CN1145928A - Drying oil-modified phenolic resin composition for laminate and phenolic resin laminate using drying oil-modified phenolic resin composition - Google Patents
Drying oil-modified phenolic resin composition for laminate and phenolic resin laminate using drying oil-modified phenolic resin composition Download PDFInfo
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- CN1145928A CN1145928A CN 95109859 CN95109859A CN1145928A CN 1145928 A CN1145928 A CN 1145928A CN 95109859 CN95109859 CN 95109859 CN 95109859 A CN95109859 A CN 95109859A CN 1145928 A CN1145928 A CN 1145928A
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Abstract
The present invention provides laminated phenolic resin plate with excellent moisture resistance, punching machinability and fireretardant property. During the prepn of bodied oil-modified phenolic resin composition, bobied oil reacts first with phenols, which consists of phenol and cresol mixture and then with formaldehyde in the presence of alkaline catalyst. The said phenolic resin composition and melamine resin-modified water-soluble phenolic resin are used in dipping paper base material to produce pre-formed material, which is stacked, with or without copper foil, heated and pressured to form laminated phenolic resin plate.
Description
The present invention relates to veneer sheet with dry oil modified phenolic resin composition and the phenolic sheet that uses this veneer sheet to make with dry oil modified phenolic resin composition.
Paper base material phenolic sheet processibility is good, thereby is used for punching processing more.Only firm and do not have plasticity-with phenols and formaldehyde synthetic resol, promptly be used in and make the paper base material phenolic sheet, can not get till now to the desired punching processing of veneer sheet.Therefore, attempt paper base material, improve punching processing with kraft paper, lint paper or the like low elasticity rate.Method in addition is for giving resol self with flexible.What give that resol self extensively adopts with the flexible method is to make phenolic resin modified method with siccative oil.
On the other hand, also knownly after being flooded water-soluble melamine resin or water soluble phenol resin, paper base material floods dry oil modified phenolic resin again, the method that its flame retardant resistance, wet fastness etc. are improved.
Dry oil modified phenolic resin before is only to use phenol as raw material phenols synthetic resin, and such dry oil modified phenolic resin exists sclerosis back cross-linking density low, wet fastness, punching processing difference and so on problem.And behind water soluble phenol resin treatment paper base material, though wet fastness improves, flame retardant resistance, punching processing variation will make the balanced raising of each characteristic very difficult.
The present invention aims to provide a kind of veneer sheet phenol resin composition, and it can make hardening thing cross-linking density height, wet fastness, flame retardant resistance and all good veneer sheet of punching processing when the preparative layer pressing plate.The present invention also aims to provide the phenolic sheet made from phenol resin composition with this veneer sheet.
Veneer sheet provided by the invention is characterized in that with dry oil modified phenolic resin composition: at the dry oil modified phenolic resin with siccative oil, phenols and formaldehyde reaction gained is in the veneer sheet usefulness dry oil modified phenolic resin composition of principal constituent, this phenols is made up of the cresols mixture that phenol and meta-cresol and p-cresol form, phenol is phenol to the mol ratio of this cresols mixture: cresols mixture=9: 1～5: 5, this dry oil modified phenolic resin be after the reaction of siccative oil and this phenols again in the presence of basic catalyst with formaldehyde reaction gained material.
The present invention also provides such phenolic sheet, and it is also dry with dry oil modified phenolic resin composition by the veneer sheet of paper base material dipping the invention described above, and several overlappings of gained preforming material with Copper Foil, or do not add Copper Foil, and heating and pressurizing forms.
The present invention also provides such phenolic sheet, it by paper base material dipping water soluble phenol resin and drying with the melamine resin modification after, the veneer sheet that floods the invention described above again is also dry with dry oil modified phenolic resin composition, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
The present invention also provides such phenolic sheet, it by the veneer sheet of paper base material dipping the invention described above with dry oil modified phenolic resin composition with the mixture and the drying of the water soluble phenol resin of melamine resin modification, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
The present invention also provides such phenolic sheet, it by paper base material dipping water soluble phenol resin and drying with the melamine resin modification after, the veneer sheet that floods the invention described above again is with dry oil modified phenolic resin composition with the mixture and the drying of the water soluble phenol resin of melamine resin modification, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
At first, to the principal constituent of veneer sheet of the present invention with dry oil modified phenolic resin composition---dry oil modified phenolic resin is illustrated.
