is good, and good weatherability also is not easy variable color under high bake.
Among the present invention, said polyimide can be N, N '-4, and 4 ' ditan bismaleimides or N-phenylmaleimide, polyimide resin can improve thermotolerance, stability to aging, chemicalstability, heat-resisting electrical insulating property.
Among the present invention; Described filler is any or the two or more mixture in titanium oxide and white lake, silicon-dioxide, these three kinds of materials of Marinco H, preferred 65～130 parts of filler, and filler of the present invention is selected the higher titanium oxide of whiteness for use; It mixes use with white lake, silicon-dioxide, these white masses of Marinco H respectively; Can make glue paste obtain higher whiteness, have good reflecting effect, and cost is not high yet.
Thermoplastic resin can improve materials processed, improves the toughness of material, increases the shearing resistance of material; Thermoplastic resin according to the invention can be one or more the arbitrary combination in vibrin, vinyl resin, phenoxy resin, the polyimide resin; The typical scope of the weight-average molecular weight of thermoplastic resin is 1000 to 5000000, preferred 5000 to 1000000; Wherein:
Vibrin according to the invention can be polyethyleneterephthalate or poly terephthalic acid 1,4-hexanaphthene dimethyl ester;
Said vinyl resin can be polymethylmethacrylate or polymethyl acrylate or polyethyl acrylate;
Said polyimide resin can be polyetherimide or PMMI;
Said phenoxy resin can for 4-hydroxymethyl phenoxy methyl resin or poly bisphenol hydroxy ethers or deuterium for dihydroxyphenyl propane base polyhydroxy ether; Epoxy group(ing) is contained at 4-hydroxymethyl phenoxy methyl resin two ends, can react with epoxy resin, increases crosslinkedly, helps the raising of Tg, through crosslinked, can also improve hardness, softening temperature and solvent resistance.
Among the present invention, described rubber is any or its compsn in paracril, the hydrorubber;
Said paracril can be NBR1704 or carboxy nitrile rubber 1072CG or carboxy nitrile rubber 1072 etc.; Paracril is had no particular limits; Yet from improving the angle of the viscosity between Copper Foil and the insulating film; The paracril that preferably contains carboxyl group, these examples that contain the paracril of carboxylic group comprise the copolymer rubber that the acrylonitrile and butadiene copolymerization produces, and vinyl cyanide is quality 5% to 70% with respect to the quality of acrylonitrile and butadiene mixture than scope; Preferred mass 10% to 50%; Wherein the molecular weight end of multipolymer is by carboxylated, also comprises vinyl cyanide, divinyl and contains the copolymer rubber that the monomer of carboxylic group forms such as vinylformic acid or toxilic acid etc., and the molecule chain end in the above-mentioned copolymer rubber carboxylated can use the monomer that contains carboxylic group such as methylacrylic acid or similar etc. to realize; Content for the carboxylic group in the above-mentioned paracril that contains carboxylic group has no particular limits; Preferred mass 1% to 10%, the mobile of product composition is controlled in this scope, can obtain good state of cure.
Said hydrorubber can be hydrorubber or F-oxygen azepine a kind of apple rubber or the P-oxygen azepine a kind of apple rubber that contains carboxy nitrile rubber.
Solidifying agent of the present invention can be any or the two or more compsns in diamino diphenyl sulfone, 4-methyl tetrahydro phthalic anhydride, Dyhard RU 100, phenylenediamine, PMA, trimellitic acid 1,2-anhydride, hexahydrophthalic anhydride, the 4-methyl tetrahydro phthalic anhydride.
Solidifying agent is the processing aid that material is solidified, and wherein, the imidazoles curing catalyst can make the resin fast setting at a certain temperature, reduces reactive temperature, and the cured article flexibility is good, helps improving thermotolerance; Diamino diphenyl sulfone, 4-methyl tetrahydro phthalic anhydride, Dyhard RU 100 etc. all have good comprehensive performances, make resin crosslinks, form netted structure, improve the mechanical property of tackiness agent, and can let product obtain long storage period, keep the stable of tackiness agent performance.
