CN102304280B - Formaldehyde-free zero-carbon environmentally-friendly board synthetized by circuit board and manufacture technology thereof - Google Patents
Formaldehyde-free zero-carbon environmentally-friendly board synthetized by circuit board and manufacture technology thereof Download PDFInfo
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Abstract
The invention discloses a formaldehyde-free zero-carbon environmentally-friendly board synthetized by circuit board and a manufacture technology thereof. The compaction raw material of the environmentally-friendly board comprises circuit board powder, isocyanate, release agent and water, and wood fiber powder and carbon filament fiber also can be added. The manufacture technology of the board comprises the following steps of: evenly stirring isocyanate and release agent; adding water to stir; drying the circuit board powder at constant temperature; adding processing accessory ingredient to be evenly mixed; feeding, paving a platen; smoothly releasing pressure to obtain the board after pressurizing; and standing and supplementing pressure. The board manufactured by the manufacture technology by the above raw material ingredients is the formaldehyde-free environmentally-friendly board which is completely free from formaldehyde, and the use amount of recovery powder of the circuit board can be above 95%, therefore improving waste use ratio. In the board manufacture process, the isocyanate and water can react to absorb water, so that the material moisture rate is lowered, no bubbles are formed, and the problem of exploring boards can be solved. The board manufactured by taking the circuit board recovery powder as the main raw material has good water-proof performance.
Description
Technical field
The present invention relates to a kind of environment-friendly sheet, relating in particular to a kind of circuit card powder synthetic that utilizes does not have aldehyde zero carbocyclic ring guarantor sheet material.The invention still further relates to a kind of circuit card powder synthetic that utilizes and do not have the ME that aldehyde zero carbocyclic ring is protected sheet material.
Background technology
The starting material of tradition woodwork board making are timber, need the deforestation resource, thereby cause soil erosion, and various natural disasteies take place, and influence physical environment and ecological balanced growth, not environmental protection and effectively energy-saving and emission-reduction.This woodwork sheet material burst size of methanal is big, and meet the water capacity and be prone to expansion, distortion, crooked, mouldy, not corrosion-resistant, not acidproof, not alkaline-resisting, and inflammable.
Along with the high speed development in city all over the world; Need use a large amount of material of construction, the dalle that industry and building are used comprises that wooden deck, wooden multi-ply wood, low middle-high density plate, shaving board or log board all do not use renewable resource circulation recovery technology, therefore needs a large amount of deforestation resources; Cause a large amount of timber resources overcut wastes; Excessively destroy ecotope, make the disturbed ecological balance state that all is at present all over the world, natural disasteies such as earthquake, rubble flow, floods, drought, snow disaster, sandstorm frequently take place; Global climate is risen suddenly warm, environmental pollution is more and more serious.The overcut forest reserves make disturbed ecological balance, soil erosion, and timber resources reduces, and soars thereby the woodwork prices of raw and semifnished materials are risen suddenly.
Current general Wood-based Panel Production technology all uses the thinner that contains aldehyde as the composition of producing gluing prescription; Because water ratio such as traditional tackiness agent urea-formaldehyde resin or resol are than higher; Can surpass 12% of tackiness agent weight, thereby tackiness agent can produce a large amount of water vapour with raw material generation chemical reaction in the making sheet this moment hot pressing.When the board making raw material is mainly the wiring board powder; The plate embryo dual function with heating power that in hot pressing, is under pressure; Water vapor can't be absorbed, and causes the generation of bubbling phenomenon easily, causes sheet material plate bursting phenomenon to take place at the outside bulging force of making sheet later stage pressure leak process bubbling greater than internal stress.
Summary of the invention
Not enough to prior art, the useless circuit card powder synthetic of utilization that the technical problem that the present invention will solve provides a kind of recyclable regenerative does not have the high fiber environmental sheet material of zero carbon and the ME thereof of plate bursting phenomenon.
In order to overcome the prior art deficiency, the technical scheme that the present invention adopts is: a kind of circuit card powder synthetic that utilizes does not have the ME that aldehyde zero carbocyclic ring is protected sheet material, it is characterized in that said ME comprises the steps:
A, isocyanic ester and releasing agent proportional mixing and stir;
B, add entry and stirring in proportion, form the making sheet batching;
C, the circuit card powder is carried out drying treatment, the moisture of control circuit board powder is no more than 3%, and the temperature in the control drying oven stirs drying in 125 ℃ constant temperature;
D, stir dried circuit card powder and making sheet batching proportional mixing, form mixing raw material and also guarantee that the weight percent of moisture is no more than 10%;
E, the even constant speed feeding of mixing raw material is got into the system of mating formation; Shakeout raw material with putting down roller; Mixing raw material gets into the slab that is compressed to unified thickness behind the preformer, sends to deburring in length and breadth by conveying belt, and then is transported to multilayer weight machine or Steel Continuous and flattens press sheet material is carried out the moulding pressurization; Pressurizeed 1 minute, the pressure of plate surface is reached more than the 8Mps, leave standstill and carry out ftercompction after 2 minutes again, ftercompction pressure reaches more than the 11Mps, the final vacuum pressure release in 3 minutes of ftercompction time remaining, and pressure leak process evenly successively decreases gently, pressure leak process at least 1 minute; The veneer sheet of said multi-daylight press is with the heating of circulating heat conduction oil, and the thermal oil temperature of said veneer sheet is controlled within 150 ℃ ~ 200 ℃;
After f, compacting finish, pull out sheet material, carry out turnover panel and air cooling then and handle;
G, sanding are decided thick, quality inspection, heap plate warehouse-in.