About the manufacturing of above-mentioned dry oil modified phenolic resin, be earlier with siccative oil and phenols reaction.
Used siccative oil can be enumerated such as tung oil, dehydrated castor oil, Semen Lini oil, Austria and carry west card wet goods in the manufacturing of dry oil modified phenolic resin.These siccative oil can a kind of independent use, also can two or morely share.
Phenols can use the cresols mixture that is formed by phenol and meta-cresol and p-cresol to form, and phenol is phenol to the mol ratio of this cresols mixture: the cresols mixture is 9: 1～5: 5 a mixture.If the mol ratio of cresols mixture is less than 1, and electric erosion resistance and punching processing can not be improved when making phenolic sheet, and if the mol ratio of cresols mixture is greater than 5, and then punching processing can not be improved.The ratio of meta-cresol and p-cresol is generally meta-cresol 60 ± 5 weight % in the cresols mixture, p-cresol 40 ± 5 weight %.
Amount with the siccative oil of phenols reaction with respect to the total amount of phenols and siccative oil, is generally 20～50 weight %, is preferably 25～40 weight %.If the amount of siccative oil is discontented 20 weight %, the punching processing reduction, and electric erosion resistance also reduces simultaneously, if surpass 50 weight %, then punching processing reduction, intensity also reduces simultaneously.
The temperature of reaction of phenols and siccative oil reaction by being 65～120 ℃, is preferably 70～100 ℃, and the reaction times is generally 30～200 minutes, is preferably 30～150 minutes.This reaction can fully be carried out under normal pressure usually.Carry out preferable under the existence that is reflected at an acidic catalysts such as tosic acid of this siccative oil and phenols.Under the situation of using an acidic catalyst, its consumption, the total amount with respect to phenols and siccative oil (as tung oil) is generally 0.05～0.4 weight %, is preferably 0.05～0.3 weight %.
After above-mentioned reaction finishes, in reaction solution, add formaldehyde and basic catalyst, usually at 60～90 ℃, 65～85 ℃ more fortunately, reacted 30～240 minutes, be preferably 30～180 minutes, obtain principal constituent---the dry oil modified phenolic resin of veneer sheet of the present invention with dry oil modified phenolic resin composition.Again, this reaction can fully be carried out under normal pressure usually.
As formaldehyde source, available formalin, paraformaldehyde etc.The consumption of formaldehyde, common 1 mole of phenols is preferably 1.0～1.5 moles with 1.0～1.7 moles.
As basic catalyst, available such as ammonia, vulkacit H, Trimethylamine 99, triethylamine etc.The consumption of basic catalyst, common 1 mole of phenols is preferably 0.01～0.04 mole with 0.01～0.05 mole.
In the dry oil modified phenolic resin that obtains like this,,, contain the mixture of products that only contains meta-cresol and/or p-cresol in the two the product, skeleton of phenol and meta-cresol and/or p-cresol in the skeleton for only containing the product of phenol in the skeleton as structure from phenols.
In the used cresols mixture of the present invention, position methyl between meta-cresol has, p-cresol has the contraposition methyl, therefore, above-mentioned dry oil modified phenolic resin as a whole, the ortho position activity is big.Therefore, be used to dry oil modified phenolic resin composition make under the situation of veneer sheet at the veneer sheet of the present invention that with this dry oil modified phenolic resin is principal constituent, cross-linking density improves, and characteristics such as wet fastness are good, there is not fragility again, so punching processing is also improved.
Veneer sheet of the present invention is principal constituent with dry oil modified phenolic resin with above-mentioned dry oil modified phenolic resin, but in case of necessity, in order to give veneer sheet with flame retardant resistance, but also flame retardant resistance compositions such as phosphoric acid ester such as bromide such as fusion brominated epoxy resin, tetrabromo-bisphenol diglycidylether, triphenylphosphate, cresyl phosphate diphenyl ester.The blended amount of flame retardant resistance composition is 25～60 weight % with respect to the total amount of dry oil modified phenolic resin and this flame retardant resistance composition usually, is preferably 25～50 weight %.
