CN1147826A - Thermoplastic resin foam and method of production thereof - Google Patents
Thermoplastic resin foam and method of production thereof Download PDFInfo
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- CN1147826A CN1147826A CN 94195083 CN94195083A CN1147826A CN 1147826 A CN1147826 A CN 1147826A CN 94195083 CN94195083 CN 94195083 CN 94195083 A CN94195083 A CN 94195083A CN 1147826 A CN1147826 A CN 1147826A
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Abstract
A foamed molded article which is light in weight and has a high bending strength and excellently balanced compressive strength and compressive permanent strain. The foam comprises a highly expanded thermoplastic resin the entire outer surface of which is covered with a lowly expanded thin film of a thermoplastic resin, and which is thermally fused through the lowly expanded thin film to another highly expanded resin.
Description
Invention field
The present invention relates to thermoplastic resin foam and manufacture method thereof.
Background technology
Thermoplastic resin foam is because of in light weight and have characteristics such as good heat insulating ability, flexibility and formability, and be widely used as various thermal insulators, for example roof thermal insulator or ground thermal insulator, cushioning material and various interior material are as the interior of motor vehicles finishing material.
In general, a kind of known preparation method of above-mentioned thermoplastic resin foam comprises, expand obtaining the step of expandable beads thermoplastic resin is pre-, thereby and implement then the expandable beads mould of packing into is made it reexpansion and makes pearl and the step of the mutual clinkering acquisition of pearl moulded parts.
Yet the shortcoming of the foam molded article that obtains with the above-mentioned method for preparing thermoplastic resin foam is intensity, particularly the flexural strength deficiency.For example, in the pearl foam molded article that is obtained by above-mentioned expandable beads, the surface of every pearl has generated the film that one deck can not be sent out.Therefore, can expect that the foam molded article that obtains in this way has high compression-strength.Yet in the foam moulded process of this pearl, the above-mentioned integument of sending out is packed in the mould, and reexpansion clinkering and being shaped mutually simultaneously then takes place, and therefore, the clinkering power between pearl and the pearl is very low.Thereby, when bending load puts on this foam molded article, be easy to cause split and/or break, so cause the flexural strength deficiency along clinkering interface between pearl and the pearl.
Japanese patent application publication No. 4-16330 discloses a kind of method that is intended to improve the flexural strength of the foam molded article that is made by above-mentioned pearl expanding method.In this prior art disclosed method, be loaded in the mould by compression by thermoplastic resin the sent out pearl that obtains of expanding in advance, in mould, feed in the pressure ratio mould height 0.2kg/cm at least then
2Degassing steam, make it reexpansion/clinkering, thereby improve the clinkering power between pearl and the pearl., in the method that this prior art is described, the foam molded article that obtains in the forming process be subjected to the outgasing compression of steam.Therefore, for the minimizing of steam flow between the sent out pearl that prevents to cause owing to supercompression, the pressure of degassing steam just can't be carried very highly.Therefore, the clinkering power between pearl and the pearl still can not fully improve, thereby still is difficult to obtain to have the foam molded article of enough flexural strengths.
In addition, the described method of above-mentioned prior art also must be carried out in two steps, is about to expandable beads and expands in advance, and then allow pre-expanded beads material reexpansion and clinkering in mould, and this just brings the low problem of production efficiency.
Goal of the invention
That main purpose of the present invention provides is in light weight, flexural strength is excellent and have compressive strength and the permanent compression strain between the thermoplastic resin foam and the manufacture method thereof of excellent balance.
Another object of the present invention provides the method for making the thermoplastic resin fat vacuole with even and tiny abscess.
Disclosure of the Invention
With regard to a generalized aspect, the invention provides a kind of foam, it is characterized in that the thermoplastic resin high expansion foam body that whole grain outside surface is wrapped in the low-expansion foam thin layer that is made of thermoplastic resin passes through the mutual hot melt knot of this low-expansion foam thin layer together.
In according to foam of the present invention, heatable plastic resin pellet or ring-type material resemble describe below expand, mutually the hot melt knot is together then.At this moment, can form the space between the low-expansion foam thin layer, some situation also can form hole.But its size generally is no more than 7mm, preferably is no more than 5mm, be most preferably not exceeding 3.5mm, the ratio of expansion that depends on low-expansion foam thin layer and high expansion foam, because if the equal variation of ability of this oversize then thickness homogeneity and maintenance shape, and every physicals also can descend.
With regard to another generalized aspect, the invention provides a kind of preparation foamy method, this method comprises and will contain the heatable plastic resin particle or the ring-type material dispersive step of whipping agent, and the step that heatable plastic resin particle or ring-type material is expanded by the blowing temperature that above-mentioned material is heated to above contained whipping agent in this heatable plastic resin.
Illustrate successively below according to the present invention and prepare foamy method and this foam.
Thermoplastic resin
Preparing according to the present invention in the foamy method, the heatable plastic resin particle or the ring-type material that at first will contain whipping agent disperse.Containing the thermoplastic resin of the heatable plastic resin of whipping agent as for formation, then can be any thermoplastic resin, as long as it is a kind of heatable plastic resin.
About this heatable plastic resin, for example can enumerate, the alkylene resin, such as new LDPE (film grade), high density polyethylene(HDPE), LLDPE is (following with new LDPE (film grade), high density polyethylene(HDPE), LLDPE or its mixture are referred to as " polyethylene "), Atactic Polypropelene, alfon and block polypropylene are (following with Atactic Polypropelene, alfon, block polypropylene, together with minute quantity, generally be no more than the ethene of 5wt%, and above-mentioned mixture is referred to as " polypropylene "), polyvinyl chloride, chlorinated polyvinyl chloride, ABS resin, polystyrene, polycarbonate, polymeric amide, poly(vinylidene fluoride), polyphenylene sulfide, polysulfones, polyether-ether-ketone and above-mentioned multipolymer, and these thermoplastic resins can use separately, or wherein two or more are used in combination.
In the middle of the above-mentioned thermoplastic resin, the alkylene resin, for example polyethylene or polypropylene and composition thereof are preferred with regard to improving acquisition foamy thermoformable, wherein the mixture of high density polyethylene(HDPE) and alfon is especially preferred the use.
The thermoplastic resin that is used to form the low-expansion foam thin layer must be the resin of same type with the thermoplastic resin that is used to form above-mentioned high expansion foam body.
And above-mentioned thermoplastic resin can be crosslinked as required.The preferred cross-linked thermoplastic resin that uses, because in this case, ratio of expansion has improved, thereby the foam that obtains can lighting, thermostability also can be improved simultaneously.
If the degree of crosslinking of above-mentioned thermoplastic resin is too high, then ratio of expansion reduction and thermoformable also reduce.On the other hand, if the thermoplastic resin degree of crosslinking is low excessively, then thermostability reduction and abscess break when expanding, thereby can't obtain the foam hole of homogeneous.In sum, above-mentioned degree of crosslinking by as degree of crosslinking exponential gel section, is preferably 10-30wt%, more preferably 10-20wt%.
Cross-linking method to above-mentioned thermoplastic resin has no particular limits, but can list several method: (1) utilizes cross-linking method, (2) of electron beam to adopt method and (3) of organo-peroxide silane-modified thermoplastic resin to be doped/also mediate subsequently together with above-mentioned thermoplastic resin fusion and obtains crosslinked method with water treatment.Serve as preferred especially wherein with the cross-linking method (3) that adopts silane-modified thermoplastic resin.
(1) illustrates that at first above-mentioned employing organo-peroxide makes the crosslinked method of thermoplastic resin.
Above-mentioned organo-peroxide is had no particular limits, but can list peroxidation dibutyl, dicumyl peroxide, tert-butyl peroxide cumyl, peroxidation di-isopropyl etc., wherein dicumyl peroxide and tert-butyl peroxide cumyl are preferred, and dicumyl peroxide then is especially preferred.
The consumption of organo-peroxide is preferably the 0.5-5 weight part for per 100 weight part thermoplastic resins, more preferably 1-3 weight part, reason is if this consumption is excessive, then resin generation decomposition reaction makes the foam band look of generation, if yet this consumption is too small, thermoplastic resin crosslinked insufficient.
(2) the following describes the above-mentioned electron beam that utilizes and make the crosslinked method of thermoplastic resin.