Curing catalyst of the present invention is 1 a cyanic acid 2-ethyl 4-methylimidazole, 2,4, any in 6-three (dimethylamino methyl) phenol, Dyhard RU 100, glyoxal ethyline, 2-ethyl imidazol(e), 2-phenyl-4 Methylimidazole or two or more compsns;
Curing catalyst and fixing agent and time spent, can improve speed of reaction, general consumption is few.
Organic solvent is to dissolve some water-fast materials, like one type of organic cpds of grease, wax, resin, rubber, dyestuff etc.Organic solvent of the present invention is butanone, N; In dinethylformamide, DMAC N,N, methyl ethyl ketone, toluene, methyl alcohol, ethanol, Virahol, acetone, pimelinketone, N, the N,N-DIMETHYLACETAMIDE any or two or more compsns.
White adhesive of the present invention; Not only have good cohesiveness and thermotolerance performance; But also having good opacifying property, whiteness, reflecting rate, these performances make it can save the coating operation that needs white ink to apply in the prior art fully, both can guarantee product performance; Improve production efficiency again greatly, reduced production cost.
Two of the object of the invention provides the preparation method of above-mentioned white adhesive.
This purpose of the present invention realizes through following technical scheme: the preparation method of the white adhesive that a kind of above-mentioned flexible print circuit is used, it comprises the steps:
(1) under 15～30 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
Three of the object of the invention provides the laminate structure that contains above-mentioned white adhesive.
This purpose of the present invention realizes through following technical scheme: a kind of laminate structure; It has bottom, middle layer and top layer; The three fits together from bottom to top, and wherein said middle layer is the white adhesive layer that the white adhesive used of said flexible print circuit forms.
Said bottom is electrical insulating film or resist, and described top layer is electrical insulating film or resist or Copper Foil.
Described electrical insulating film is polyimide film, polyethylene terephthalate film, poly (ethylene naphthalate) film or polyphenylene sulfide film, and described resist is polyethylene film, polypropylene screen, polyester film, applying paper or pearl paper.
Four of the object of the invention provides the preparation method who contains above-mentioned laminate structure.
This purpose of the present invention is through following technology, and a kind of method for preparing above-mentioned laminate structure is characterized in that:
(1) under 15～30 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution;
(3) with the white adhesive solution coat at bottom, toast, storing temperature is 80 ℃～180 ℃; Storing time is 2～10 minutes, removes organic solvent and drying compsn, forms the middle white adhesive layer; Then with itself and top layer pressing; Be pressed into the laminate structure of an integral body, carry out completely solidified in 50～180 ℃, obtain the laminate structure product.
Compared with prior art, the present invention has and is showing effect as follows:
1, because this tackiness agent adds white fillers such as titanium oxide; Has higher whiteness; Make tackiness agent itself have opacifying property preferably, reflecting rate is high, has saved the operation that also need apply white ink layer in original technology behind the adhesive coating again; Simplify working process and simply can obviously enhance productivity, reduce cost;
2, add a large amount of fillers in the present invention's prescription, help making the overall product cost to reduce;
3, white adhesive of the present invention has good cohesiveness and thermotolerance performance simultaneously;
4, the present invention can add the filler of flame retardant resistance, plays the good flame effect, matches with the development trend of the printed wiring of advocating the halogen-free stibium-free antiflaming type.
Embodiment
Embodiment 1
The white adhesive that a kind of flexible print circuit is used, its feed composition comprises thermosetting resin, filler, thermoplastic resin, rubber, solidifying agent and curing catalyst, wherein:
Thermosetting resin is a novolac epoxy
Filler be titanium oxide and white lake or mixture
Thermoplastic resin is the 4-hydroxymethyl phenoxy methyl resin of phenoxy resin
Rubber is carboxy nitrile rubber 1072CG
Solidifying agent is the 4-methyl tetrahydro phthalic anhydride
Curing catalyst is 1 cyanic acid 2-ethyl 4-methylimidazole
Organic solvent is butanone and N, the mixture of dinethylformamide
The weight part proportioning of each feed composition is seen table 1.