When making phenolic sheet with dry oil modified phenolic resin composition with veneer sheet of the present invention, this veneer sheet is dissolved in methyl alcohol with dry oil modified phenolic resin composition, make lacquer in the organic solvents such as mixed solvent of toluene, methyl alcohol and toluene, base materials such as impregnated paper, make preforming material after the drying, with several overlappings of this preforming material, heating and pressurizing promptly obtains phenolic sheet of the present invention.At this moment, in order to improve base material and veneer sheet with the binding property of dry oil modified phenolic resin composition, also can be singly with water soluble phenol resin, water-soluble melamine resin etc. or share them base material is handled.
Using under the situation of paper base material, present inventors find, use separately or merging use water soluble phenol resin, water-soluble melamine resin etc. with it, not as water soluble phenol resin treatment paper base material in order to the melamine resin modification, can obtain all good phenolic sheet of each characteristic, and finish phenolic sheet of the present invention.Promptly, fusion is with the water soluble phenol resin of melamine resin modification in above-mentioned veneer sheet usefulness dry oil modified phenolic resin composition, dry oil modified phenolic resin is improved the affinity of paper base material, and the binding property of resin and base material improves, and wet fastness, punching processing obtain improvement.And, water soluble phenol resin with the melamine resin modification has flame retardant effect, simultaneously also good with the intermiscibility of dry oil modified phenolic resin, so the flame retardant resistance of gained phenolic sheet, thermotolerance improve, stripping strength also improves under the situation of copper-clad laminate.
The used water soluble phenol resin with the melamine resin modification of the present invention can prepare like this: for example, in the presence of basic catalyst, trimeric cyanamide and formaldehyde are reacted 90～150 minutes (was good with 100～140 minutes) down 60～80 ℃ (are good with 65～75 ℃), in reaction mixture, add phenols, formaldehyde and basic catalyst then, in 70～100 ℃ (are good with 80～95 ℃) reaction 20～45 minutes (was good with 25～45 minutes) down, this reaction can fully be carried out under normal pressure usually.
As formaldehyde source, available formalin, paraformaldehyde etc.With the reaction of trimeric cyanamide in, the consumption of formaldehyde is generally 0.5～0.8 times of weight of trimeric cyanamide weight, is preferably 0.55～0.75 times of weight, the amount of the formaldehyde that adds simultaneously with phenols is generally 0.25～0.45 times of weight of phenols weight, is preferably 0.3～0.4 times of weight.
As above-mentioned basic catalyst, available such as ammonia, vulkacit H, Trimethylamine 99, sodium hydroxide, calcium hydroxide etc.Be generally 0.5～3 weight % of trimeric cyanamide in the reaction neutral and alkali catalyst consumption of trimeric cyanamide and formaldehyde, be preferably 0.7～2.5 weight %, the amount of the basic catalyst that adds simultaneously with phenols and formaldehyde is generally 2～10 weight % of phenols, is preferably 3～7 weight %.
As phenols, common available phenol, and other various alkylphenols etc. also can use.These phenols can a kind of independent use, also can share more than 2 kinds.
The ratio of trimeric cyanamide and phenols, trimeric cyanamide is 0.25～0.5 times of weight of phenols weight usually, is preferably 0.3～0.4 times of weight.
Like this, the phenolic sheet of the present invention that the veneer sheet of the invention described above is share gained with dry oil modified phenolic resin and water soluble phenol resin with the melamine resin modification is the veneer sheet that floods the invention described above after dipping on the paper base material is with the water soluble phenol resin of trimerization ammonia polyimide resin modification and drying again with dry oil modified phenolic resin composition and drying, several overlappings of the preforming material of gained, with Copper Foil or do not add Copper Foil, heating and pressurizing and the phenolic sheet made.
As paper base material, available lint paper, kraft paper etc.
Veneer sheet with dry oil modified phenolic resin composition and with the water soluble phenol resin of melamine resin modification when paper base material soaks into, can use the lacquer that is dissolved in solvent respectively.Can be used for veneer sheet as mentioned above with the solvent of dry oil modified phenolic resin composition modulation lacquer, can be used for solvent, the mixed solvent of organic solvents such as available methyl alcohol, water or organic solvent and water etc. with the water soluble phenol resin modulation lacquer of melamine resin modification.