The dosage of electron beam irradiation is preferably 1-20Mrad, and with 3-10Mrad for especially preferred, because, if dosage is excessive, then owing to applied the crosslinked foam expansion ratio reduction that makes acquisition of over-drastic, and too small as if dosage, then thermostability reduces, and foam hole breaks, so that can not get the foam hole of homogeneous.
For the method that applies electron beam and without particular limitation, still, for example can enumerate and adopt two electron-beam generators, thereby allow thermoplastic resin from passing through method between the two with electron beam irradiation thermoplastic resin.
Then, (3) illustrate the cross-linking method that adopts silane-modified thermoplastic resin, i.e. preferable methods.
Can not add any above-mentioned silane-modified thermoplastic resin that especially restrictedly uses, as long as it is general the employing.About this one type of silane modified thermoplastic resin, can list silane modified polyethylene thermoplastic resin, silane-modified polypropylene thermoplastic resin, silane-modified ethylene-vinyl acetate copolymer thermoplastic resin and silane-modified thermoplastic polystyrene resin.Owing to have high expandability, silane modified polyethylene thermoplastic resin, the silane-modified polypropylene thermoplastic resin of fat and silane-modified thermoplastic polystyrene resin are preferred, and silane modified polyethylene thermoplastic resin and silane-modified polypropylene thermoplastic resin are more preferred.
Silane-modified thermoplastic resin for example can carry out graft modification to thermoplastic resin with unsaturated silane compound and prepare.
Above-mentioned unsaturated silane compound refers to general formula R
1SiR
2 mY
3-mRepresented compound.
In this general formula, R
1Example can list organo-functional group, kiki alkenyl group for example is such as vinyl, allyl group, propenyl, cyclohexenyl etc.; Glycidyl; Amino; The 2-methacryloyl; And haloalkyl, as γ-chloroethyl and γ-bromotrifluoromethane.
In this general formula, R
2Represent aliphatic saturated hydrocarbon base or aromatic hydrocarbyl, wherein can list methyl, ethyl, propyl group, decyl or phenyl.
In addition, m represents 0,1 or 2.
In this general formula, Y represents the hydrolyzable organic radical, and it is amino wherein can to list methoxyl group, oxyethyl group, formyloxy, acetoxyl, propionyloxy, alkyl or virtue; When m was 0 or 1, Y can mutually the samely also can differ from one another.
In the above-mentioned unsaturated silane compound, general formula is CH
2=CHSi (OA)
3Compound be preferred.In this general formula, A is an alkyl, preferably contains 1-8 carbon atom, more preferably contains 1-4 carbon atom, for example can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl nitrilotriacetic base silane etc. as preferred unsaturated compound.
When above-mentioned silane-modified thermoplastic resin contained methoxyl group, methoxyl group touched just hydrolysis and generate hydroxyl of water.
The hydroxyl interreaction of this hydroxyl and other molecules generates the Si-O-Si key, thereby silane-modified thermoplastic resin is just crosslinked mutually.At this moment, preferably use the crosslinked with silicane catalyzer.
The gel section of the silane-modified thermoplastic resin after crosslinked is preferably 60-85wt%, because, if this numerical value is low excessively, then cross-linking density reduces, the result has just reduced the expandability of heatable plastic resin, and therefore from improving the angle of the stability that expands, this is worth 70-80wt%. more preferably
By the present invention, gel section refers to resin and soaks the residual weight after 24 hours and the weight percent of resin weight before the dimethylbenzene immersion in 120 ℃ dimethylbenzene.
The preferred standard of the melting index of silane-modified thermoplastic resin is, this silane-modified thermoplastic resin and added this resin and the thermoplastic resin of common with it fusion and kneading between the melting index difference be no more than 15g/10min.
This be because, if this difference greater than 1g/10min, then silane-modified thermoplastic resin just can not be dissolved in the middle of the thermoplastic resin equably.
With respect to 100 weight part thermoplastic resins, the quantity of silane-modified thermoplastic resin is preferably the 1-50 weight part, more preferably 5-40 weight part, and further preferred 10-30 weight part, because if this quantity is big, then cross-linking density improves, and the result reduces gained foamy ratio of expansion, and makes lightweight characteristic variation; And if this quantity is too little, then the expandables composition will not have the necessary shear viscosity that expands in the thermal expansion process, and expansion stability also can variation.
In order to come the cross-linked thermoplastic resin, can use a kind of crosslinked with silicane catalyzer as required with silane-modified thermoplastic resin.
Above-mentioned crosslinked with silicane catalyzer is had no particular limits, as long as it can promote the crosslinking reaction between the silane-modified thermoplastic resin, for example can enumerate dibutyltin diacetate, dibutyl tin dilaurate, two lauric acid, two hot tin, the fine stannous octoate of iodobenzene (tin octanoate), oleic acid tin, the fine lead octoate 36 of iodobenzene (leadoctanoate), 2 ethyl hexanoic acid zinc, the fine cobalt octoate of iodobenzene (cobalt octanoate), lead naphthenate, zinc octoate, Zinic stearas etc.
Be preferably the 0.001-2.5 weight part with respect to the above-mentioned crosslinked with silicane catalyst consumption of 100 weight part thermoplastic resins, more preferably 0.01-2 weight part, further preferred 0.1-1.5 weight part, because if consumption height, then the expandability of heatable plastic resin reduces, if and consumption has lacked, then the crosslinking reaction speed of silane-modified thermoplastic resin reduces.
The method that silane-modified thermoplastic resin is joined in the thermoplastic resin does not limit especially, as long as this method can add resin equably, as long as this method can join thermoplastic resin and silane-modified thermoplastic resin in the middle of single screw rod or the Bitruder and it be carried out solvent mediate, for example can enumerate the drum-type solvent and mediate method and kneader solvent kneading method.
Method with water treatment comprises, except resin being immersed in the method in the water, also can adopt resin is exposed to method in the water vapour, and in this case, if treatment temp surpasses 100 ℃, then this method can be carried out adding to depress.
The temperature of water and steam that is used for water treatment is preferably at 50-130 ℃, and especially preferred 90-120 ℃, because if temperature is low excessively, then crosslinking reaction speed is too low, and if temperature is too high, then heatable plastic resin particle or ring-type material can mutual clinkerings.
Time for water treatment was preferably 5 minutes-12 hours, because if the time is too short, then crosslinking reaction may be carried out not exclusively, and if overlong time, then heatable plastic resin particle or ring-type material can mutual clinkering together.
Whipping agent
To whipping agent above-mentioned and without particular limitation, as long as its blowing temperature is higher than the melt temperature of the thermoplastic resin that is adopted, for example can enumerate inorganic pyrolysis whipping agent, such as sodium bicarbonate, volatile salt, bicarbonate of ammonia, triazo-compound and sodium borohydride; With organic pyrolysis whipping agent, such as azodicarbonamide, Diisopropyl azodicarboxylate, N, N '-dinitrosopentamethylene tetramine, P, P '-dinitrosopentamethylene tetramine, P, P '-oxygen two benzol sulfohydrazides, barium azo-biscarbonate and trihydrazinotriazine, wherein consider that from the health angle azodicarbonamide is fabulous, owing to be easy to adjust decomposition temperature and rate of decomposition and a large amount of gas can be produced so be preferred.In the present invention, blowing temperature refers to the decomposition temperature of decomposition-type foaming agent.
With respect to 100 weight part thermoplastic resins, the quantity of whipping agent is preferably the 1-25 weight part, more preferably is the 5-15 weight part, because if this quantity is excessive, then can not get uniform abscess owing to abscess breaks, and if this quantity is too small, then can't realize the foaming.
The preferred embodiment of heatable plastic resin
In according to preparation method of the present invention, the heatable plastic resin particle or the ring-type material that contain above-mentioned whipping agent have been adopted, and the preferred above-mentioned heatable plasticity tree of adopting of conduct is by two kinds of almost inconsistent each other non-crosslinked thermoplastic resins and silane-modified thermoplastic resin composition's blend of being made by one of these two kinds of non-crosslinked thermoplastic resins are prepared.Because this resin contains two kinds of almost inconsistent each other non-crosslinked thermoplastic resins, so will describe below when resin is crosslinked by above-mentioned silicon modified thermoplastic resin, just generating " sea-island " the type structure.