As the improvement of such scheme, said circuit card powder is that waste printed circuit board or circuit card scrap stock are disassembled the pulverulent material of wearing into, or the circuit boring powder that directly reclaims; Before the c step is carried out drying, the circuit card powder with vibrator screening and the assorted slag of magnetic metal, is made its not conglomeration of raw material.
Improvement as such scheme; Before the d step, increase the c1 step; High fiber accessories is carried out coarse breaking; And then pulverize to grind and make high fiber accessories change into the above wood fiber powder of 80 orders, carry out moisture drying in the temperature environment more than 100 ℃ and handle, control its moisture content 2%～4%; Under 180 ℃, stir the mixed carbon fibre powder that forms to wood fiber powder then; Stir circuit card powder and carbon fibre powder proportional mixing; Said high fiber accessories is agricultural crop straw, wooden saw powder or bamboo matter saw powder.
As the improvement of such scheme, before the d step, increase the c2 step, add processing aid and evenly mixed once more in proportion; Said processing aid comprises oxidation inhibitor, solidifying agent, carbon filament fiber.
As the improvement of such scheme, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester, 1～5 part of releasing agent, 1～8 part of water.
Environment-friendly sheet for no plate bursting that recyclable regenerative is provided; The technical scheme that the present invention adopts is: a kind of no aldehyde zero carbocyclic ring that adopts above-mentioned ME to prepare is protected sheet material; The compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 50～97 parts of circuit card powder; 3～20 parts of isocyanic ester, 1～5 part of releasing agent, 1～8 part of water.
As the improvement of such scheme, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester, 1～5 part of releasing agent, 3～6 parts of water.
As the improvement of such scheme, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～20 parts of isocyanic ester, 1～5 part of releasing agent, 2～8 parts of water, 10～20 parts of wood fiber powders, 5～12 parts of carbon filament fibers.
As the improvement of such scheme, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～20 parts of isocyanic ester; 1～5 part of releasing agent, 3～6 parts of water, 30～40 parts of wood fiber powders; 3～5 parts of water-resisting agents, 3～5 parts of fireproofing agents, 7～10 parts of carbon filament fibers; 1.5～2 parts in solidifying agent, 1.5～2 parts in oxidation inhibitor.
As the improvement of such scheme, said releasing agent is a paraffin, and said circuit card powder is that discarded circuit board reclaims powder.
The invention has the beneficial effects as follows: utilize circuit card powder synthetic not have in the aldehyde zero carbocyclic ring guarantor sheet material process for making and earlier isocyanic ester and releasing agent are mixed; Mixing with water makes water-soluble isocyanic ester and water fully merge again; Mix to stir form uniform making sheet batching, moisture content prevents its excessive moistening and can't can't uniform mixing and form local conglomeration with the making sheet major ingredient at subsequent process in the control making sheet batching.Moisture makes making sheet batching and the making sheet major ingredient can be crosslinked as crosslinking medium (medium); The existence that does not have moisture then powder can't synthetic plate; And powder contains moisture and can avoid airborne dust, thereby moisture can't omit in the making sheet process, but for the content of avoiding stirring inhomogeneous then moisture unsuitable too high; The making sheet process must be controlled the content of moisture in making sheet major ingredient and making sheet batching, so moisture suits to be present in respectively in major ingredient and the batching.Moisture mixes the degrees of fusion that can improve moisture and isocyanic ester with isocyanic ester earlier, effectively reduces the risk that the making sheet process receives the thermosetting bubbling.
In the mask-making technology later stage, the pressure of pressure leak process trigger squeeze evenly successively decreases gently, and whole pressure leak process continues 1 minute at least, thereby avoids the suffered external pressure sudden change of sheet material.In causing, making sheet process sheet material internal stress and heating power press the pressure difference that exceeds external pressure greater than the sheet material tolerance range; Moisture is in time drained by thermogenesis water vapor or other gasification substances generation expansion simultaneously, and both act on simultaneously and then cause the plate bursting phenomenon to take place easily.The mild step-down of pressure leak process helps in the plate bubble and is effectively drained and avoid forming bubbling, effectively reduces the risk of plate bursting.
