CN1055045C - Production of layered board and production of layered board for electric use - Google Patents
Production of layered board and production of layered board for electric use Download PDFInfo
- Publication number
- CN1055045C CN1055045C CN94101229A CN94101229A CN1055045C CN 1055045 C CN1055045 C CN 1055045C CN 94101229 A CN94101229 A CN 94101229A CN 94101229 A CN94101229 A CN 94101229A CN 1055045 C CN1055045 C CN 1055045C
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- priming paint
- laminated plate
- phenolic resins
- weight
- layered board
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Abstract
The present invention relates to layered board material and a production method of a layered board for electricity. A kind of chartaceous base material is impregnated in water primer with amino modified phenolic resin as a main component; then, the base material is dried at the temperature of 10 to 120 DEG C to make the base material have the water content of 5 to 25% (weight); the base material is impregnated in secondary paint with phenolic resin of a hydrophilic radical and a hydrophobic radical as a main component; finally, the base material is dried at 100 to 170 DEG C for obtaining the layered board material impregnated in the primer and the secondary paint; a plurality of blocks of the layered board material are superposed for obtaining a layered board. The layered board obtained by the present invention has excellent performance at the aspects of electric insulating performance, water resistance performance, fire retardance performance, etc.
Description
What the present invention relates to be used as circuit board in electronic instrument, the electrical equipment and insulating materials is electric with laminate and constitute the manufacture method of the laminated plate material of this laminate.
In recent years, to being widely used in the electric laminate of using of TV, video recording, stereo set, computer, office equipment, household electric appliances etc., except performances such as electric insulating quality, resistance to water, mouldability, processability, also require it to have anti-flammability.For making material satisfy these performance requirements, existing before people proposes, allow infiltrate for the first time amino modified phenolic resins priming paint of electric insulating quality, resistance to water and anti-flammability of tool excellence of papery matrix material, thereafter, infiltration has the floating coat material of the phenolic resins of excellent mouldability and processability again, and the laminated plate material that forms is thus made laminate.This situation, be to make the infiltrate priming paint of amino modified phenolic resins of papery matrix material, dry under the high temperature more than 130 ℃ again, floating coat material then infiltrates, but, in this high temperature drying process, along with the volatilization of solvent in the priming paint, the amino modified phenolic resins in the priming paint moves and the covering substrates surface to the surface direction of matrix material.Like this, not only the inner infiltration of base material quantity not sufficient has also hindered floating coat material infiltration base material inside, and its result is can not fully carry out the reaction of above-mentioned two kinds of phenolic resins in matrix material inside, is difficult to obtain as electric with the desired above-mentioned performance of laminate.
The invention provides a kind of manufacture method and electric manufacture method that overcomes laminate former the problems referred to above, useful with laminate, according to the present invention, can make the laminated plate material and the electrical layer pressing plate that have electric insulating quality, resistance to water, mouldability, processability and anti-flammability simultaneously.
The method according to this invention, to the papery matrix material of forming by cellulose fibre, infiltrating with amino modified phenolic resins for the first time is the aqueous priming paint of principal component, then, this papery matrix material of the priming paint that infiltrated is dry under 70-120 ℃ temperature, and water content is a laminated plate material of 5～25% (weight) in the manufacturing paper substrates; Then, making a laminated plate material infiltration is the floating coat material of principal component with the phenolic resins with hydrophilic group and hydrophobic group, and then, the papery matrix material of dry infiltrated priming paint and floating coat material obtains laminated plate material under 100-170 ℃ temperature.
By the paper substrates of the dry priming paint that infiltrated under 70～120 ℃ temperature, the amino modified phenolic resins in the priming paint is transferred to surface one side of base material, does not harden at this, and can keep roughly being dispersed in state in the base material.Then, can be in base material, fully mix with phenolic resins in the floating coat material of infiltration, these two kinds of resins can fully react, and obtain desirable performance.Dry priming paint under above-mentioned 70-120 ℃ temperature, moisture in the base material can be adjusted to 5～25% (weight), when moisture is in this scope, resin in priming paint and the floating coat can fully mix in base material, what need supplementary notes is, when the moisture in the base material after the laminated plate material drying during less than 5% (weight), the condensation reaction of the amino modified phenolic resins in the priming paint that has infiltrated in phenolic resins in the floating coat and the base material is just insufficient; And when the moisture in the base material during greater than 25% (weight), then the resin in the floating coat can't deeply be impregnated into base material inside.Promptly have only within the water content in the matrix material is in above-mentioned scope, the resin in the floating coat material could soak into the matrix material inside of the resin in the priming paint that infiltrates fully, at two kinds of interlaminar resins condensation reaction takes place fully, and obtains desirable performance.