The preparation method of the white adhesive that above-mentioned flexible print circuit is used, it comprises the steps:
(1) under 15 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
A kind of white mulch film of flexible print circuit; It has bottom, middle layer and top layer, and the three fits together from bottom to top, and said bottom is an electrical insulating film; Described top layer is a resist, and described middle layer is the white adhesive layer that the white adhesive used of said flexible print circuit forms.
Described electrical insulating film is a poly (ethylene naphthalate) film; Also can adopt polyethylene terephthalate film, polyimide film or polyphenylene sulfide film; Described resist is a polyethylene film, also can adopt polypropylene screen, polyester film, applying paper or pearl paper.
A kind of method for preparing above-mentioned white mulch film is characterized in that:
(1) under 15 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution;
(3) with the white adhesive solution coat at electrical insulating film, toast, storing temperature is 130 ℃; Storing time is 10 minutes, removes organic solvent and drying compsn, forms the middle white adhesive layer; With itself and resist pressing, be pressed into the laminate structure of an integral body then, baking 10 hours in constant temperature oven under 50 ℃ of conditions; Make the white adhesive completely solidified, obtain the white mulch film of laminate structure.
Choose corresponding testing method to this white mulch film material characteristic test, test result is listed in the table 1.
Embodiment 2
The white adhesive that a kind of flexible print circuit is used, its feed composition comprises:
Thermosetting resin is bisphenol A type epoxy resin E-44
Filler is the mixture of titanium oxide and silicon-dioxide
Thermoplastic resin is the 4-hydroxymethyl phenoxy methyl resin of phenoxy resin
Solidifying agent is a diamino diphenyl sulfone
Curing catalyst is 1 cyanic acid 2-ethyl 4-methylimidazole
Organic solvent is butanone and N, the mixture of dinethylformamide
The weight part proportioning of each feed composition is seen table 1.
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 1 in embodiment 2 hurdles; Identical among the preparation of white mulch film material and the embodiment 1; The testing method of also describing according to the back to this flexible copper-clad panel material characteristic test, the result lists in the table 1.
Embodiment 3
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 1 in embodiment 3 hurdles; Identical among the preparation of white mulch film material and the embodiment 1; The testing method of also describing according to the back to this white mulch film material characteristic test, the result lists in the table 1.
Embodiment 4
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 1 in embodiment 4 hurdles; Identical among the preparation of white mulch film material and the embodiment 1; The testing method of also describing according to the back to this white mulch film material characteristic test, the result lists in the table 1.
The weight part proportioning of each feed composition of the white mulch film of table 1 preparation flexible print circuit
Embodiment 5
The white adhesive that a kind of flexible print circuit is used, its feed composition comprises thermosetting resin, filler, thermoplastic resin, rubber, solidifying agent and curing catalyst, wherein:
Thermosetting resin is the compsn of bisphenol A type epoxy resin and novolac epoxy
Filler is that titanium oxide and white lake are or/and the compsn of silicon-dioxide
Thermoplastic resin is a phenoxy resin
Rubber is carboxy nitrile rubber 1072CG
Solidifying agent is the 4-methyl tetrahydro phthalic anhydride
Curing catalyst is 1 cyanic acid 2-ethyl 4-methylimidazole
Organic solvent is butanone and N, the compsn of dinethylformamide
The weight part proportioning of each feed composition is seen table 2.
The preparation method of the white adhesive that above-mentioned flexible print circuit is used, it comprises the steps:
(1) under 20 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
A kind of white stiffening plate of flexible print circuit; It has bottom, middle layer and top layer; The three fits together from bottom to top; Said bottom is an electrical insulating film, and described top layer is resist or electric insulation layer, and described middle layer is the white adhesive layer that the white adhesive used of said flexible print circuit forms.