Veneer sheet is generally 40～65 weight % with the adhesive capacity of dry oil modified phenolic resin composition in the preforming material, is preferably 40～60 weight %.Adhesive capacity with the water soluble phenol resin of melamine resin modification in the preforming material is generally 10～30 weight %, is preferably 10～25 weight %.
With several overlappings of preforming material, heating and pressurizing promptly obtains phenolic sheet of the present invention, can not add the Copper Foil heating and pressurizing therebetween, perhaps the single or double of preforming material laminate repeatedly on Copper Foil, heating and pressurizing is made the single or double copper-clad laminate.
The condition of heating and pressurizing, usually, Heating temperature is 150～200 ℃, is preferably 160～190 ℃, pressure 5～20MPa is preferably 9～15MPa; Time is 30～180 minutes, is preferably 60～120 minutes.
Phenolic sheet of the present invention be make paper base material with above-mentioned veneer sheet of the present invention with dry oil modified phenolic resin composition with the mixture of the water soluble phenol resin of melamine resin modification, be preferably contain dry oil modified phenolic resin 100 weight parts, with the impregnation mixture and the drying of water soluble phenol resin 3～20 weight parts (being more preferred from 3～15 weight parts) of melamine resin modification, several overlappings of gained preforming material, with Copper Foil or do not add Copper Foil, heating and pressurizing and the phenolic sheet made.In the mixture with the amount of the water soluble phenol resin of melamine resin modification if less than 3 weight parts, the effect that improves the phenolic sheet wet fastness is just little, if surpass 20 weight parts, then has and the intermiscibility of lacquer, the problem of punching processing reduction.
Solid formation branch in the lacquer (in solvent beyond the dissolved solvent total concn of composition) is advisable with 50～80 weight % usually.
Veneer sheet is generally 40～65 weight % with dry oil modified phenolic resin composition with the adhesive capacity of the mixture of the water soluble phenol resin of melamine resin modification in the preforming material, is preferably 45～60 weight %.
Other condition, same as described above.
Phenolic sheet of the present invention, be after making the water soluble phenol resin impregnation drying of paper base material in order to the melamine resin modification, (be preferably and contain dry oil modified phenolic resin 100 weight parts with dry oil modified phenolic resin composition with the mixture of the water soluble phenol resin of melamine resin modification with above-mentioned veneer sheet of the present invention, water soluble phenol resin 3～20 weight parts with the melamine resin modification, be more preferred from the mixture of 3～15 weight parts) impregnation drying, several overlappings of the preforming material of gained, with Copper Foil or do not add Copper Foil, heating and pressurizing and the phenolic sheet made.
The paper base material dipping solid formation branch concentration in the used lacquer during with the water soluble phenol resin of melamine resin modification (in solvent outside the dissolved solvent total concn of composition) is generally 10～20 weight %.
Veneer sheet is generally 40～65 weight % with the adhesive capacity of dry oil modified phenolic resin composition in the preforming material, the total adhesive capacity that is preferably in 45～60 weight %, the preforming material with the water soluble phenol resin of melamine resin modification is generally 10～30 weight %, is preferably 10～25 weight %.
Other condition is same as described above.
With embodiments of the invention and comparative example thereof the present invention is made more specific description below, but the present invention is not limited by these embodiment.Embodiment 1
With tung oil 35g, phenol 57.6g, cresols mixture (meta-cresol 60 weight %, p-cresol 40 weight %) 7.4g and tosic acid 0.1g in 80 ℃ the reaction 60 minutes after, add paraformaldehyde 30g and ammoniacal liquor (ammonia content 25 weight %) 5g, in 70 ℃ of reactions 120 minutes.Behind the reaction solution concentrating under reduced pressure, add methyl alcohol, obtain the tung oil modified phenolic resin lacquer (tung oil-modified rate 35 weight %) that solid formation is divided into 70 weight %.Solid formation to this lacquer divides 100 weight parts, fusion triphenylphosphate 30 weight parts, tetrabromo-bisphenol diglycidylether (epoxy equivalent (weight) 400) 20 weight parts, the mixed solvent (toluene and methanol=1/1 weight ratio) that adds methyl alcohol and toluene is made the face that solid formation divides 60 weight % and is coated with lacquer 1.