As the papery matrix material, can use brown paper and lint paper etc.
As the amino modified phenolic resins in the priming paint, can use with Lauxite, melamine resin, the resin modified phenolic resins of guanamine, its infiltration amount in a dried laminated plate material is preferably in 5～25% (weight).As the most handy methanol aqueous solution of solvent that is used for priming paint, can use the solution of 0.5～4 part of weight methyl alcohol of dissolving to the water of 1 part of weight, the resin content of regulating in the priming paint is 23～38% (weight).At this moment, under the temperature conditions below the azeotropic point of methanol aqueous solution, more than 70 ℃, carry out the drying of a laminated plate material, can make the resin in the priming paint soak into the papery matrix material fully.Though the infiltration method about priming paint is also unrestricted, priming paint is distributed in the method for the one side of papery matrix material with roller coat.Because of the infiltration amount that the quantity of solvent that can be used in priming paint reduces and can regulate resin, this method is industrial.Has favourable part.
As the phenolic resins in the floating coat, preferably use tung oil modified phenolic resin, the cellulosic inserts that also can contain in case of necessity, inorganic powder inserts, glass fibre, asbestos fibre, paper pulp fiber, synthetic fibers, ceramic fibres etc. such as talcum, clay, silica, calcium carbonate, aluminium hydroxide.Above-mentioned phenolic resins, together with the resin in the priming paint, 35～75% (weight) of in dried final laminated plate material, preferably infiltrating.As the solvent that is used for floating coat, preferably methyl alcohol is adjusted to 40-60% (weight) with the resin content in the floating coat.Tung oil modified phenolic resin, though its tung oil has hydrophobic group, wherein hydroxyl is the hydrophilic group to the fine compatibility of papery matrix material tool, therefore, can be fine infiltrate in the papery matrix material in the laminated plate material of water content and go, and fully react with amino modified phenolic resins in the priming paint.
By the prepared laminated plate material of said method, but multilayer is overlapping, makes the electric laminate of using after the heating pressurization.In case of necessity, also can in this laminate, add metal foil laminatedly,, can use elemental metals paper tinsel and their Alloy Foil or the composite insulating foil of steel, aluminium, nickel, brass, iron etc. as metal forming.Lamination can at random be selected hardening temperature, firm time, briquetting pressure according to the thickness of laminated plate material and metal forming, and can select impact style for use, double belt mode, multiple roll molding mode etc.
The following describes embodiments of the invention and comparative example.Embodiment 1
Use 126g/m
2Brown paper as the papery matrix material, make this papery matrix material infiltration priming paint and drying after, the floating coat material that infiltrates again behind the heat drying paper substrates, is made laminated plate material.Priming paint uses melamine-modified phenolic resins, and the floating coat material uses tung oil modified phenolic resin, following preparation respectively:
The preparation of priming paint
Make formalin (formalin) the 70 weight portions reaction of phenol 100 weight portions and 37% (weight), generate bakelite type phenol reaction product A, make the reaction of melamine 100 weight portions and formalin (solid constituent 37% (weight)) 100 weight portions, generate melamine reaction product B.Then, with the phenol reaction product A50 weight portion of bakelite type and the mixture of melamine reaction product B50 weight portion, the methanol aqueous solution dilution of water and methyl alcohol to mix at 1: 1, the preparation solid constituent is the priming paint of 30% (weight).
The preparation of floating coat material
Make formalin 80 weight portions, the reaction of tung oil 30 weight portions of phenol 100 weight portions and 37% (weight), generate tung oil-modified bakelite type phenol reaction product, to this reaction product to be the ratio adding fire retardant tetrabromobisphenol A of 20% (weight), after the methyl alcohol dilution, obtaining the solid composition is the floating coat material of 55% (weight).In this tung oil-modified bakelite type phenolic resins, tung oil is hydrophobic group, and hydroxyl is a hydrophilic group.
The manufacturing of laminated plate material
With roller priming paint is coated this paper substrates by one of papery matrix material side, infiltrate first, drying is 30 seconds in 120 ℃ drier, gets a semi-harden laminated plate material of resin.Resin containing ratio in this laminated plate material is 15% (weight) of papery matrix material, and its water content is 6% (weight).Then, make this laminated plate material above-mentioned floating coat material that infiltrates again, heat drying is 100 seconds in 155 ℃ drier, obtains the semi-harden laminated plate material of resin.Resin content in this laminated plate material adds up to 52% (weight) with the resin and the resin in the floating coat material of priming paint.