When resin contains two kinds of almost inconsistent each other non-crosslinked thermoplastic resins, their mixed weight ratio is preferably 3: 7-7: 3, more preferably 4: 6-6: 4, and more preferably 5: 5, a kind of resin was dispersed in the another kind, the extremely slick high expansion ratio foam in surface so that obtain.
When the difference of melting index between above-mentioned two kinds of almost inconsistent each other non-crosslinked thermoplastic resins increases, can obtain very coarse sea-island structure, also can not get the foam of high expansion ratio simultaneously.And on the other hand, when the difference of melting index between the two reduces, then can not generate the foam that high expansion ratio was constructed thereby also be can not get on uniform sea-island.Therefore, above-mentioned melting index difference is preferably 3-25g/10min., so that obtain the thin and foam structure uniformly of particle, yet in order to obtain the higher foam of ratio of expansion, more preferably is 5-13g/10min., and 7-11g/10min. more preferably.
In according to foam manufacture method of the present invention, more preferably, with the 1-50 weight part and silane-modified thermoplastic resin one of two kinds of non-crosslinked thermoplastic resins identical type, above-mentioned crosslinked with silicane catalyzer and above-mentioned whipping agent, with the thermoplastic resin of above-mentioned two types non-crosslinked thermoplastic resin of containing of 100 weight parts.
Because above-mentioned two kinds of non-crosslinked thermoplastic resins are compatible hardly each other, when above-mentioned heatable thermoplastic resin composition during through the equipment blend of a kind of extruding machine and so on, just form a kind of extremely fine and closely woven sea-island structure, wherein a kind of non-crosslinked thermoplastic resin evenly and compactly is dispersed in the another kind of non-crosslinked thermoplastic resin.
And, adopt can be dissolved in according to qualifications in a kind of non-crosslinked thermoplastic resin because of the thermoplastic resin lipid species is identical with the silane-modified thermoplastic resin of one of two kinds of non-crosslinked thermoplastic resins same resin.In addition, though silane-modified thermoplastic resin can be in the expandables composition equably diffusion and it be dissolved in the non-crosslinked thermoplastic resin that constitutes the sea and press down or be dissolved in the non-crosslinked thermoplastic resin that constitutes the island because these two kinds of thermoplastic resins have been taked extremely fine sea-island structure form.
When the silane-modified thermoplastic resin that adopts belongs to same type with the non-crosslinked thermoplastic resin that constitutes the sea, this silane-modified thermoplastic resin is dissolved in the non-crosslinked thermoplastic resin that constitutes the sea according to qualifications, then silane-modified thermoplastic resin through take place with water treatment crosslinked after a kind of crosslinked configuration of formation in successive layers (part in sea) preferably just, sea as successive layers in the expansion process, thereby just above-mentioned heatable plastic resin, just acquisition is fit to the melt viscosity of bulk expansion.
On the other hand, when the silane-modified thermoplastic resin that adopts belongs to same type with the non-crosslinked thermoplastic resin that constitutes the island, this silane-modified thermoplastic resin is dissolved in the non-crosslinked thermoplastic resin that constitutes the island according to qualifications, then silane-modified thermoplastic resin through take place with water treatment crosslinked after a kind of crosslinked configuration of formation in discontinuous layer (part on island) preferably just, this moment, supposition was suitable for expansion because following effect resin becomes, although this mechanism is proved as yet fully.
The non-crosslinked thermoplastic resin that constitutes the island evenly and compactly is scattered here and there, and the size of particles that constitutes the non-crosslinked thermoplastic resin on island is compared very little usually with the bubble diameter that the pyrolysis whipping agent decomposes generation, the island is compared also very little with the gap on island with bubble diameter simultaneously, therefore, from microcosmic angle, the non-crosslinked thermoplastic resin that the bubble that the decomposition of pyrolysis whipping agent produces is configured the island basically is closed continuously.Like this, gas is closed in viscosity and is suitable for also foam not to be burst in the expansible layer, so the melt viscosity that the expandables composition that the present invention adopts has just had suitable bulk expansion.
With the foam that above-mentioned heatable plastic resin is made, wherein there is the lower part of some cross-linking densities, therefore because these parts have flowability in foaming process, so whole resin heat has high formability.
And this lower crosslink density part can be by fusion again, and certain filler is also recyclable be used again and the high crosslink density part can be used as.
On the other hand, allow the quantity of silane-modified thermoplastic resin is reduced to below per 100 weight part thermoplastic resin compositions, 50 weight parts, so that because of the crosslinked internal stress that causes, and the foam of this expandables composition through expand obtaining has excellent size stability in the reduction forming process.
The viscosity that constitutes the composition of above-mentioned heatable plastic resin particle or ring-type material is the scope of 5000 pools-20000 pools in the time of 190 ℃.When not reaching 5000 pools, then viscosity is too low, and the blow(ing) pressure when incessantly expand owing to foam bears this moment is easy to break, thereby can not get the foam of high expansion ratio.On the other hand, when viscosity at 20000 pools when above, then too viscosity is too high, also can not get high expansion ratio foam because whipping agent decomposes the blow(ing) pressure deficiency that the foam gas that produces causes this moment.The melt viscosity value system that the disclosure provides records according to JISK7199.
In addition, the gel section in the above-mentioned heatable plastic resin preferably is defined as 10-30wt%, more preferably 10-20wt%.If this numerical value is lower than 10wt%, then thermostability reduces, and foam hole is burst in the expansion process, so can not get uniform foam gap.On the other hand, when gel section was higher than 30wt%, then ratio of expansion descended, and thermoformable is also owing to excessive crosslinked decline.
Pellet or ring-type material
It is also without particular limitation to prepare the method that is used for heatable plastic resin particle of the present invention or ring-type material, but can enumerate a kind of method, to constitute the thermoplastic resin of heatable plastic resin particle or ring-type material (is pellet to call particle or ring-type material in the following text), feeding such as pyrolysis whipping agent extruding machine, with its fusion and kneading under the temperature that is lower than the pyrolysis foaming agent decomposition temperature, subsequently it is extruded into sheet and with its cooling, again it is cut off to prepare heatable plastic resin pellet, and (2) a kind of method, with thermoplastic resin, feeding such as pyrolysis whipping agent extruding machine, with its fusion and kneading under the temperature that is lower than the pyrolysis foaming agent decomposition temperature, subsequently it is extruded into the line material and with its cooling, again it is cut off to prepare heatable plastic resin particle or ring-type material.
The shape of heatable plastic resin particle or ring-type material also has no particular limits, but for example can be sexangle, garden post or spheroid, wherein with sexangle for most preferably, because heatable plastic resin pellet can not roll when they are disperseed.
When heatable plastic resin particle or ring-type material are sexangle, hexagonal each edge lengths is also without particular limitation, but be preferably 0.1-50mm, and especially be preferably 0.5-20mm, because if this length is long, the ratio of low-expansion foam thin layer reduces in the foam molded article of then making, thereby flexural strength also can reduce, if and this length is too short, then the dissipation of foam gas increases.
Disperse
According to the present invention, the heatable plastic resin particle or the ring-type material that need to prepare in a manner described disperse.This kind dispersion for example can be carried out on translational surface, as carrying out on the travelling belt of producing apparatus shown in Figure 1, also can carry out on the immobilized surface.
And, heatable plastic resin particle or ring-type material can be disperseed to make like this particle or ring-type material not overlapping along thickness direction, promptly form single one deck, heatable plastic resin particle or ring-type material are overlapped each other along thickness direction.
About heatable plastic resin particle or ring-type material are disperseed, make it the preferred method that do not overlap each other along thickness direction, for example can enumerate (1) is dispersed into a large amount of heatable plastic resin pellets minimum edge is equally high basically one by one rectangular parallelepiped and is keeping minor face to make it become the method for individual layer by high-frequency vibration in the thickness direction orientation, (2) a large amount of heatable plastic resin pellets is dispersed into equally high basically cubes and makes it become the method for individual layer by high-frequency vibration, and (3) will be transformed into the method for individual layer by a large amount of heatable plastic resin pellet that the eclipsed mode is dispersed into equally high basically cubic form by the equipment of coating machine and so on, yet difference according to circumstances also can adopt the mutual method that is not arranged in overlappingly together of the same highly substantially one by one heatable plastic resin pellet.