Raw materials such as circuit card powder and isocyanic ester are complete formaldehydeless aldehyde-free health environment-friendly sheet by the sheet material that above-mentioned ME makes; Isocyanic ester usage quantity in this technology can be low to moderate 3%; Wiring board reclaims the powder consumption and can reach more than 95%, improves the efficient of utilization of waste material greatly, reduces the cost of sheet material; And wiring board reclaims powder itself and has extraordinary water resistance, and the sheet material that therefore makes also has extraordinary water resistance.Thereby making sheet process isocyanic ester can react with water and absorb moisture, makes the material water ratio reduce, and has reduced the emissions of water vapor, reduces the incidence of bubble/bubbling, does not produce bubbling and bubble basically, thereby has solved the plate bursting problem in the lump.
Embodiment
Specifically describe in the face of embodiment of the present invention down.
A kind of circuit card powder synthetic that utilizes of the present invention does not have the ME that aldehyde zero carbocyclic ring is protected sheet material, and said ME comprises the steps:
A, isocyanic ester and releasing agent proportional mixing and stir;
B, add entry and stirring in proportion, form the making sheet batching;
C, the circuit card powder is carried out drying treatment, the moisture of control circuit board powder is no more than 3%, and the temperature in the control drying oven stirs drying in 125 ℃ constant temperature, make material be convenient to uniform mixing.Drying process is preferably in the stirring type dryer tool carries out, and whipping process should use the alr mode of conversion from low speed to high speed, makes that mixing is more even.
D, stir dried circuit card powder and making sheet batching proportional mixing, form mixing raw material and also guarantee that the weight percent of moisture is no more than 10%;
E, the even constant speed feeding of mixing raw material is got into the system of mating formation; Shakeout raw material with putting down roller; Mixing raw material gets into the slab that is compressed to unified thickness behind the preformer, sends to deburring in length and breadth by conveying belt, and then is transported to multilayer weight machine or Steel Continuous and flattens press sheet material is carried out the moulding pressurization; Pressurizeed 1 minute, the pressure of plate surface is reached more than the 8Mps, leave standstill and carry out ftercompction after 2 minutes again, ftercompction pressure reaches more than the 11Mps, the final vacuum pressure release in 3 minutes of ftercompction time remaining, and pressure leak process evenly successively decreases gently, pressure leak process at least 1 minute; The veneer sheet of said multi-daylight press is with the heating of circulating heat conduction oil; The thermal oil temperature of said veneer sheet is controlled within 150 ℃ ~ 200 ℃; Make veneer sheet continue to keep higher temperature; Guarantee the temperature of pressing plate, use mobile oil to heat and to make each position of veneer sheet receive thermal equilibrium, avoid each position excessive temperature differentials of veneer sheet to influence board materials production and board quality.
Wherein, pressure process does not settle at one go, but the process of adherence pressure progressively makes that various interaction between component are tightr, has interactional surge time simultaneously.Be provided with pressure maintaining period in the pressure process, supply raw materials, make the board quality of its formation more stable with the time of crosslinked action.Stress-relief process also is the process that progressively reduces pressure; Avoid rapid step-down to form the inconsistent sheet material explosion that causes of sheet material inside and outside pressure; Sheet material flaws such as the inconsistent or layering of the local performance of stealthy explosion of avoiding causing thus and sheet material; Further improve the quality of sheet material and consistence, the stability of sheet material, make sheet material durable.
After f, compacting finish, pull out sheet material, carry out conventional making sheet operations such as turnover panel and air cooling processing then.
G, sanding are decided thick, quality inspection, heap plate warehouse-in.
Utilizing circuit card powder synthetic not have in the aldehyde zero carbocyclic ring guarantor sheet material process for making mixes isocyanic ester and releasing agent earlier; Mixing with water makes water-soluble isocyanic ester and water fully merge again; Mix to stir form uniform making sheet batching, moisture content prevents its excessive moistening and can't can't uniform mixing and form local conglomeration with the making sheet major ingredient at subsequent process in the control making sheet batching.Moisture makes making sheet batching and the making sheet major ingredient can be crosslinked as crosslinking medium (medium); The existence that does not have moisture then powder can't synthetic plate; And powder contains moisture and can avoid airborne dust, thereby moisture can't omit in the making sheet process, but for the content of avoiding stirring inhomogeneous then moisture unsuitable too high; The making sheet process must be controlled the content of moisture in making sheet major ingredient and making sheet batching, so moisture suits to be present in respectively in major ingredient and the batching.Moisture mixes the degrees of fusion that can improve moisture and isocyanic ester with isocyanic ester earlier, effectively reduces the risk that the making sheet process receives the thermosetting bubbling.
In the mask-making technology later stage, the pressure of pressure leak process trigger squeeze evenly successively decreases gently, and whole pressure leak process continues 1 minute at least, thereby avoids the suffered external pressure sudden change of sheet material.In causing, making sheet process sheet material internal stress and heating power press the pressure difference that exceeds external pressure greater than the sheet material tolerance range; Moisture is in time drained by thermogenesis water vapor or other gasification substances generation expansion simultaneously, and both act on simultaneously and then cause the plate bursting phenomenon to take place easily.The mild step-down of pressure leak process helps in the plate bubble and is effectively drained and avoid forming bubbling, effectively reduces the risk of plate bursting.