The manufacturing of laminate
With 8 overlaids of the above laminated plate material that makes, be equipped with the thick Copper Foil of 0.035mm in the superiors with binding agent, as laminated body, with this laminated body at pressure 100kg/cm
2, 160 ℃ of temperature condition under heating pressurization 60 minutes, obtain the electric laminate of using of temperature 1.6mm.
Embodiment 2
Papery matrix material, priming paint and floating coat material use material similarly to Example 1, make the papery matrix material priming paint that infiltrates first, in 100 ℃ drier dry 30 seconds, obtain a semi-harden laminated plate material of resin.Resin containing ratio in this laminated plate material is 15% (weight) to paper substrates, and water content is 9% (weight).Then, infiltration floating coat material and dry is made laminated plate material under condition similarly to Example 1, and this laminated plate material is overlapping under condition similarly to Example 1, makes the electric laminate of using of thickness 1.6mm.Embodiment 3
Papery matrix material, priming paint and floating coat material use material similarly to Example 1, make the papery matrix material priming paint that infiltrates first, in 80 ℃ drier dry 30 seconds, obtain a semi-harden laminated plate material of resin.Resin containing ratio in this laminated plate material is 15% (weight) to paper substrates, and water content is 12% (weight).Then, infiltration floating coat material and dry is made laminated plate material under condition similarly to Example 1, and this laminated plate material is overlapping under condition similarly to Example 1, makes the electric laminate of using of thickness 1.6mm.Embodiment 4
Papery matrix material, priming paint and floating coat material use material similarly to Example 1, make the papery matrix material priming paint that infiltrates first, in 70 ℃ drier dry 30 seconds, obtain a semi-harden laminated plate material of resin.Resin containing ratio in this laminated plate material is 15% (weight) to paper substrates, and water content is 18% (weight).Then, infiltration floating coat material and dry is made laminated plate material under condition similarly to Example 1, and this laminated plate material is overlapping under condition similarly to Example 1, makes the electric laminate of using of thickness 1.6mm.Comparative example
Papery matrix material, priming paint and floating coat material use material similarly to Example 1, make the papery matrix material priming paint that infiltrates first, in 135 ℃ drier dry 30 seconds, obtain a semi-harden laminated plate material of resin.Resin containing ratio in this laminated plate material is 15% (weight) to paper substrates, and water content is 2% (weight).Then, infiltration floating coat material and dry is made laminated plate material under condition similarly to Example 1, and this laminated plate material is overlapping under condition similarly to Example 1, makes the electric laminate of using of thickness 1.6mm.
Evaluation test
| Baking temperature (℃) | Drying time (second) | Water content % (weight) | |
| Embodiment 1 | 120 | 30 | 6 |
| Embodiment 2 | 100 | 30 | 9 |
| Embodiment 3 | 80 | 30 | 12 |
| Embodiment 4 | 70 | 30 | 18 |
| Comparative example | 135 | 30 | 2 |
According to following method, electricly done test with regard to its electrical insulating property (insulaion resistance of normality, after boiling insulaion resistance), scolding tin hear resistance, water absorption rate, anti-flammability etc. with laminate to the foregoing description 1～4 and comparative example are resulting.
About electrical insulating property,, measure and in the atmosphere of 20 ℃ of temperature, relative humidity 65%, to place the insulaion resistance after 96 hours and to impregnated in the high-temperature-hot-water through boiling insulaion resistance after boiling processing in 2 hours according to JIS C6481 standard.
About the scolding tin hear resistance, be to measure on the scolding tin that floats over 260 ℃ elapsed time until expanding.
About water absorption rate, be to remove Copper Foil with the acid-hatching of young eggs comprehensively, test film was placed 24 hours in the atmosphere of 50 ℃ of temperature, measure its weight before suction is handled, then, record in the water of 23 ℃ of temperature absorbed water in 24 hours weight after handling of dipping again, trying to achieve the weight rate of the weight before weight before suction is handled back and suction and handled is handled with respect to suction, and should be worth as water absorption rate.
About anti-flammability, be 94V-O test method according to the UL specification, measure the required time of fray-out of flame of lighting, with the average fall time judgement of 10 test films.