Formalin 240g, trimeric cyanamide 125g, Trimethylamine 99 1.5g are added phenol 370g, paraformaldehyde 140g, Trimethylamine 99 20g in reaction under 70 ℃ after 120 minutes again, in 90 ℃ of reactions 30 minutes.After this, carry out the concentrating under reduced pressure of reaction solution, remove condensation water and unreacted reactant etc.Add methyl alcohol therein, obtain the water soluble phenol resin with the melamine resin modification (the trimeric cyanamide amount is 20 weight %) the primary coat lacquer that solid formation is divided into 60 weight %.
At the heavy 125g/m of paper
2Kraft paper on dipping with the water soluble phenol resin primary coat of melamine resin modification with lacquer, drying, making the resin adhesive capacity is 17～20 weight %, the dipping face is coated with lacquer 1 in the above again, drying, making full resin (dividing Gu form) adhesive capacity is 50～54 weight %, gets preforming material.
With 8 overlappings of this preforming material, adhere to the Copper Foil (copper thickness 35 μ m, adhesive thickness 30 μ m) that conforms to agent on repeatedly in the above again, in 160 ℃, 9.8MPa heating 80 minutes, obtain the single side copper-clad laminate that thickness is 1.6mm.Embodiment 2
With tung oil 35g, phenol 30.2g, cresols mixture (meta-cresol 60 weight %, p-cresol 40 weight %) 34.8g and tosic acid 0.1g in 80 ℃ the reaction 60 minutes after, add paraformaldehyde 30g and ammoniacal liquor (ammonia content 25 weight %) 5g, in 70 ℃ of reactions 120 minutes.With the reaction solution concentrating under reduced pressure, add methyl alcohol then, obtain the tung oil modified phenolic resin lacquer (tung oil-modified rate 35 weight %) that solid formation is divided into 70 weight %.
Solid formation to this lacquer divides 100 weight parts, fusion triphenylphosphate 30 weight parts, tetrabromo-bisphenol diglycidylether (epoxy equivalent (weight) 400) 20 weight parts, the mixed solvent (toluene and methanol=1/1 weight ratio) that adds methyl alcohol and toluene is made the face that solid formation divides 60 weight % and is coated with lacquer 2.
Except the face with embodiment 1 be coated with the lacquer 1 change into face be coated with the lacquer 2, similarly to Example 1 the operation, obtain the single side copper-clad laminate that thickness is 1.6mm.Embodiment 3
Divide 100 weight parts to solid formation of synthetic tung oil modified phenolic resin lacquer among the embodiment 1, the water soluble phenol resin lacquer in the melamine resin modification that mixes embodiment 1 divides 5 weight parts by solid formation, and triphenylphosphate 30 weight parts, tetrabromo-bisphenol diglycidylether (epoxy equivalent (weight) 400) 20 weight parts, the mixed solvent (toluene and methanol=1/1 weight ratio) that adds methyl alcohol and toluene is made the face that solid formation divides 60 weight % and is coated with lacquer 3.
Except the face with embodiment 1 be coated with the lacquer 1 change into face be coated with the lacquer 3, similarly to Example 1 the operation, obtain the single side copper-clad laminate that thickness is 1.6mm.Embodiment 4
Divide 100 weight parts to solid formation of synthetic tung oil modified phenolic resin lacquer among the embodiment 2, the water soluble phenol resin lacquer in the melamine resin modification that mixes embodiment 1 divides 10 weight parts by solid formation, and triphenylphosphate 30 weight parts, tetrabromo-bisphenol diglycidylether (epoxy equivalent (weight) 400) 20 weight parts, the mixed solvent (toluene and methanol=1/1 weight ratio) that adds methyl alcohol and toluene is made the face that solid formation divides 60 weight % and is coated with lacquer 4.
Do not making the heavy 125g/m of paper that primary coat is handled
2Kraft paper on the dipping face be coated with the lacquer 4, drying, the resin adhesion amount be the preforming material of 50～54 weight %.