Raw materials such as circuit card powder and isocyanic ester are complete formaldehydeless aldehyde-free health environment-friendly sheet by the sheet material that above-mentioned ME makes; Isocyanic ester usage quantity in this technology can be low to moderate 3%; Wiring board reclaims the powder consumption and can reach more than 95%, improves the efficient of utilization of waste material greatly, reduces the cost of sheet material; And wiring board reclaims powder itself and has extraordinary water resistance, and the sheet material that therefore makes also has extraordinary water resistance.Thereby making sheet process isocyanic ester can react with water and absorb moisture, makes the material water ratio reduce, and has reduced the emissions of water vapor, reduces the incidence of bubble/bubbling, has solved the plate bursting problem.
The sheet material dual function with heating power that in hot pressing, is under pressure, the moisture content start vaporizer in the fiber, the evaporation of moisture content can destroy gelatinous layer, and when sheet material carried out release in the press outlet, its outside expansible power caused plate bursting greater than interfibrous internal stress.Isocyanic ester can generate amine and carbonic acid gas with the water reaction, and amine further generates with isocyanate reaction and replaces urea.Owing to contain unsaturated link(age) in the isocyanic ester structure, therefore have high reactivity, organic or inorganic things easy and some band reactive groups react, and generate polyurethane elastomer.The tackiness agent that adds the MDI isocyanic ester can reduce sheet material bubbling rate in process of production, avoids plate bursting.
Along with the global electronic industrial expansion; Waste household appliances reclaims system and progressively sets up; Various places are set up the waste household appliances recovery center of disassembling accordingly and are disassembled waste electrical equipment, and electrical equipment is disassembled the back MAT'L recyclings such as plastics, metals, and the deleterious material of keeping under strict control is transferred to the relevant center processing of disposing; Remaining circuit card major part is made landfill disposal, the not enough science of such disposal options.Electronic industry produces the discarded scrap stock of a large amount of circuit cards, extracts metal after most of enterprise directly becomes piece to burn to extract metallic copper or reclaim the scrap stock fragmentation, PCB (circuit card) the direct landfill of powder residue or clear.Clear simultaneously or the copper-clad plate, the boring powder that also have the electronic industry production process to produce of landfill, so just produce a large amount of depleted electronic wastes.Only CHINESE REGION all produces waste printed circuit board more than 5,000,000 tons every year, and the circuit card powder is the thermosetting fibre resin-oatmeal that is not easy to degrade, and directly discarded or landfill does not meet the requirement of energy-saving and emission-reduction.For the renewable resource recycling provides abundant raw material sources; Utilize correlation technique of the present invention; Circuit card after disassembling waste electrical equipment and industrial waste circuit card reclaim; After employing electrostatic separation technique extraction metal after the circuit card fragmentation, directly press prescription provided by the invention to remaining circuit card powder as the staple synthetic plate.
More preferably, said circuit card powder is that waste printed circuit board or circuit card scrap stock are disassembled the pulverulent material of wearing into, or the circuit boring powder that directly reclaims.Before the c step is carried out drying, the circuit card powder with vibrator screening and the assorted slag of magnetic metal, is made its not conglomeration of raw material.
More preferably; Before the d step, increase the c1 step, high fiber accessories is carried out coarse breaking, and then pulverize to grind and make high fiber accessories change into the above wood fiber powder of 80 orders; Carry out moisture drying in the temperature environment more than 100 ℃ and handle, control its moisture content 2%～4%; Under 180 ℃, stir the mixed carbon fibre powder that forms to wood fiber powder then.Thereby can using impeller to stir drying, whipping process can be mixed the carbon fibre powder that is easier to form the floor easily with other material generation crosslinked action; The carbon fibre powder that high-speed stirring obtains has snappiness more, keeps its good toughness.Simultaneously also can add water-resisting agent, fireproofing agent stirs, and prevents the high temperature material of burning, water-resisting agent is able to wood fiber powder is carried out premix, thereby wood fiber powder is formed better waterproof fireproofing protection.Stir circuit card powder and carbon fibre powder proportional mixing then.
Said high fiber accessories is agricultural crop straw, wooden saw powder or bamboo matter saw powder.Saw the wood fiber powder mixing of powder, the making of bamboo wood saw powder with the recovery powder of depleted circuit card and by various stalks or timber; And add various additive synthesis; With various material mixing evenly and to suppress waterproof, fire prevention, anti-expansion, preventing deformation, anti-bending, mildew-resistant, anticorrosion, acidproof, alkaline-resisting and burst size of methanal through powerful pressure be that zero circuit card powder synthetic does not have aldehyde zero carbocyclic ring and protects sheet material; Realized various waste materials are reclaimed the purpose of the cyclic regeneration of making sheet material; Avoid the overcut forest, help keeping and the natural environment rehabilitation and the eubiosis, reduce natural disaster; Stablize the sheet material price, reach the effect that the environmental protection low-carbon energy-saving reduces discharging.