The height here refers to the height that is orientated when heatable one by one plastic resin pellet disperses according to quilt.
In above-mentioned dispersion process, the preferred dispersing mode of above-mentioned particle or ring-type material should make dispersed heatable plastic resin particle or ring-type material shadow area down account for the 10-75% of this area that is surrounded by dispersed particle or the shared region outer edge of ring-type material.
By expandables pellet shadow area sum after disperseing is limited in the 10-75% of above-mentioned All Ranges shadow area summation, just can guarantee has certain degassing space in the heatable plastic resin pellet expansion process, thereby so that is making void-free foam by each expandables pellet being sandwiched in to expand when therebetween air is driven out of.And, each expandables pellet clinkering mutually/be combined into integral body expansion space deficiency of needn't worrying, thus can prevent from the foam of making, to form the cavity.
In addition, can also obtain the foam of flexural strength and flexibility coupling, its method is the heatable plastic resin particle after disperseing or the shadow area of ring-type material are limited in the 10-75% of the above-mentioned various region projection total areas, thereby confined expansion is than the thickness of scope and low-expansion foam thin layer.
Expanded foamed
According to preparation method of the present invention, above-mentioned particle or ring-type material are disperseed, with particle or the heating of ring-type material, make its temperature subsequently to the blowing temperature that surpasses whipping agent contained in the above-mentioned heatable plastic resin, so particle or ring-type material just expand.
When heatable plastic resin particle or ring-type material expand because of heating, the surface of each particle or ring-type material and inside just become low-expansion foam thin resin layer and high expansion foam body, wherein be positioned at low-expansion foam thin resin layer mutual clinkering when expanding on surface, become as a whole, so just can obtain the thin layer moulded parts, wherein entire exterior surface be wrapped in above-mentioned thermoplastic resin low-expansion foam thin layer thermoplastic resin high expansion foam body by the mutual hot melt knot of this low-expansion foam thin layer together.
Preparation method of the present invention can be by disperseing heatable plastic resin pellet, and be heated and expansion makes it this very simple method of clinkering and obtains foam, can save heatable plastic resin particle or the pre-expansion step of ring-type material, be the high a kind of preparation method of productivity therefore.
To heating means above-mentioned and without particular limitation, can arbitrarily adopt any heating means, as long as it can be heated to pellet the blowing temperature above whipping agent.For example, the heating installation of can adopt electric heater, far infra-red heater, making by the circulation of the heating medium such as deep fat or air heats pellet.
Have again, with the heating of heatable plastic resin particle or ring-type material and expand and make it fritted method and except that limiting its thickness, also have no particular limits.For example, above-mentioned heatable plastic resin particle or ring-type material can be dispersed between two tabular objects, so that keeping two distances between plates to let alone simultaneously to expand from constant.Another kind method is, heatable plastic resin particle or ring-type material are disperseed, and holds it in then between two tabular bodys, allows it expand then, constantly increases distance between two tabular bodys simultaneously until reaching certain size.In addition, heatable plastic resin particle or ring-type material can also be disperseed, then it is kept between two tabular bodys, increase distance between two tabular bodys simultaneously from two sides by the swelling pressure that produce in heatable plastic resin particle or the ring-type material expansion process then.
Can be with any plate-like articles as above-mentioned tabular object, for example iron plate, steel plate, tetrafluoroethylene band etc. all can use.
And, better be with composite sheet, promptly use fibre-reinforced thermoplastic resin sheet, for example place between above-mentioned tabular body and heatable plastic resin particle or the ring-type material.In such cases, above-mentioned thermoplastic resin sheet section bar material can be arranged in the only side between tabular body and heatable plastic resin particle or the ring-type material.
When adopting above-mentioned composite sheet, preferably in advance heatable plastic resin particle or ring-type material are dispersed on the composite sheet, the foam of composite sheet and acquisition is become one.In the time of in this way, second composite sheet is layered on heatable plastic resin particle scattered or above the ring-type material, thereby obtains laminated thing.Subsequently will this laminated thing be heated to blowing temperature, thereby heatable plastic resin particle or ring-type material be expanded obtain constituting the foam of one with laminated thing sheet material above whipping agent.
Having as above-mentioned at least one side surface in the foam of the thermoplastic resin sheet material of making one, the flexural strength of foam integral body is improved effectively because of the laminated thermoplastic resin sheet of going up.
Except that above-mentioned composite sheet, can also adopt such as glassine paper and staple fiber felt various materials such as (they are called as the enhancing sheet material from kind).
If yet be used for the glass fibre preponderance of glassine paper and staple fiber felt, can't reach the purpose that alleviates finished foam weight.On the other hand, if glass fibre weight is too light, then can't reach the purpose of improving finished foam intensity again.Therefore, above-mentioned glass fibre consumption be preferably 10-500g/m
2, 50-300g/m more preferably
2
In addition, also also without particular limitation for the thermoplastic resin that is used for above-mentioned composite sheet, however can enumerate for example polyethylene, polypropylene, polyethylene terephthalate etc.Have again,, preferably adopt its thermoplastic resin and foam thermoplastic resin symbolic animal of the birth year composite sheet of the same type in order to improve the bounding force of composite sheet and foam segment.
About fiber as composite sheet, except that glass fibre and can also enumerate inorganic fibre such as carbon fiber, such as organic fibres such as aramid fiber or nylon fiber and steel fiber etc., and the woven cloths of these fibers or non-woven all have supply.
If the thickness of above-mentioned enhancing sheet material is excessive, then can't reach the purpose that alleviates finished foam weight, and if thickness is too small, then reinforced effects is not enough.So composite sheet thickness preferably is decided to be 0.05-1mm, more preferably 0.1-0.5mm.
For according to preparation method of the present invention with as preferred embodiment, be that raw material makes foam by the heatable plastic resin made with silane-modified thermoplastic resin, used water is handled silane-modified thermoplastic resin and is made it to be cross-linked with each other, be heated to blowing temperature then, just obtain this foam above whipping agent.
As required, can add strongthener at the thermoplastic resin that is used for above-mentioned heatable plastic resin, for example staple glass fibre, carbon chopped fiber or polyester staple fiber and filler, for example lime carbonate, aluminium hydroxide or glass powder are so that improve the foamy flexural strength.
When adding staple fibre as strongthener, with respect to 100 weight part thermoplastic resins, its preferred consumption is the 1-20 weight part, especially preferred 3-10 weight part, because if consumption is excessive, then abscess can break in expansion process so can not get high expansion ratio, and if consumption is too small, then can not get improving the effect of gained foamy body.
The length of staple fibre is preferably 1-20mm, and especially preferred 3-5mm because if length is long, does not then reach the purpose that alleviates finished foam weight, and if length is too short, then do not reach to strengthen finished product foamy purpose.
When adding filler, preferred consumption is per 100 weight part thermoplastic resin 10-100 weight parts, especially preferred 30-50 weight part, because if consumption is too much, then do not reach the purpose that alleviates finished foam weight, and if consumption is very few, then do not reach to strengthen finished product foamy purpose.
Foam
According to foam of the present invention is a kind of thin layer moulded parts, and wherein whole grain outside surface is wrapped in the thermoplastic resin high expansion foam body of thermoplastic resin low-expansion foam thin layer and ties together by the mutual hot melt of this low-expansion foam thin layer.
Because the high expansion foam body by the mutual clinkering of low-expansion foam thin layer together, so each low-expansion foam thin layer provides compressive strength, it is flexible that high expansion foam then provides, simultaneously because expansion has taken place this low-expansion foam thin layer, so high thermal insulation also is provided.And, whole grain outside surface be wrapped in the high expansion foam body that constitutes foamy low-expansion foam thin layer by blow(ing) pressure in the expansion process by the low-expansion foam thin layer each other securely hot melt form integral body, therefore these foams can not separate along the hot melt junction interface and/or break, and very soft again when keeping high bending strength.
Above-mentioned suitable thermoplastic resins can be as the thermoplastic resin that forms above-mentioned high expansion foam and low-expansion foam thin layer, and foam of the present invention can also adopt the heatable plastic resin that whipping agent and other any compositions is mixed with thermoplastic resin and make to obtain.