The following table as a result of above-mentioned evaluation test is represented.As the table shows, can confirm that the electrical layer pressing plate of present embodiment is compared with comparative example, arbitrary feature all is good.
| Insulaion resistance normality (Ω) | Insulaion resistance boils back (Ω) | Scolding tin hear resistance (second) | Water absorption rate (%) | Anti-flammability (second) | |
| Embodiment 1 | 7.0×10 12 | 7.1×10 9 | 35 | 0.711 | 2.5 |
| Embodiment 2 | 7.8×10 12 | 8.9×10 9 | 37 | 0.708 | 2.0 |
| Embodiment 3 | 8.3×10 12 | 9.3×10 9 | 38 | 0.703 | 1.7 |
| Embodiment 4 | 8.1×10 12 | 9.2×10 9 | 37 | 0.702 | 1.7 |
| Comparative example | 4.4×10 12 | 3.1×10 8 | 25 | 0.748 | 4.0 |
As mentioned above, the electrical layer pressing plate that the present invention makes is that the baking temperature with the papery matrix material of the priming paint that infiltrated is controlled at 70-120 ℃, moisture in the papery matrix material can be adjusted in 5-25% (weight), and, can keep the amino modified phenolic resins roughly uniform dispersity in the papery matrix material in the priming paint thus, then, phenolic resins in the floating coat material of resin and infiltration in this priming paint is fully mixed, sufficient condensation reaction can take place, its result, as above commentary estimates that test confirms, can obtain at electrical insulating property, an electric laminate of using of excellent specific property is all had in aspect such as resistance to water and anti-flammability.
Claims (5)
1. the manufacture method of a laminated plate material is characterized in that
Making the papery stock of being made up of cellulose fibre infiltrate with amino modified phenolic resins first is in the aqueous priming paint of principal component;
The papery matrix material of the dry priming paint that infiltrated under 70-120 ℃ temperature obtains that water content is the laminated plate material of 5-25% (weight) in this papery matrix material;
Making a laminated plate material infiltration is in the floating coat material of principal component with the phenolic resins with hydrophilic group and hydrophobic group;
Then, the paper substrates of infiltrated as mentioned above priming paint and floating coat material is dry under 100-170 ℃ temperature.
2. the phenolic resins in the method for claim 1, wherein described floating coat material is tung oil modified phenolic resin.
3. method as claimed in claim 1 or 2, wherein, the amino modified phenolic resins in the described priming paint is melamine-modified phenolic resins.
4. method as claimed in claim 1 or 2, wherein, the solvent in the described priming paint is the mixture of water and alcohol, will the infiltrate papery matrix material of priming paint of described method is dry under the temperature of the azeotropic point from 70 ℃ to this mixture.
5. method as claimed in claim 1 or 2 is comprising the infiltration method first of described priming paint being coated the one side of described papery matrix material by the print roll coating method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6010198A JPH06287329A (en) | 1993-02-02 | 1994-02-01 | Production of prepreg and production of electrical laminate using the prepreg |
| CN94101229A CN1055045C (en) | 1993-02-02 | 1994-02-07 | Production of layered board and production of layered board for electric use |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1573193 | 1993-02-02 | ||
| CN94101229A CN1055045C (en) | 1993-02-02 | 1994-02-07 | Production of layered board and production of layered board for electric use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1106337A CN1106337A (en) | 1995-08-09 |
| CN1055045C true CN1055045C (en) | 2000-08-02 |
Family
ID=36940641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94101229A Expired - Lifetime CN1055045C (en) | 1993-02-02 | 1994-02-07 | Production of layered board and production of layered board for electric use |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH06287329A (en) |
| CN (1) | CN1055045C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001343200A (en) * | 2000-05-31 | 2001-12-14 | Fuugetsu:Kk | Used paper mold spheric crust for skyrocket and method for manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52747A (en) * | 1975-06-24 | 1977-01-06 | Nippon Almit Kk | Ultrasonic aluminium solder plating method |
| JPH04142338A (en) * | 1990-10-04 | 1992-05-15 | Hitachi Chem Co Ltd | Preparation of laminated sheet |
-
1994
- 1994-02-01 JP JP6010198A patent/JPH06287329A/en active Pending
- 1994-02-07 CN CN94101229A patent/CN1055045C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52747A (en) * | 1975-06-24 | 1977-01-06 | Nippon Almit Kk | Ultrasonic aluminium solder plating method |
| JPH04142338A (en) * | 1990-10-04 | 1992-05-15 | Hitachi Chem Co Ltd | Preparation of laminated sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1106337A (en) | 1995-08-09 |
| JPH06287329A (en) | 1994-10-11 |
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Expiration termination date: 20140207 Granted publication date: 20000802 |
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