The annual agricultural crop straw output of China is several hundred million tons, comprises corn straw, wheat stalk, rice straw, bagasse and other agricultural crop straw.Along with the policy support of the whole world to agricultural, APEC member states carries out the technological cooperation that the comprehensive reprocessing cycle waste resource of agricultural crop straw utilizes the aspect each other in order to promote Agriculture Ecological Environment Protection in own country.There are a large amount of farm crop in China; Like the corn straw in northeast, cotton stalk, North China and East China and the southern rice straw and the wheat stalk and very abundant of northwest with resources such as bagasse; And these residue agricultural crop straws all do not add and have utilized; All be direct landfill or burned on the field, burning process produces a large amount of sulfurous gas bigger spinoff is played in climate warming, environmental disruption, does not utilize the eubiosis.Yet agricultural crop straw all contains many lignocellulose compositions, can reprocessing cycle recycles, and can grind becomes fragmental and become wood fiber powder, as the formula material of sheet material.Renewable wooden resources such as agricultural crop straw that China's various places agriculture prodn forms and bamboo wood saw powder are not utilized effectively and landfill or burning, are unfavorable for the implementation of environmental protection low-carbon (LC).
Produce a large amount of timber or bamboo wood saw powder in wood industry goods industries (furniture, floor) and the bamboo product industry production process; These saw powder are that wooden chip does not all have effectively regeneration recycling; Basically all be to do to burn or landfill disposal, not only waste resource, and contaminate environment.Present timber floor, laminated flooring are popular; But its common work-ing life is about 3 to 5 years; Because these floor surfaces have overlayed fireproofing and have played fire-retardant effect, can't burn and can only handle after discarding as garbage loading embeading, increase the weight of the burden of environment protection.And the wood powder that these waste and old consolidated floors can be made into more than 80 orders after through milled processed is a wood fiber powder, uses as the sheet material stopping composition.
Use agricultural crop straw, wooden saw powder or bamboo matter saw powder as high fiber accessories; Be that recyclable waste resource avoids waste and avoids influencing environment; The weight that alleviates sheet material again improves the toughness and the intensity of sheet material; Near the performance of timber, make sheet material to saw and to bore, can carry out abnormity processing more, also can carry out special-shaped pressing plate.
More preferably, before the d step, increase the c2 step, add processing aid and evenly mixed once more in proportion.Said processing aid comprises oxidation inhibitor, solidifying agent, carbon filament fiber.Elder generation is with the main raw material uniform mixing, and then the interpolation processing aid, and more evenly crosslinked action is closer thereby guarantee to mix between the main raw material.Can comprise water-resisting agent in the processing aid, said water-resisting agent is one or more in paraffin, silicone oil, white oil, the middle palm wax.Can add water-resisting agent earlier, in advance high fibre material formed the appearance protection.Thereby the sheet material that uses this technology to make can dig, can follow closely, can saw as solid wood timber, and is easy to process, and renewable recycling use.Added and short cut carbon filament fiber and the corresponding interior external stress ability to bear that has improved sheet material of various composite assistant, improved resistance to impact shock and static strength, the MOR of sheet material simultaneously.
More preferably, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester, 1～5 part of releasing agent, 1～8 part of water.The sheet material plate bursting probability for preparing in the component of this ratio allotment is near zero, and has that higher internal bond strength is high, MOR is strong, Young's modulus is high, hold screw power, and density variation is little in the plate, and density is high.
Carry out the sheet material manufacturing through above-mentioned sheet material ME; Environment-friendly sheet for no plate bursting that recyclable regenerative is provided; The material matching that the present invention adopts is: a kind of no aldehyde zero carbocyclic ring is protected sheet material, and the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 50～97 parts of circuit card powder, 3～20 parts of isocyanic ester; 1～5 part of releasing agent, 1～8 part of water.
More preferably, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester, 1～5 part of releasing agent, 3～6 parts of water.
More preferably, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～20 parts of isocyanic ester, 1～5 part of releasing agent, 2～8 parts of water, 10～20 parts of wood fiber powders, 5～12 parts of carbon filament fibers.
The high-intensity performance that the wood fiber powder synthetic plate that circuit card powder and stalk, timber or bamboo wood saw powder are made has promptly been inherited circuit card has the excellent toughness of wood fibre and less density again; Make sheet material that following effect arranged: both to alleviate the proportion of sheet material, alleviated the product bearing capacity of buildings; The static strength of reinforcement plate section product and MOR again; Also make plate product process easily, can suppress different shape.