The high expansion foam body that whole grain outside surface is wrapped in the low-expansion foam thin layer can be shaped as an individual layer that does not overlap each other along thickness direction, in this case, this high expansion foam body is along the section all directions, and promptly longitudinally with horizontal, the hot melt knot together mutually.Therefore, except that foam flexibility above-mentioned, because the low-expansion foam thin layer generates along thickness direction equably along the extension of foamy thickness direction and this low-expansion foam thin layer, so foam constitutes a kind of accurate truss-frame structure, thereby flexural strength is further enhanced.
On the other hand, this foam can also have multi-ply construction, and wherein the high expansion foam body is piled up along the thickness direction multilayer, and in this case, foam can and/or not break along the clinkering interfacial separation when foam is subjected to adding bending load.Therefore, can obtain flexible excellent foam.
When thermoplastic resin contains the advantage crosslink part of high crosslink density and few crosslink part of lower crosslink density, and the two is when having sea-island structure, and this lower crosslink density has flowable when partially-formed, so this foam has excellent thermoformable.
Cross when low when the ratio of expansion of above-mentioned low-expansion foam thin layer, foamy is flexible just to be reduced, and thermal conductivity improves simultaneously.On the other hand, when the ratio of expansion of low-expansion foam thin layer is too high, then can not get the foam of high bending strength.Therefore, the ratio of expansion of low-expansion foam thin layer is preferably 1.1-10 doubly, and more preferably 1.2-7 times, and especially be preferably 1.2-5 doubly.
If the low-expansion foam thin layer is blocked up, then do not accomplish the foamy lighting, and if the low-expansion foam thin layer is thin excessively, then can not get the foam of high bending strength.Therefore, the thickness of low-expansion foam thin layer is preferably 30 μ m-500 μ m, 40 μ m-400 μ m more preferably, and especially preferred 50 μ m-400 μ m.
The thickness of low-expansion foam thin layer can not be uniformly, and can be uneven.
Here the low-expansion foam thickness of thin layer of being mentioned refers to the mean thickness of low-expansion foam thin layer along the foam cross-sectional direction.
According to the present invention, consider the coupling between lighting and the flexural strength, the ratio of expansion of above-mentioned low-expansion foam thin layer and thickness are preferably 1.1-10 respectively doubly and 30 μ m-500 μ m, more preferably be 1.2-7 doubly and 40 μ m-400 μ m, and especially be preferably 1.2-5 doubly with 50 μ m-400 μ m.
If the ratio of expansion of high expansion foam is low excessively, then be difficult to reach the foamy lighting, and its thermal conductivity raises, cause gained foamy heat-insulating property to reduce, and if this ratio of expansion is too high, then can not get the foam of high bending strength.Therefore, the ratio of expansion of high expansion foam is preferably 20-50 doubly, and more preferably 5-50 times, especially preferred 10-35 doubly.
If (particle) of high expansion foam is oversize, then gained foamy flexural strength reduces, and if this is undersized, then gained foamy surface smoothness reduction.Therefore, (particle) gravel size decision ground of high expansion foam is 5-10mm, especially preferred 7-50mm.
High expansion foam (particle) size can not be uniformly, and can be uneven.
Here (particle) size of the high expansion foam of mentioning refers to numerical value maximum in the middle of all directions size of transverse section.
In constituting according to foamy structure of the present invention, the high expansion foam body is tied by the mutual hot melt of low-expansion foam thin layer, and is somebody's turn to do structure usually in the form of sheets.
In according to foam of the present invention, a kind of composite sheet of forming by above-mentioned fortifying fibre and thermoplastic resin can be stacked on its at least one surface, thus can further improve flexural strength.
Preparation is not to be confined to above-mentioned preparation method with invention particularly according to foamy method of the present invention, but can list according to qualifications (1) heatable plastic resin pellet is disperseed, heats, makes it to expand and the hot melt knot to make the foamy method, can also according to circumstances adopt (2) to make the thermoplasticity granular foam in advance simultaneously and by the hot melt knot it is piled into the monoblock foam then.
The invention effect
In aforesaid foam with invention, the thermoplastic resin high expansion foam body that whole grain outside surface is wrapped in thermoplastic resin low-expansion foam thin layer by the mutual hot melt knot of this low-expansion foam thin layer together.This low-expansion foam thin layer can improve the foamy compressive strength, and it also provides high thermal insulation owing to the foaming that the low bulk degree has been arranged simultaneously.In addition, this low-expansion foam thin layer also becomes an integral body with the mutual securely clinkering of each high expansion foam body, so it also provides the inaccessible sufficient flexibility of foam by the expanded foamed preparation of traditional bead material.
And, according to this above-mentioned foamy method of preparation, can easily prepare foam with high productivity with above-mentioned excellent properties with invention.
Have again, according to a preferred aspect of the present invention, melt viscosity is the expandables composition of 3000 pools-20000 pools when adopting a kind of 190 ℃, thereby makes the stability that expands obtain further to improve, and thereby can provide the high expansion foam that contains even abscess structure, flexural strength excellence.
(1) when the part of resin gel in the heatable plastic resin is controlled in 10-30wt%, be suitable then, so just can make the foam of producing between formability and thermostability, obtain balance to the crosslinked of resin enforcement.
(2) when employing contains the heatable plastic resin of mixture of specific non-crosslinked thermoplastic resin of specific silane-modified thermoplastic resin, crosslinked with silicane catalyzer and whipping agent and specified quantity, form the lower crosslink density part, this part has flowability when being shaped, thereby hot-forming property excellence, so can obtain excellent heat stability, even and careful foam hole, because degree of crosslinking is grasped suitably on the whole, so melt viscosity is suitable, the flexural strength of finished foam also becomes very excellent simultaneously.
Therefore, can provide the foam that is suitable as various thermal insulators, comprise roof thermal insulator and ground thermal insulator, cushioning material and various interior material, comprise the interior of motor vehicles finishing material according to the present invention.
The accompanying drawing summary
Fig. 1 is the front elevation view for preparing the foamy device instance according to the inventive method.
Fig. 2 is another front elevation view for preparing the foamy device instance according to the inventive method.
Fig. 3 is the electron photomicrograph of 20,000 times of the amplifications of the high dilation of example 23 gained foams.
Implement optimal mode of the present invention
Fig. 1 is the front elevation view that is used for preparing according to the inventive method the foamy device instance, wherein 1 and 2 expressions strengthen sheet material, 3 expressions contain the thermoplastic resin particle or the ring-type material of whipping agent, 5 and 6 expression travelling belts, 9 and 9 expression heating installations, 10 and 10 expression cooling apparatuss, 11 expression foams.
Strengthen sheet material 1 by feeding travelling belt 5, so heatable plastic resin particle or ring-type material 3 just are dispersed on the enhancing sheet material 1 by the particle or the ring-type material decollator 4 that are positioned at midway.Strengthen sheet material 2 subsequently by feeding travelling belts 6 and be layered on particle or above the ring-type material 3, so material is fed preliminary heating device 8 and 8, heating installation 9 and 9 and cooling apparatus 10 and 10 in succession.7 expression vibrating devices are used to make strengthen the sheet material vibration so that heatable plastic resin particle or the ring-type material 3 after the homogenizing dispersion.
The preheating and in heating installation 9 and 9, being heated in preliminary heating device 8 and 8 of heatable plastic resin particle or ring-type material 3 above the whipping agent blowing temperature, so whipping agent decomposes and thermoplastic resin particle or the 3 fusion/expansions of ring-type material, these resin particles or the mutual clinkering of ring-type material and clinkering simultaneously strengthening on sheet material 1 and 2 surfaces.
It is the blowing temperature of whipping agent at least that Heating temperature in the heating installation 9 and 9 generally is decided to be, and is no more than blowing temperature+20 ℃, for example about 200 ℃.
Expand and fritted laminate film cools off in cooling apparatus (cooling temperature such as about 30 ℃) 10 and 10, so that repression of swelling and adjust to the thickness of regulation.
Better be, above-mentioned heating installation 9 and 9 and cooling apparatus 10 and 10 in, heating surface 91 and 91 and cooling surface 101 and 101 have many vacuum take-off grooves 92 and 92 and 102 and 102 so that keep all even any surface finish of thickness.