Described electrical insulating film is the polyethylene terephthalate film, also can adopt polyimide film, poly (ethylene naphthalate) film or polyphenylene sulfide film, and described resist can adopt polyethylene film, polypropylene screen or polyester film.
A kind of method for preparing above-mentioned white stiffening plate is characterized in that:
(1) under 20 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution;
(3) with the white adhesive solution coat at electrical insulating film, toast, storing temperature is 110 ℃; Storing time is 10 minutes, removes organic solvent and drying compsn, forms the middle white adhesive layer; With the resist or the electric insulation layer pressing of itself and top layer, be pressed into the laminate structure of an integral body then, baking 11 hours in constant temperature oven under 50 ℃ of conditions; Make the white adhesive completely solidified, obtain the white stiffening plate of laminate structure.
Choose corresponding testing method to this white stiffening plate material characteristic test, test result is listed in the table 2.
Embodiment 6
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 2 in embodiment 6 hurdles; Identical among the preparation of white stiffening plate material and the embodiment 5; The testing method of also describing according to the back to this white stiffening plate characteristic test, the result lists in the table 2.
Embodiment 7
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 2 in embodiment 7 hurdles; Identical among the preparation of white stiffening plate material and the embodiment 5; The testing method of also describing according to the back to this white stiffening plate characteristic test, the result lists in the table 2.
Embodiment 8
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 2 in embodiment 8 hurdles; Identical among the preparation of white stiffening plate material and the embodiment 5; The testing method of also describing according to the back to this white stiffening plate characteristic test, the result lists in the table 2.
The weight part proportioning of each feed composition of the white stiffening plate of table 2 preparation flexible print circuit
Embodiment 9
The white adhesive that a kind of flexible print circuit is used, its feed composition comprises thermosetting resin, filler, thermoplastic resin, solidifying agent and curing catalyst, wherein:
Thermosetting resin is the compsn of bisphenol A type epoxy resin and multiple functionality epoxide resin
Filler is that titanium oxide and Marinco H are or/and the compsn of silicon-dioxide
Thermoplastic resin is a phenoxy resin
Solidifying agent is the compsn of diamino diphenyl sulfone and Dyhard RU 100
Curing catalyst is 1 cyanic acid 2-ethyl 4-methylimidazole
Organic solvent be butanone and compsn
The weight part proportioning of each feed composition is seen table 3.
The preparation method of the white adhesive that above-mentioned flexible print circuit is used, it comprises the steps:
(1) under 25 ℃ of temperature, earlier said thermosetting resin and thermoplastic resin are put into said organic solvent and dissolve, and stir, the formation solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
A kind of white bonding sheet of flexible print circuit; It has bottom, middle layer and top layer; The three fits together from bottom to top, and said bottom and top layer are resist, and described middle layer is the white adhesive layer that the white adhesive used of said flexible print circuit forms.
Described resist is an applying paper, also can adopt polyethylene film, polypropylene screen, polyester film or pearl paper.
A kind of method for preparing above-mentioned white bonding sheet is characterized in that:
(1) under 25 ℃ of temperature, earlier said thermosetting resin and thermoplastic resin are put into said organic solvent and dissolve, and stir, the formation solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution;
(3) with the white adhesive solution coat at resist, toast, storing temperature is 150 ℃; Storing time is 6 minutes, removes organic solvent and drying compsn, forms the middle white adhesive layer; With the resist pressing of itself and top layer, be pressed into the laminate structure of an integral body then, baking 10 hours in constant temperature oven under 50 ℃ of conditions; Make the white adhesive completely solidified, obtain the white bonding sheet of laminate structure.
Choose corresponding testing method to this white bonding sheet material characteristic test, test result is listed in the table 3.
Embodiment 10
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 3 in embodiment 9 hurdles; Identical among the preparation of white bonding sheet material and the embodiment 9; The testing method of also describing according to the back to this white bonding sheet characteristic test, the result lists in the table 3.