Utilize useless electronic circuit board regenerative powder or/and wiring board boring powder is main builder, can the waste resource reprocessing cycle be used, help environmental protection and energy-saving and emission-reduction.Because circuit card (CCL, PCB) powder mainly is made up of epoxy resin and spun glass; Have waterproof, preventing deformation, anti-expansion, mildew-resistant, effect such as anticorrosion, acidproof, alkaline-resisting with its plate product of doing the raw material manufacturing; And can reach zero formaldehyde standard, recovery more also capable of circulation.
Add the proportion that carbonization lignocellulosic mixture powder mainly can alleviate sheet material; The gravity that bears of practicing thrift transportation cost and using sheet material; Increase the inside and outside stress of sheet material, static strength and MOR are effectively improved, strengthen the use properties of sheet material simultaneously; Can suppress the Z-Correct bump mapping Z-correct of different shape, make it that sensation modelled after an antique more arranged.Add the lignocellulosic mixture powder and can make sheet material have more the fiber bond strength, make the better elasticity of having of sheet material, in the later stage use course of processing superior use properties being provided.
More preferably, the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～20 parts of isocyanic ester; 1～5 part of releasing agent, 3～6 parts of water, 30～40 parts of wood fiber powders; 3～5 parts of water-resisting agents, 3～5 parts of fireproofing agents, 7～10 parts of carbon filament fibers; 1.5～2 parts in solidifying agent, 1.5～2 parts in oxidation inhibitor.Wherein, said carbon filament fiber is a spun glass.
More preferably, said releasing agent is a paraffin, and said circuit card powder is that discarded circuit board reclaims powder, uses wiring board to reclaim powder manufacturing sheet material and can recycle refuse, turns waste into wealth.
Wherein paraffin has the effect of water-resisting agent concurrently; And can increase and add in paraffin, silicone oil, white oil, the middle palm wax one or more as water-resisting agent; The best is to add paraffin emulsion; To the effect that the wood fibre composition and the circuit card meal component of high fiber environmental sheet material plays water resisting protection, prevent the distortion of sheet material water-swellable, reach mildew-resistant, rot-resistant effect.Said fireproofing agent is that ammonium chloride, salt of wormwood, carbon are joined one or more in the ammonium dihydrogen; Said carbon filament fiber is a spun glass; Said solidifying agent is one or more in ammonia chloride, oxalic acid, phenolic aldehyde amine, polyetheramine, the fragrant fat amine, and said oxidation inhibitor is one or more in fragrant fat amine antioxidants, phenolic antioxidant, thioesters, the phosphite.
More preferably; Said fireproofing agent is that ammonium chloride, salt of wormwood, carbon are joined one or more in the ammonium dihydrogen; Said formaldehyde is caught and caught agent is in polynite, trimeric cyanamide, the phenol one or more; Said solidifying agent is one or more in ammonia chloride, oxalic acid, phenolic aldehyde amine, polyetheramine, the fragrant fat amine, and said oxidation inhibitor is one or more in fragrant fat amine antioxidants, phenolic antioxidant, thioesters, the phosphite.
Wherein, add ammonium chloride, salt of wormwood, carbon and join in the ammonium dihydrogen one or more as fireproofing agent, also can add phosphorus nitrogen boron molybdenum magnesium zinc-aluminium compsn is the sheet material fireproofing agent, and making fireproofing agent is that fire retardant is uniformly distributed in tiny fiber surface.Fire retardant is met high thermogenesis acid, forms dewatering agent, and along with the rising of temperature, fire retardant systems will carry out vigorous reaction, and producing water vapour and non-flammable gases is flame retardant resistance gas, simultaneously the expanded foamed formation porous foam of system charring layer.Because the combustiblematerials concentration that water vapour and not so gas can dilute sheet material, charring layer plays the effects such as effusion of resistance heat, resistance oxygen and prevention degradation product, is spatial, omnibearing thereby make whole fire-retardant process, makes the product fire resistance reach the Bf1 level.Can add the efficient fumicants that presses down in the fireproofing agent and effectively reduce smokescope.
Wherein, the carbon filament fiber of interpolation is a spun glass, and the carbon filament fiber of interpolation should be short and cuts the carbon filament fiber, and its length is 3 millimeters to 25 millimeters, thereby can increase the intensity of sheet material and strengthen the bearing capacity of whole sheet material.
Wherein, Add in ammonia chloride, oxalic acid, phenolic aldehyde amine, polyetheramine, the fragrant fat amine one or more as solidifying agent, most preferably with ammonia chloride as solidifying agent, can make sheet material accelerate to solidify in process of production; Shorten the production cycle; Raise the efficiency, plate product is produced the back can carry out next step sheet material processed and applied, also can prevent the phenomenon that the next product of harsh output breaks up easily simultaneously at once.
Wherein, Add in fragrant fat amine antioxidants, phenolic antioxidant, thioesters, the phosphite one or more as oxidation inhibitor; Most preferably add in the sheet material as oxidation inhibitor, can prevent to receive in the long-time use of the plate product of producing the climate temperature influence and generation oxidation or solarization with phosphite.