So just obtained foam 11, thereby it is made of thermoplastic resin particle or ring-type material 3 foam layer 112 that forms and clinkering be configured as one on its two sides the enhancing sheet layer that expands.
Fig. 2 represents that another prepares the foamy device instance according to the inventive method.Among the figure, strengthen sheet material 1b and fed travelling belt 5a.On the sloping portion that strengthens sheet material 1b, be spread out from heatable plastic resin particle or the ring-type material 3a of particle decollator 4a.The inclined surface of above-mentioned thermoplastic resin sheet 1b partly has hot-platen 8a, and it is heated to 200-210 ℃ temperature.Therefore, the surface that strengthens sheet material 1b just becomes molten state, thereby heatable plastic resin particle 3a just is bonded at and strengthens above the sheet material 1b, and unnecessary particle then falls.And the particle that falls can be reused.
Then, second strengthens sheet material 2a is laid down on above the stickiness thermoplastic resin particle 3a, so thereby heatable plastic resin particle or ring-type material 3a are expanded by the hot-platen 9a heating that is heated to about 200 ℃ of temperature.So, just obtained moulded parts 11a.
The following describes specific examples according to foam preparation processes of the present invention and froth product.
The preparation of heatable plastic resin pellet
(petroleum chemistry company of Mitsubishi produces high density polyethylene(HDPE), trade(brand)name: EY40H, melting index (to call MI in the following text): 1.5g/10min.), (petroleum chemistry company of Mitsubishi produces polypropylene (1), trade(brand)name: MA3, MI:11g/10min.), (petroleum chemistry company of Mitsubishi produces polypropylene (2), trade(brand)name: MH8, MI:0.3g/10min.), (petroleum chemistry company of Mitsubishi produces polypropylene (3), trade(brand)name: MA2A, MI:25g/10min.) and silane-modified polypropylene (petroleum chemistry company of Mitsubishi produces, trade(brand)name: LINKLON XPM800HM, MI:11g/10min., crosslinked back gel section: 80wt%) weigh according to the process of consumption shown in the following table 1-3, further with dibutyl tin dilaurate and 5 weight part azodicarbonamides (the Otsuka Chemical company product of 0.1 weight part as crosslinking catalyst, trade(brand)name: SO-20, blowing temperature=210 ℃) mix, be admitted in the twin shaft extruding machine of diameter 30mm fusion under 180 ℃ of temperature/mediate and be extruded into thickness shown in table 1-3 then, width is the sheet material of 300mm.Sheet material soaked 2 hours in 98 ℃ water through cooling off and cut into the size of wide 5mm, long 5mm subsequently, and is dry then, obtains heatable plastic resin pellet A at last.
Example 1,3,5,9,11,13,15,17,19,21 and 23
Adopt the heatable plastic resin pellet A that obtains as stated above and as shown in Figure 1 producing apparatus produce foam.Yet, in producing apparatus as shown in Figure 1, do not use thermoplastic resin sheet 1 and 2, but above-mentioned heatable plastic resin pellet A directly be dispersed on the travelling belt 5.When disperseing, the ratio (disperseing projected area ratio) of grasping the actual downward shadow area sum that occupies the zone of dispersed heatable plastic resin pellet A and this area that is surrounded by dispersed particle or the shared region outer edge of ring-type material is ratio shown in the table 1-3, and makes it to become double-deck.Being used for the heating installation 9 of heatable plastic resin pellet A and 9 Heating temperature is 210 ℃, and pellet expanded through heating in 10 minutes, then cooling apparatus 10 and 10 internal cooling 10 minutes, so obtain the thick foam of 5mm.
Ratio of expansion, foam state, foam voids state, flexural strength numerical value, 25% compression strength values, permanent compression strain, thermoformable grade and the thermostability grade of the thickness of gained foamy ratio of expansion, low-expansion foam thin layer, the ratio of expansion of low-expansion foam thin layer, high expansion foam are all measured by following method.The result also is stated from table 1-3 in the lump.
(ratio of expansion)
Pressing JISK6767 measures.
(low-expansion foam thickness of thin layer)
Observed the foam section that forms and measured by the microscope that has scale.
(low-expansion foam thin layer ratio of expansion)
Cut the low-expansion foam thin layer from foam, measure according to JISK6767 then.
(high expansion foam ratio of expansion)
Cut high expansion foam from foam, measure according to JISK6767 then.
(foam outward appearance)
Foamy surface and section have been observed.
(foam voids situation)
By the microscopic examination that has scale the foam section to measure various spaces, comprise the maximum inner diameter value of gap, hole and foam hole etc., so that divide 4 grades evaluation with regard to the foam voids state according to following standard.
: foam hole maximum inner diameter value is less than 2mm, and do not have the space basically.
Zero: the maximum interspace inner diameter values is less than 3.5mm.
△: the maximum interspace inner diameter values is greater than 3.5mm and less than 7mm.
X: the maximum interspace inner diameter values is at least 7mm.
(flexural strength)
Foam is cut into 50mm * 150 mm * 50mm, under the bending load condition of span 100mm, pressing speed 50mm/min., pressure rod R=5 and n=5, has carried out three point bending test to measure the flexural strength value.
(part of breaking)
The part of breaking detects by an unaided eye after applying above-mentioned bending load.
(25% compressive strength)
Measure according to JISK6767.
(permanent compression strain)
Measure according to JISK6767.
(thermoformable)
The uncovered separately part of the band round-ended cylinder of several opening end part R=5, diameter=70mm and the prescribed depth foam with 20mm * 20mm * 5mm is covered, foam is heated to 180 ℃, be that the garden column piece of 70mm is pressed into uncovered sunk part with diameter then, when beginning to break, measures foam the degree of depth h (mm) that foam is pressed into uncovered sunk part, try to achieve the support pressure ratio by following formula, divide Pyatyi evaluation thermoformable according to following standard then:
Support pressure ratio (%)=(h/80) * 100
Thermoformable:
The support pressure ratio is more than or equal to 75% ... 5
The support pressure ratio is more than or equal to 60%, less than 75% ... 4
The support pressure ratio is more than or equal to 50%, less than 60% ... 3
The support pressure ratio is more than or equal to 30%, less than 50% ... 2
The support pressure ratio is not more than 30% ... 1
(thermostability)
Foam is cut into 20mm * 20mm * 5mm, placed 5 minutes in 210 ℃ atmosphere, place 23 ℃ of coolings down then, water is displacement densimeter measurement volume V (mm down
3), try to achieve volume change (%) by following formula then, divide the level Four assess thermal stability by following standard at last:
Volume change (%)={ (2000-V) }/2000 * 100
Thermostability: volume change is not more than 20%
Volume change is more than or equal to 20%, less than 30% ... zero volume change is more than or equal to 30%, less than 50% ... the △ volume change is more than or equal to 50% ... X
Example 2,4,6,10,12,14,16,18,20,22 and 24
The heatable plastic resin pellet A that will obtain by above-mentioned mode does not overlap the to each other dispersion along thickness direction like that shown in table 1-3, by producing apparatus shown in Figure 1, produce foam with the method that is similar to example 1.But being used for the heating installation 9 of thermoplastic resin pellet A and 9 Heating temperature is 210 ℃, and pellet is heated 10 minutes, expands, and transfers in the cooling apparatus 10 and 10 that temperature is set in 30 ℃ cooling then 10 minutes, obtains the thick foam of 10mm.
Carried out every characteristic test of similar example 1 at the foam that obtains, its result is stated from following table 1-3.
Example 7
Adopt the heatable plastic resin pellet A and the producing apparatus shown in Figure 1 that obtain in a manner described to produce foam.In example 7,, adopt a kind of 45g/m that uses as the enhancing sheet material 1 on the travelling belt 5 that places producing apparatus shown in Figure 1
2Glassine paper (ORIBEST company produces, trade(brand)name: FVP-045) enhanced 90g/m
2(petroleum chemistry company of Mitsubishi produces high density polyethylene(HDPE), trade(brand)name: JX10, MI:20g/10min.) composite sheet made of sheet material.Above-mentioned heatable plastic resin pellet A is dispersed on this composite sheet, and the dispersion projected area ratio that obtains is shown in table 1, and it is a multiwalled.