With 8 overlappings of this preforming material, repeatedly go up the Copper Foil (copper thickness 35 μ m, adhesive thickness 30 μ m) of adhesive bonding agent more in the above, in 160 ℃, 9.8MPa heating 80 minutes, obtain the single side copper-clad laminate that thickness is 1.6mm.Embodiment 5
Do not making the heavy 120g/m of paper that primary coat is handled
2Kraft paper on, the face of direct impregnation embodiment 1 be coated with the lacquer 1, drying, the resin adhesion amount be the preforming material of 50～54 weight %.Embodiment 6
Except dividing adding 5 weight parts to change into 2 weight parts by solid formation in the water soluble phenol resin lacquer in the melamine resin modification among the embodiment 3, operation obtains the single side copper-clad laminate that thickness is 1.6mm similarly to Example 3.Embodiment 7
Except dividing adding 5 weight parts to change into 25 weight parts by solid formation in the water soluble phenol resin lacquer in the melamine resin modification among the embodiment 3, operation obtains the single side copper-clad laminate that thickness is 1.6mm similarly to Example 3.Comparative example 1
Tung oil 35g, phenol 65g and tosic acid 0.1g after 6 hours, are added paraformaldehyde 30g and ammoniacal liquor (ammonia content 25 weight %) 5g in 80 ℃ of reactions, in 70 ℃ of reactions 120 minutes.Behind gained reaction solution concentrating under reduced pressure, add methyl alcohol, make the tung oil modified phenolic resin lacquer (tung oil-modified rate 35 weight %) that solid formation is divided into 70 weight %.
Solid formation to this tung oil modified phenolic resin lacquer divides 100 weight parts, fusion triphenylphosphate 30 weight parts, tetrabromo-bisphenol diglycidylether (epoxy equivalent (weight) 400) 20 weight parts, the mixed solvent (toluene and methanol=1/1 weight ratio) that adds methyl alcohol and toluene is made the face that solid formation divides 60 weight % and is coated with lacquer 5.
Except the face with embodiment 1 be coated with the lacquer 1 change into face be coated with the lacquer 5, similarly to Example 1 the operation, obtain the single side copper-clad laminate that thickness is 1.6mm.Comparative example 2
Do not making the heavy 120g/m of paper that primary coat is handled
2Kraft paper on, the face of direct impregnation comparative example 1 be coated with the lacquer 5, drying, the resin adhesion amount be the preforming material of 50～54 weight %.
With 8 overlappings of this preforming material, repeatedly go up the Copper Foil (copper thickness 35 μ m, adhesive thickness 30 μ m) of adhesive bonding agent again, in 160 ℃, 9.8MPa heating 80 minutes, obtain the single side copper-clad laminate that thickness is 1.6mm.
For the single side copper-clad laminate of above embodiment and comparative example gained, studied flame retardant resistance, punching processing, wet fastness, it the results are shown in Table 1.
Test method is as follows:
Flame retardant resistance (UL94): will vertically place with the test film that the etch method is removed Copper Foil fully, and leave flame in 10 seconds of following end in contact torch flame, and measure fire and extinguish required time.After fire extinguishes, contact 10 seconds of flame again, leave flame, measure fire and extinguish required time.Calculate the population mean of 10 measured values of 5 test films.The appearance scope means the minimum and maximum value of each measured value.
Wet fastness (water-intake rate): in the saturation vapour pressure of 121 ℃ of potheaters, test film is carried out the processing that 2128hPa kept 8 hours, measure the changes in weight before and after handling, calculate water-intake rate.
Punching processing: under 40 ℃ of temperature, go out the hole of pitch of holes 1.78mm with 80 tons of punch presses, check to have or not and peels off and and hole (order is white).In the table 1, zero expression as the punching processing metewand peel off and the hole does not occur respectively, △ represents slightly, * expression is quite a lot of.