Adding fireproofing agent at prescription, shortly cut carbon filament fiber, solidifying agent, oxidation inhibitor, stablize composite assistant (stablize, dispersion, activity) etc. mainly makes sheet material melt mutually; Bond strength is higher; The sheet material stable curing does not receive the weather oxygenizement; Can also have natural wood material smell, and can solve various performance requriementss such as dalle fire prevention.
Through analyzing repeatedly and verification experimental verification, obtain followingly can satisfying the moulding manufacturing and utilizing circuit card powder synthetic not have the embodiment of material matching that aldehyde zero carbocyclic ring is protected the various components of sheet material.
Embodiment one: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 97 parts of circuit card powder, 3 parts of isocyanic ester, 1 part of paraffin, 4 parts of water.
Embodiment two: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 97 parts of circuit card powder, 20 parts of isocyanic ester, 5 parts of paraffin, 8 parts of water.
Embodiment three: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 50 parts of circuit card powder, 8 parts of isocyanic ester, 3 parts of paraffin, 1 part of water.
Embodiment four: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 75 parts of circuit card powder, 12 parts of isocyanic ester, 2 parts of paraffin, 3 parts of water.
Embodiment five: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 50 parts of circuit card powder, 10 parts of isocyanic ester, 4 parts of paraffin, 3 parts of water.
Embodiment six: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 12 parts of isocyanic ester, 4 parts of paraffin, 5 parts of water.
Embodiment seven: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 97 parts of circuit card powder, 12 parts of isocyanic ester, 5 parts of paraffin, 6 parts of water.
Embodiment eight: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 3 parts of isocyanic ester, 1 part of paraffin, 3 parts of water.
Embodiment nine: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 90 parts of circuit card powder, 8 parts of isocyanic ester, 3 parts of paraffin, 4 parts of water.
Embodiment ten: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 12 parts of isocyanic ester, 4 parts of paraffin, 6 parts of water, 10 parts of wood fiber powders, 8 parts of carbon filament fibers.
Embodiment 11: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 97 parts of circuit card powder, 12 parts of isocyanic ester, 5 parts of paraffin, 8 parts of water, 20 parts of wood fiber powders, 5 parts of carbon filament fibers.
Embodiment 12: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 3 parts of isocyanic ester, 1 part of paraffin, 2 parts of water, 20 parts of wood fiber powders, 12 parts of carbon filament fibers.
Embodiment 13: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 90 parts of circuit card powder, 8 parts of isocyanic ester, 3 parts of paraffin, 4 parts of water, 15 parts of wood fiber powders, 12 parts of carbon filament fibers.
Embodiment 14: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 12 parts of isocyanic ester, 4 parts of paraffin; 5 parts of water, 10 parts of wood fiber powders, 3 parts of ammonium chlorides; 8 parts of carbon filament fibers, 1.5 parts of ammonia chlorides, 1.8 parts of phosphites.
Embodiment 15: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 97 parts of circuit card powder, 12 parts of isocyanic ester, 5 parts of paraffin; 6 parts of water, 20 parts of wood fiber powders, 4 parts of ammonium chlorides; 10 parts of carbon filament fibers, 1.5 parts of ammonia chlorides, 1.5 parts of phosphites.
Embodiment 16: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 80 parts of circuit card powder, 3 parts of isocyanic ester, 1 part of paraffin; 3 parts of water, 20 parts of wood fiber powders, 5 parts of ammonium chlorides; 7 parts of carbon filament fibers, 1.8 parts of ammonia chlorides, 1.8 parts of phosphites.
Embodiment 17: the compacting raw material that no aldehyde of the present invention zero carbocyclic ring is protected sheet material comprises the component that weight ratio is following: 90 parts of circuit card powder, 8 parts of isocyanic ester, 3 parts of paraffin; 4 parts of water, 15 parts of wood fiber powders, 5 parts of ammonium chlorides; 7 parts of carbon filament fibers, 2 parts of ammonia chlorides, 2 parts of phosphites.
According to the sheet material of the component manufacturing of the foregoing description, through test each item performance index, its experimental data is following: (is that the LY/T1611-2003 standard detects by national high-density artificial board standard)
Wherein part performance perameter detected result such as following table:
In addition, the sheet material for preparing through ME of the present invention of the outfit raw material among each embodiment has following good performance perameter.Wherein detected burst size of methanal is zero (standard-required E0≤0.5mg/100g); Secondly, the density of sheet material is greater than 1.39kg/m
3(standard-required>=0.8 kg/m
3); In addition, the density variation scope is in the plate :+0.63% ,-1.26% (standard-required≤± 4.0%).
In above-mentioned each embodiment; Paraffin that the combination raw materials replacement of one or more in interpolation paraffin, silicone oil, white oil, the middle palm wax is original or silicone oil are as water-resisting agent; Experiment test plate product repeatedly; Its various performance parameters phase residual quantity is that acceptable substitutes composition mutually less than 3.5%.