Subsequently, adopt and form sheet material conduct as shown in Figure 1 the enhancing sheet material 2 identical, make heatable plastic resin pellet A between two composite sheets, expand and be shaped with top composite sheet.In this case, heating installation 9 and 9 Heating temperature are decided to be 210 ℃, and material is through heating expansion in 10 minutes, transfer to then in the cooling apparatus 10 and 10 that temperature is set in 30 ℃, make its cooling 30 minutes, so obtain the thick foam of 10mm.
Carried out every characteristic test of similar example 1 at the foam that obtains, its result also is stated from following table 1.
Example 8
Be similar to example 7 and produce foam like that.But in example 8, the speed that heatable plastic resin pellet is distributed to above the fiber-reinforced thermoplastic resin sheet is as shown in table 1, and is not overlapped along thickness direction when simultaneously heatable plastic resin pellet disperses.Other condition that is shaped all is similar to example 7, obtains the foam of thickness 10mm.
Copy example 1 to measure the every characteristic of gained foamy.The result also is stated from table 1.
Reference examples 1
The heatable plastic resin pellet A that will obtain according to top mode is 210 ℃ a gear stove internal heating 10 minutes a temperature, and its is expanded, and carries out air cooling then, obtains foaming granule material.Foaming granule material is added in the mould that interior dimensions is 10mm * 200mm * 200mm,, makes it clinkering, transfer to subsequently in the cooling apparatus of 30 ℃ of design temperatures, cooled off 10 minutes, obtain the thick foam of 10mm with 170 ℃ handpress heating 5 minutes.
Copy example 1 to measure the every characteristic of gained foamy.The result also is stated from the following table 1.
Table 1
Table 2
Table 3
| Example | |||||||||
| ????1 | ?????2 | ????3 | ?????4 | ????5 | ????6 | ????7 | ????8 | ||
| The resin compounding ratio | HDPE | ||||||||
| PP(1) | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | |
| PP(2) | |||||||||
| PP(3) | |||||||||
| Crosslinked with silicane PP | ????80 | ????80 | ????80 | ????80 | ????80 | ????80 | ????80 | ????80 | |
| Crosslinked | Crosslinked back viscosity (pool) | ????21000 | ????2100 | ????2100 | ????21000 | ????2100 | ????2100 | ????2100 | ????2100 |
| Gel section (wt%) | ????36 | ????36 | ????36 | ????36 | ????36 | ????36 | ????36 | ????36 | |
| Resin granular material | Particle thickness (mm) | ????1.2 | ????1.2 | ????3 | ????3 | ????2 | ????2 | ????2 | ????2 |
| Disperse projected area ratio (%) | ????34.7 | ????41.7 | ????13.9 | ????16.7 | ????20.8 | ????25.0 | ????20.8 | ????25.0 | |
| Dispersion state | Multilayer | Individual layer | Multilayer | Individual layer | Multilayer | Individual layer | Multilayer | Individual layer | |
| Foam | Low bulk film thickness (μ m) | ????540 | ????650 | ????17 | ????20 | ????125 | ????150 | ????125 | ????150 |
| Low bulk film ratio of expansion (multiple) | ????1.05 | ????1.05 | ????17 | ????14 | ????4 | ????3.5 | ????4 | ????3.5 | |
| High swelling film ratio of expansion (multiple) | ????38 | ????40 | ????23 | ????23 | ????28 | ????32 | ????28 | ????32 | |
| Not composite sheet is arranged | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have | |
| Foam state | Fabulous | Fabulous | Fabulous | Fabulous | Fabulous | Fabulous | Fabulous | Fabulous | |
| Foam voids state (4 grade) | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
| The foam physics performance | Flexural strength (kgf/cm 2) | ????0.20 | ????0.22 | ????0.20 | ????0.21 | ????0.27 | ????0.29 | ????0.51 | ????0.57 |
| The part of breaking | Foam | Foam | Foam | Foam | Foam | Foam | Foam | Foam | |
| 25% compressive strength (kgf/cm 2) | ????0.39 | ????1.12 | ????0.65 | ????0.78 | ????1.18 | ????1.28 | ????1.12 | ????1.35 | |
| Permanent compression strain (%) | ????8.8 | ????8.2 | ????5.5 | ????5.1 | ????6.5 | ????6.1 | ????7.5 | ????7.3 | |
| Thermoformable (5 ranking) | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | |
| Thermostability (3 ranking) | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
In the dispersion process of the thermoplastic resin pellet A of example 1-24, each routine disperse weight is 250g/m
2Though unlisted in table 1-3, the overall expansion ratio of the foam molded article that each example obtains in example 1-24 and the Comparative Examples 1 is 20 times.
As what find out significantly from table 1-3, foamy flexural strength numerical value has significantly improvement in the example 1 to 24, all is at least 0.12kg/cm
2Yet the flexural strength of the foam molded article that obtains in the Comparative Examples but has only 0.076g/cm
2, what the latter adopted is to implement the pre-bead material expansion/manufacturing process that expands and reexpand in forming process.This be because, foam among example 1-6 and the example 9-24 is to adopt manufacture method of the present invention to obtain, in these foams, the whole grain outside surface of high expansion foam body all is wrapped in the low-expansion foam thin layer, and the low density foam pellet strikes up partnership by the mutual hot melt of these low-expansion foam thin layers as a result.
In addition, should be appreciated that the foam multi-layered foamed comparison identical that does not overlap each other when those high expansion foam bodies are shaped, have higher flexural strength with composition along thickness direction.For example example 1 and example 2 are compared mutually, as can be seen, the high expansion foam body of example 2 does not overlap each other bending strength ratio example 1 height along thickness direction.Be appreciated that the flexural strength numeric ratio example 3,5,7,9,11,13,15,17,19,21 and 23 height of example 4,6,8,10,12,14,16,18,20,22 and 24 similarly.
Have again, be to be understood that, in example 5-8 and example 13-24, the ratio of expansion of low-expansion foam thin layer is 1.1-10 times, and its thickness is 30-500 μ m, compare with example 1-4 and example 9-12, its flexural strength numerical value is higher, is therefore realizing that light-weight has also obtained the higher foam of flexural strength simultaneously.
In addition, should see also that in example 7 and 8, the foam two sides all is lined with the composite sheet of being made up of fortifying fibre and thermosetting resin, so its flexural strength is improved as 0.51kg/cm respectively significantly
2And 0.57kg/cm
2
On the other hand in example 9-12, all the other examples of bending strength ratio low, reason is that the dispersion projected area ratio of thermosetting resin pellet A has exceeded the scope of 10-75%.Therefore should understand, the dispersion projected area ratio of thermosetting resin pellet A is controlled at the foam that can obtain high bending strength in the scope of 10-75%.
It should also be understood that, foam hole state among example 15,16 and the 19-24 is very good, the melt viscosity numerical value of heatable plastic resin in the time of 190 ℃ that wherein is used to prepare thermoplastic resin pellet A is in the scope of 5000-20000 pool, thereby foam hole homogeneous and tiny, disperses evenly.Therefore, can know, obtain foam than high bending strength.For example, example 13 and 15 is close on the implementation each other, just changing to some extent aspect the melt viscosity value of above-mentioned thermosetting resin and the gel section, so 15 flexural strength is brought up to 0.29kg/cm
2, and the flexural strength of example 13 has only 0.27kg/cm
2Similarly, the flexural strength of example 16 is brought up to 0.30kg/cm
2, the flexural strength of example 14 then is 0.29kg/cm
2Further example 17 and example 19 are compared, as can be seen, the flexural strength in the example 19 is brought up to 0.29 kg/cm
2Yet in the example 17 but is 0.28kg/cm
2Although be the viscosity numerical value difference of heatable thermosetting resin.This shows, be controlled at by melt viscosity in the scope of stipulating above, just can make the foamy foam hole of acquisition be shaped to such an extent that more all even tiny while foam flexural strength also obtains further improvement heatable plastic resin.
Further as can be seen, in example 17-24, the gel section of heatable thermosetting resin is 10-30wt%, can obtain the appropriate balance between thermoformable and the thermostability.In other words, the thermoformable grade of example 17-24 is chosen as 3 at least, and simultaneously, the thermostability grade also remains on △ at least.On the other hand, in example 1-16, then fail to obtain to resemble the result that can aspect two of thermoformable and thermostabilitys, all be satisfied with described above.