Table 1
| Project | Embodiment | Comparative example | |||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????1 | ????2 | |
| Anti-flammability (second) scope evaluation moisture-proof (%) punching processing on average occurs and peels off and the hole | 2.4 0～7 V-0 3.3 ○ ○ | 2.4 0～6 V-0 3.2 ○ ○ | 1.7 0～4 V-0 3.1 ○ ○??? | 4.7 3～8 V-0 4.7 ○ ○ | 4.9 3～8 V-0 4.7 ○ ○ | 2.4 0～6 V-0 3.4 ○ ○ | 1.1 0～3 V-0 2.7 × △ | 2.5 0～8 V-0 3.5 △ △ | 4.9 3～8 V-0 5.0 ○ ○ |
From the comparison of embodiment 1～7 with comparative example 1,2, as seen use veneer sheet dry oil modified phenolic resin composition of the present invention, can make the punching processing raising of veneer sheet.
From the comparison of comparative example 2 with embodiment 5, visible veneer sheet of the present invention has the effect of giving the veneer sheet wet fastness preferably with dry oil modified phenolic resin composition than existing dry oil modified phenolic resin, and has equal punching processing.
Shown in the comparison of comparative example 1 and comparative example 2, when existing tung oil modified phenolic resin share with water soluble phenol resin with the melamine resin modification, the punching processing variation, and flame retardant resistance and wet fastness improve.Yet shown in the comparison of embodiment 1～7 and comparative example, when veneer sheet of the present invention share with dry oil modified phenolic resin composition and with the water soluble phenol resin of melamine resin modification, the flame retardant resistance and the wet fastness of veneer sheet more improved.
Embodiment 3 and embodiment 6,7 show, using veneer sheet of the present invention with under dry oil modified phenolic resin composition and the situation with the mixture of the water soluble phenol resin of melamine resin modification, in the mixture corresponding to dry oil modified phenolic resin 100 weight parts, during with cyanurotriamide modified water soluble phenol resin less than 3 weight parts, mix the effect that is produced with dry oil modified phenolic resin little, and when surpassing 20 weight parts, the punching processing reduction.
Above result shows, manufacturing for phenolic sheet, be used veneer sheet of the present invention with dry oil modified phenolic resin and water soluble phenol resin with the melamine resin modification, can obtain wet fastness, punching processing, flame retardant resistance improvement, these character can the balanced phenolic sheet that improves simultaneously.
Veneer sheet of the present invention is also made with meta-cresol and p-cresol except that phenol with dry oil modified phenolic resin composition, as a whole, its ortho position is active high, be used for to obtain high cross-linking density when phenolic sheet is made, its result has and gives the effect of phenolic sheet with good wet fastness and punching processing etc.Merge to use veneer sheet of the present invention with dry oil modified phenolic resin composition and the phenolic sheet of the present invention made with the water soluble phenol resin of melamine resin modification, because the effect of share with water soluble phenol resin with the melamine resin modification, have good wet fastness and punching processing etc., flame retardant resistance is also good simultaneously.
Claims (9)
1. veneer sheet dry oil modified phenolic resin composition, it is characterized in that: at the dry oil modified phenolic resin with siccative oil, phenols and formaldehyde reaction gained is in the veneer sheet usefulness dry oil modified phenolic resin composition of principal constituent, this phenols is made up of the cresols mixture that phenol and meta-cresol and p-cresol form, phenol is phenol to the mol ratio of this cresols mixture: cresols mixture=9: 1～5: 5, this dry oil modified phenolic resin be after the reaction of siccative oil and this phenols again in the presence of basic catalyst with formaldehyde reaction gained material.
2. by the described veneer sheet dry oil modified phenolic resin composition of claim 1, wherein said cresols mixture is made up of meta-cresol 60 ± 5 weight % and p-cresol 40 ± 5 weight %.
3. by the described veneer sheet dry oil modified phenolic resin composition of claim 2, its feature also is: with described dry oil modified phenolic resin is principal constituent, also contain at least a flame retardant resistance composition that is selected from brominated epoxy resin, bromo diphenyl ether and phosphoric acid ester, its amount is 25～60 weight % of described dry oil modified phenolic resin and described flame retardant resistance composition total amount.
4. phenolic sheet, it is characterized in that: described being used for property of the veneer sheet oil modified phenolic resin composition of one of paper base material dipping claim 1～3 also after drying, with several overlappings of gained preforming material, with Copper Foil or do not add Copper Foil, heating and pressurizing forms.