One or more the combination raw materials of joining in the ammonium dihydrogen with salt of wormwood, carbon replaces original ammonium chloride as fireproofing agent, experiment test plate product repeatedly, and its various performance parameters phase residual quantity is that acceptable substitutes composition mutually less than 5%.
Said carbon filament fiber is a short glass fiber.
One or more combination raw materials with in oxalic acid, phenolic aldehyde amine, polyetheramine, the fragrant fat amine replaces original ammonia chloride as solidifying agent, experiment test plate product repeatedly, and its various performance parameters phase residual quantity is that acceptable substitutes composition mutually less than 3%.
With fragrant fat amine antioxidants, phenolic antioxidant, thioesters, in one or more combination raw materials replace original phosphite as oxidation inhibitor; Experiment test plate product repeatedly; Its various performance parameters phase residual quantity is that acceptable substitutes composition mutually less than 3.6%.
The above disclosed the preferred embodiments of the present invention that are merely can not limit the present invention's interest field certainly with this, so according to the equivalent variations that claim of the present invention is done, still belong to the scope that the present invention is contained.
Claims (6)
1. one kind is utilized circuit card powder synthetic not have the ME that aldehyde zero carbocyclic ring is protected sheet material, it is characterized in that said ME comprises the steps:
A, isocyanic ester and releasing agent proportional mixing and stir;
B, add entry and stirring in proportion, form the making sheet batching;
C, the circuit card powder is carried out drying treatment, the moisture of control circuit board powder is no more than 3%, and the temperature in the control drying oven stirs drying in 125 ℃ constant temperature;
D, stir dried circuit card powder and making sheet batching proportional mixing, form mixing raw material and also guarantee that the weight percent of moisture is no more than 10%;
E, the even constant speed feeding of mixing raw material is got into the system of mating formation; Shakeout raw material with putting down roller; Mixing raw material gets into the slab that is compressed to unified thickness behind the preformer, sends to deburring in length and breadth by conveying belt, and then is transported to multilayer weight machine or Steel Continuous and flattens press sheet material is carried out the moulding pressurization; Pressurizeed 1 minute, the pressure of plate surface is reached more than the 8Mps, leave standstill and carry out ftercompction after 2 minutes again, ftercompction pressure reaches more than the 11Mps, the final vacuum pressure release in 3 minutes of ftercompction time remaining, and pressure leak process evenly successively decreases gently, pressure leak process at least 1 minute; The veneer sheet of said multi-daylight press is with the heating of circulating heat conduction oil, and the thermal oil temperature of said veneer sheet is controlled within 150 ℃ ~ 200 ℃;
After f, compacting finish, pull out sheet material, carry out turnover panel and air cooling then and handle;
G, sanding are decided thick, quality inspection, heap plate warehouse-in;
The compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester, 1～5 part of releasing agent, 1～8 part of water.
2. the circuit card powder synthetic that utilizes according to claim 1 does not have the ME that aldehyde zero carbocyclic ring is protected sheet material; It is characterized in that; Said circuit card powder is that waste printed circuit board or circuit card scrap stock are disassembled the pulverulent material of wearing into, or the circuit boring powder that directly reclaims; Before the c step is carried out drying, the circuit card powder with vibrator screening and the assorted slag of magnetic metal, is made its not conglomeration of raw material.
3. the circuit card powder synthetic that utilizes according to claim 1 does not have the ME that aldehyde zero carbocyclic ring is protected sheet material; It is characterized in that; Before the d step, increase the c1 step, high fiber accessories is carried out coarse breaking, and then pulverize to grind and make high fiber accessories change into the above wood fiber powder of 80 orders; Carry out moisture drying in the temperature environment more than 100 ℃ and handle, control its moisture content 2%～4%; Under 180 ℃, stir the mixed carbon fibre powder that forms to wood fiber powder then; Stir circuit card powder and carbon fibre powder proportional mixing; Said high fiber accessories is agricultural crop straw, wooden saw powder or bamboo matter saw powder.
4. the circuit card powder synthetic that utilizes according to claim 3 does not have the ME that aldehyde zero carbocyclic ring is protected sheet material, it is characterized in that, before the d step, increases the c2 step, adds processing aid and evenly mixed once more in proportion; Said processing aid comprises solidifying agent, oxidation inhibitor, carbon filament fiber, and said carbon filament fiber is a short glass fiber.
5. the circuit card powder synthetic that utilizes according to claim 1 does not have the ME that aldehyde zero carbocyclic ring is protected sheet material; It is characterized in that the compacting raw material of said environment-friendly sheet comprises the component that weight ratio is following: 80～97 parts of circuit card powder, 3～12 parts of isocyanic ester; 1～5 part of releasing agent, 3～6 parts of water.
6. the circuit card powder synthetic that utilizes according to claim 5 does not have the ME that aldehyde zero carbocyclic ring is protected sheet material, it is characterized in that said releasing agent is a paraffin, and said circuit card powder is that discarded circuit board reclaims powder.
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| CN102304280A (en) | 2012-01-04 |
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