Embodiment 11
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 3 in embodiment 11 hurdles; Identical among the preparation of white bonding sheet material and the embodiment 9; The testing method of also describing according to the back to this white bonding sheet characteristic test, the result lists in the table 3.
Embodiment 12
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 3 in embodiment 12 hurdles; Identical among the preparation of white bonding sheet material and the embodiment 9; The testing method of also describing according to the back to this white bonding sheet characteristic test, the result lists in the table 3.
The weight part proportioning of each feed composition of the white bonding sheet of table 3 preparation flexible print circuit
Embodiment 13
The white adhesive that a kind of flexible print circuit is used, its feed composition comprises thermosetting resin, filler, thermoplastic resin, rubber, solidifying agent and curing catalyst, wherein:
Thermosetting resin is the compsn of six glycidyl ether tripolyphosphazenes and multiple functionality epoxide resin
Filler is that titanium oxide and white lake are or/and the compsn of silicon-dioxide
Thermoplastic resin is a phenoxy resin
Rubber is carboxy nitrile rubber 1072CG
Solidifying agent is the compsn of diamino diphenyl sulfone and 4-methyl tetrahydro phthalic anhydride
Curing catalyst is 2,4,6-three (dimethylamino methyl) phenol
Organic solvent is butanone and N, the compsn of dinethylformamide
The weight part proportioning of each feed composition is seen table 4.
The preparation method of the white adhesive that above-mentioned flexible print circuit is used, it comprises the steps:
(1) under 30 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
A kind of white board substrate of flexible print circuit; It has bottom, middle layer and top layer; The three fits together from bottom to top; Said bottom is an electrical insulating film, and described top layer is a Copper Foil, and described middle layer is the white adhesive layer that the white adhesive used of said flexible print circuit forms.
Described electrical insulating film is the polyethylene terephthalate film, also can adopt polyimide film, poly (ethylene naphthalate) film or polyphenylene sulfide film.
A kind of method for preparing above-mentioned white board substrate is characterized in that:
(1) under 30 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution;
(3) with the white adhesive solution coat at electrical insulating film, toast, storing temperature is 100 ℃; Storing time is 8 minutes, makes compsn get into semi-cured state, this material is toasted 2 hours in the program baking oven under 80 ℃ of conditions again; Constant speed is warming up to 160 ℃ then, and the temperature-rise period time is 2 hours, toasts 2 hours down in 160 ℃ of constant temperatures again; Make the white adhesive completely solidified, remove organic solvent and drying compsn, form the middle white adhesive layer; Use the roll forming laminating machine under 100 ℃, it to be laminated on the rolled copper foil then, be pressed into the laminate structure of an integral body, obtain the white board substrate of laminate structure.
Choose corresponding testing method to this white board substrate material characteristic test, test result is listed in the table 4.
Embodiment 14
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 4 in embodiment 8 hurdles; Identical among the preparation of white board substrate material and the embodiment 13; The testing method of also describing according to the back to this white board substrate characteristic test, the result lists in the table 4.
Embodiment 15
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 4 in embodiment 15 hurdles; Identical among the preparation of white board substrate material and the embodiment 13; The testing method of also describing according to the back is tested the characteristic of this white board substrate, and the result lists in the table 4.
Embodiment 16
Except every kind of component of white adhesive mixture and the blending ratio of organic solvent are to list in the ratio that is labeled as in the table 4 in embodiment 16 hurdles; Identical among the preparation of white board substrate material and the embodiment 13; The testing method of also describing according to the back to this white board substrate characteristic test, the result lists in the table 4.
The weight part proportioning of each feed composition of table 4 preparation flexible printing white board substrate
The testing method that the present invention adopted is following:
Stripping strength (Peel strength, kgf/cm)
According to IPC-TM-650 2.4.9 test stripping strength; Its process is: it is rectangular that white mulch film material is cut into the 3.175mm width; Pressing Copper Foil two hours under 140 ± 10 ℃ of temperature, 600 ± 200 PSI pressure conditions then; Obtain specimen, test becomes an angle of 90 degrees with white mulch film material surface, peels off the power of white mulch film material require with speed 50mm/min.