5. phenolic sheet, it is characterized in that: behind the water soluble phenol resin and drying of paper base material dipping with the melamine resin modification, flood the described veneer sheet of one of claim 1～3 again with dry oil modified phenolic resin composition and drying, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
6. phenolic sheet, it is characterized in that: the described veneer sheet of one of paper base material dipping claim 1～3 is with dry oil modified phenolic resin composition with the mixture and the drying of the water soluble phenol resin of melamine resin modification, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
7. by the described phenolic sheet of claim 6, its feature also is: veneer sheet is with dry oil modified phenolic resin composition with the water soluble phenol resin mixture of melamine resin modification, contain veneer sheet with dry oil modified phenolic resin 100 weight parts, with water soluble phenol resin 3～20 weight parts of melamine resin modification.
8. phenolic sheet, it is characterized in that: behind the water soluble phenol resin and drying of paper base material dipping with the melamine resin modification, flood the described veneer sheet of one of claim 1～3 again with dry oil modified phenolic resin composition with the mixture and the drying of the water soluble phenol resin of melamine resin modification, several overlappings of gained preforming material, with Copper Foil, or not adding Copper Foil, heating and pressurizing forms.
9. by the described phenolic sheet of claim 8, its feature also is: veneer sheet is with dry oil modified phenolic resin composition with the mixture of the water soluble phenol resin of melamine resin modification, contain veneer sheet with dry oil modified phenolic resin 100 weight parts, with water soluble phenol resin resin 3～20 weight parts of melamine resin modification.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95109859A CN1068361C (en) | 1995-09-22 | 1995-09-22 | Drying oil-modified phenolic resin composition for laminate and phenolic resin laminate using drying oil-modified phenolic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95109859A CN1068361C (en) | 1995-09-22 | 1995-09-22 | Drying oil-modified phenolic resin composition for laminate and phenolic resin laminate using drying oil-modified phenolic resin composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00132986 Division CN1287981C (en) | 1995-09-22 | 1995-09-22 | Phenolic resin laminated board using dry oil modified phenolic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1145928A true CN1145928A (en) | 1997-03-26 |
| CN1068361C CN1068361C (en) | 2001-07-11 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95109859A Expired - Lifetime CN1068361C (en) | 1995-09-22 | 1995-09-22 | Drying oil-modified phenolic resin composition for laminate and phenolic resin laminate using drying oil-modified phenolic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1068361C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434450C (en) * | 2005-04-08 | 2008-11-19 | 任庆祥 | Phenol resin for dipping papery decorative antifiring plate in highpressure, and fabricating technique thereof |
| CN103071830A (en) * | 2011-10-25 | 2013-05-01 | 钜橡企业股份有限公司 | Laminated base plate for drilling |
| CN102132212B (en) * | 2008-09-04 | 2013-08-28 | 日立化成株式会社 | Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030230382A1 (en) * | 2001-11-14 | 2003-12-18 | Westvaco Corporation | Method for releasing laminated materials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS508359A (en) * | 1973-05-24 | 1975-01-28 | ||
| JPS5339175B2 (en) * | 1974-07-31 | 1978-10-19 | ||
| JPS5241691A (en) * | 1975-09-30 | 1977-03-31 | Mitsubishi Gas Chem Co Inc | Prcess for producing eat resistant laminates and preparing a modified phenol resin suitable for them |
| JPS5573721A (en) * | 1978-11-27 | 1980-06-03 | Mitsubishi Gas Chem Co Inc | Preparation of oil-modified phenolic resin |
| JPS6293835A (en) * | 1985-10-18 | 1987-04-30 | Hitachi Ltd | Electrode structure for ion source |
| JPH057940A (en) * | 1991-06-28 | 1993-01-19 | Cycle Hitsuto:Kk | Curving method for gutter-like metallic member |
-
1995
- 1995-09-22 CN CN95109859A patent/CN1068361C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434450C (en) * | 2005-04-08 | 2008-11-19 | 任庆祥 | Phenol resin for dipping papery decorative antifiring plate in highpressure, and fabricating technique thereof |
| CN102132212B (en) * | 2008-09-04 | 2013-08-28 | 日立化成株式会社 | Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component |
| CN103071830A (en) * | 2011-10-25 | 2013-05-01 | 钜橡企业股份有限公司 | Laminated base plate for drilling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1068361C (en) | 2001-07-11 |
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