In addition as can be seen, in example 23 and 24, two kinds of almost inconsistent non-crosslinked thermoplastic resins are according to 3: 7-7: the ratio intermingling of 3 scopes, and its thermoformable and thermostability are all good, and flexural strength is also further brought up to 0.30kg/cm respectively simultaneously
2And 0.31kg/cm
2
Fig. 3 be according to of the present invention, contain the high expansion foam body and wrap up that low density foam partly amplifies 20 in the foam of low-expansion foam thin layer of its outside surface, 000 times electron photomicrograph, as what can find out from this photo, can confirm, the high crosslink density part of being selected the superior crosslinked, i.e. few crosslink part of high-density part in the photo and lower crosslink density, be the low density part in the photo, constituted sea-island structure together.Owing to wherein exist few crosslink part of lower crosslink density part, and these parts tool in forming process can have flowability, make according to foam of the present invention excellent in performance aspect the thermoformable.
It is said that 25% compressive strength of roofing thermal insulator must be 0.6kgf/cm at least
2, and the permanent compression strain must be not more than 10%, and among example 1-24,25% compression strength values just is 0.6kgf/cm at least
2, and permanent compression has just accomplished to be not more than 10%.This shows, obtained appropriate equilibrated foam between compressive strength and permanent compression strain.
Claims (13)
1. foam, it contains:
The high expansion foam body that constitutes by thermoplastic resin; And
By being wrapped in the said low-expansion foam thin layer high expansion foam external surface, that thermoplastic resin constitutes that constitutes by thermoplastic resin,
Many said high expansion foam bodies by the mutual hot melt knot of said low-expansion foam thin layer together.
2. according to the foam of claim 1, wherein entire exterior surface is wrapped in high expansion foam body described low-expansion foam thin layer, that be made of thermoplastic resin and does not overlap the to each other along thickness direction and be arranged in one deck, and by said low-expansion foam thin layer along the mutual hot melt knot of section direction together.
3. according to the foam of claim 1 or 2, wherein the ratio of expansion of low-expansion foam thin layer is 1.1-10 times, and its thickness is 30-500 μ m.
4. according to the foam of claim 1 or 2, wherein the ratio of expansion of high expansion foam is 20-50 times.
5. according to any one foam among the claim 1-4, it further comprises and is laid in its composite sheet of one side at least, and this sheet material is made of fortifying fibre and thermoplastic resin.
6. according to the foam of claim 1 or 2, wherein said thermoplastic resin contains the advantage crosslink part of high crosslink density and few crosslink part of lower crosslink density part, and above-mentioned two portions form sea-island structure.
7. one kind prepares the foamy method, comprise the heatable plastic resin particle or the ring-type material dispersive step that will contain whipping agent, and by above-mentioned material being heated to the blowing temperature that surpasses contained whipping agent in the described heatable plastic resin, the step that this heatable plastic resin particle or ring-type material are expanded.
8. make the foamy method according to claim 7, wherein heatable plastic resin particle or ring-type material are dispersed into the one deck that does not overlap each other along thickness direction.
9. make the foamy methods according to claim 7 or 8, the dispersing mode of wherein said heatable plastic resin particle or ring-type material should make dispersed heatable plastic resin particle or ring-type material shadow area down account for the 10-75% of this area that is surrounded by the outward flange of dispersed particle or ring-type material area occupied.
10. make the foamy method according to claim 7 or 8, wherein said heatable plastic resin particle or the melt viscosity of ring-type material in the time of 190 ℃ are the 5000-20000 pool.
11. make the foamy step according to claim 7 or 8, the resin gel in the wherein heatable plastic resin partly is 10-3wt%.
12. make the foamy methods according to claim 7 or 8, wherein said heatable plastic resin contain 100 weight parts by two kinds of almost inconsistent non-crosslinked thermoplastic resins by 3: 7-7: the thermoplastic resin composition that 3 weight ratios are mixed and made into;
The 1-50 weight part adopts the silane-modified thermoplastic resin of the thermoplastic resin identical with one of said non-crosslinked thermoplastic resin;
The crosslinked with silicane catalyzer and
Whipping agent.
13. one kind prepares the foamy method, comprising:
Heatable plastic resin particle or ring-type material are dispersed in step on the composite sheet that is made of fortifying fibre and said thermoplastic resin;
At dispersed above-mentioned heatable plastic resin particle or spread the composite sheet that the second layer is made of fortifying fibre and thermoplastic resin above the ring-type material, thereby obtain the step of laminated thing; And
The said layer compound is heated to the blowing temperature that surpasses described whipping agent makes heatable plastic resin particle or the foaming of ring-type material, thus the step that laminated thing is struck up partnership.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94195083 CN1147826A (en) | 1994-12-14 | 1994-12-14 | Thermoplastic resin foam and method of production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94195083 CN1147826A (en) | 1994-12-14 | 1994-12-14 | Thermoplastic resin foam and method of production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1147826A true CN1147826A (en) | 1997-04-16 |
Family
ID=5039615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94195083 Pending CN1147826A (en) | 1994-12-14 | 1994-12-14 | Thermoplastic resin foam and method of production thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1147826A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574358A (en) * | 2009-10-29 | 2012-07-11 | 井上株式会社 | Fiber-reinforced molded product and method for producing same |
| CN104705163A (en) * | 2015-03-04 | 2015-06-17 | 沧州银龙塑业有限公司 | Water seepage pipe for agricultural irrigation and preparing method thereof |
| CN105252876A (en) * | 2015-12-01 | 2016-01-20 | 重庆三易塑胶制品有限公司 | Foamed plastic belt-type hot-melting compound structure and hot-melting compound equipment thereof |
| CN109982917A (en) * | 2016-07-28 | 2019-07-05 | 泽菲罗斯有限公司 | For absorbing the multistage deformation reinforcement structure of impact |
| CN110545979A (en) * | 2016-12-29 | 2019-12-06 | 积水沃尔泰克有限责任公司 | Heterogeneous foam compositions and methods |
| CN113677512A (en) * | 2019-03-25 | 2021-11-19 | 泽菲罗斯有限公司 | Dual expansion foam for closed mold composite manufacture |
| CN113677512B (en) * | 2019-03-25 | 2024-05-28 | 泽菲罗斯有限公司 | Dual expansion foam for closed mold composite manufacture |
-
1994
- 1994-12-14 CN CN 94195083 patent/CN1147826A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574358A (en) * | 2009-10-29 | 2012-07-11 | 井上株式会社 | Fiber-reinforced molded product and method for producing same |
| CN102574358B (en) * | 2009-10-29 | 2015-04-22 | 井上株式会社 | Fiber-reinforced molded product and method for producing same |
| CN104705163A (en) * | 2015-03-04 | 2015-06-17 | 沧州银龙塑业有限公司 | Water seepage pipe for agricultural irrigation and preparing method thereof |
| CN104705163B (en) * | 2015-03-04 | 2017-05-03 | 沧州银龙塑业有限公司 | Water seepage pipe for agricultural irrigation and preparing method thereof |
| CN105252876A (en) * | 2015-12-01 | 2016-01-20 | 重庆三易塑胶制品有限公司 | Foamed plastic belt-type hot-melting compound structure and hot-melting compound equipment thereof |
| CN105252876B (en) * | 2015-12-01 | 2017-10-27 | 重庆三易塑胶制品有限公司 | The continuous belt hot melt composite construction of bubble and its hot melt equipment complex |
| CN109982917A (en) * | 2016-07-28 | 2019-07-05 | 泽菲罗斯有限公司 | For absorbing the multistage deformation reinforcement structure of impact |
| CN110545979A (en) * | 2016-12-29 | 2019-12-06 | 积水沃尔泰克有限责任公司 | Heterogeneous foam compositions and methods |
| CN113677512A (en) * | 2019-03-25 | 2021-11-19 | 泽菲罗斯有限公司 | Dual expansion foam for closed mold composite manufacture |
| CN113677512B (en) * | 2019-03-25 | 2024-05-28 | 泽菲罗斯有限公司 | Dual expansion foam for closed mold composite manufacture |
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