2. scolding tin thermal test method
According to IPC-TM-650 2.4.13 test scolding tin thermotolerance; Its process is: white mulch film material pressing Copper Foil two hours under 140 ± 10 ℃ of temperature, 600 ± 200 PSI pressure conditions; Be cut into the specimen of 5cm * 5cm, directly immerse the plumbous liquid tin of the high temperature tin furnace temperature 30sec of constant temperature, and test does not have bubble when test sample book; Peeling, or the top temperature when fading.
3. light reflectance:
According to define among the JIS-Z-8722 method confirm.
4. flame retardant resistance:
At first complete etching prepares sample on the white board substrate material from printing with Copper Foil with etch processes, has tested the flame retardant resistance of this sample according to flame-retardant standard UL94VTM-0.If sample satisfies the needs of flame-retardant standard UL94VTM-0, then estimate it and be " good ", if sample has burnt, estimate it and be " poor ".
Claims (8)
1. white adhesive that flexible print circuit is used, its feed composition comprises thermosetting resin, filler, thermoplastic resin, rubber, solidifying agent and curing catalyst, the weight part proportioning of each feed composition is following:
Described filler is any or the two or more mixture in titanium oxide and white lake, silicon-dioxide, these three kinds of materials of Marinco H.
2. the white adhesive that a kind of flexible print circuit according to claim 1 is used is characterized in that: said thermosetting resin is one or more the arbitrary combination in epoxy resin, vinyl resin, the polyimide resin.
3. the white adhesive that a kind of flexible print circuit according to claim 1 is used is characterized in that: said thermoplastic resin is one or more the arbitrary combination in vibrin, vinyl resin, phenoxy resin, the polyimide resin.
4. the white adhesive that a kind of flexible print circuit according to claim 1 is used is characterized in that: described rubber is any or its compsn in paracril, the hydrorubber.
5. the white adhesive that a kind of flexible print circuit according to claim 1 is used is characterized in that: described solidifying agent is any or the two or more compsn in diamino diphenyl sulfone, 4-methyl tetrahydro phthalic anhydride, Dyhard RU 100, diaminodiphenyl-methane, phenylenediamine, PMA, trimellitic acid 1,2-anhydride, hexahydrophthalic anhydride, the 4-methyl tetrahydro phthalic anhydride.
6. the white adhesive that a kind of flexible print circuit according to claim 1 is used; It is characterized in that: described curing catalyst is 1 a cyanic acid 2-ethyl 4-methylimidazole, 2; 4, any in 6-three (dimethylamino methyl) phenol, Dyhard RU 100, glyoxal ethyline, 2-ethyl imidazol(e), 2-phenyl-4 Methylimidazole or two or more compsns.
7. the white adhesive that a kind of flexible print circuit according to claim 1 is used; It is characterized in that: described organic solvent is butanone, N; In dinethylformamide, DMAC N,N, methyl ethyl ketone, toluene, methyl alcohol, ethanol, Virahol, acetone, pimelinketone, N, the N,N-DIMETHYLACETAMIDE any or two or more compsns.
8. the preparation method of the white adhesive used of a flexible print circuit as claimed in claim 1, it comprises the steps:
(1) under 15～30 ℃ of temperature, earlier said thermosetting resin, thermoplastic resin and rubber are put into said organic solvent and dissolve, and stir, form solution A;
(2) more said filler, solidifying agent and curing catalyst are put into solution A and continue to stir, obtain white adhesive solution.
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| CN2009100402367A CN101575489B (en) | 2009-06-15 | 2009-06-15 | White adhesive for flexible printed circuit and preparation method thereof |
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| CN2009100402367A CN101575489B (en) | 2009-06-15 | 2009-06-15 | White adhesive for flexible printed circuit and preparation method thereof |
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| CN101575489B true CN101575489B (en) | 2012-07-18 |
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