CN101850639A - Polyurethane foam laminate, manufacturing method thereof, and gasket - Google Patents
Polyurethane foam laminate, manufacturing method thereof, and gasket Download PDFInfo
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- CN101850639A CN101850639A CN201010143220A CN201010143220A CN101850639A CN 101850639 A CN101850639 A CN 101850639A CN 201010143220 A CN201010143220 A CN 201010143220A CN 201010143220 A CN201010143220 A CN 201010143220A CN 101850639 A CN101850639 A CN 101850639A
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- polyurethane foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0278—Polyurethane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2581/00—Seals; Sealing equipment; Gaskets
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- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Gasket Seals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a polyurethane foam laminated body, a manufacturing method thereof and a washer. The manufacturing method includes: mixing foam materials including polyisocyanate, polyhydric alcohol and flame retardant and gas to generate a gas-liquid mixture; then, supplying the gas-liquid mixture to a resin film; heating the gas-liquid mixture, making the foam materials react and solidify, and obtaining the resin film layer having the resin film and the laminated body having the foam layer including the generated polyurethane foam; the flame retardant contained in the foam materials includes metal hydroxide powders composed of aluminium hydroxide and etc, and liquid flame retardants such as phosphor flame retardant; when the polyhydric alcohol is 100 shares by mass, the metal hydroxide powders are 20-60 shares by mass; the liquid flame retardants are 5-20 shares by mass; furthermore, the density of the foam layer is 100-280kg/m3. The laminated body is able to be made into the washer.
Description
Technical field
The present invention relates to polyurethane foam laminate and manufacture method thereof and packing ring.In more detail, the present invention relates to comprise: contain specific fire retardant, fire retardant does not ooze out, soft and be difficult to abrade, polyurethane foam that aesthetic appearance is good; And good polyurethane foam laminate and the manufacture method thereof of the anti-flammability of resin film layer, and adopt that this polyurethane foam laminate constitutes, anti-flammability and the good packing ring of sealing.
Background technology
Originally, drove at portable communications equipments such as mobile phone, digital camera, automobile in the electronic instruments such as the navigation system of speeding, pocket sound equipment, entered its inside in order to suppress moisture, dust etc., at configuration packing rings such as the peripheries of housing.This packing ring, particularly electronic instrument that under rigorous environment such as high-temperature atmosphere, uses and precision instrument, or when being provided with on the high electronic instrument of heat generation and precision instrument etc., packing ring must have the fire-retardant benchmark of UL94 defined, promptly meets the anti-flammability of HBF specification.In order to give this anti-flammability, propose to adopt the packing ring of the resin foam that has cooperated fire retardants such as halogen based flame retardant, antimony trioxide, organophosphorus compound, metal hydroxides such as organbromine compound, organochlorine compound.
Patent documentation 1 discloses relative polyalcohol 100 weight portions, and the foam raw material that mixes fire retardant metal hydroxides 25～50 weight portions with specific density foams and the flame resistant sealing material with foam portion that forms.In this patent documentation 1, be low-density if put down in writing foam portion, then the contact area with air becomes big, and anti-flammability reduces.In addition, put down in writing in this flame resistant sealing material, when the use level of metal hydroxides during greater than 50 weight portions, foam portion presents sclerosis or embrittlement, and sealing has problems.In addition, put down in writing method, adopted the diluent media of polyalcohol, entered in the molecule of polyurethane, prevented to become the method for volatilization of surfactant of the important hindering factor of fire-retardantization by making surfactant as surfactant as this problem of processing.
In addition, patent documentation 2 disclose have base material film, with this base material film on the article of the polyurethane foaming body layer that forms, as these article, can enumerate the containment member that uses in the display etc. of mobile phone etc.In addition, put down in writing also and can in foam raw material, add additive arbitrarily,, can enumerate fire retardant as additive.
The previous patent document
[patent documentation 1] spy opens the 2005-171102 communique
[patent documentation 2] spy opens the 2007-44972 communique
Summary of the invention
Invent problem to be solved
In order to form the foam portion that satisfies above-mentioned fire-retardant benchmark, when adopting above-mentioned fire retardant, then there is the following problems point respectively.
The halogen based flame retardant produces the big halide of carrying capacity of environment during owing to burning, so not preferred.
Antimony trioxide has confirmed that carrying capacity of environment is big and harmful, not preferred.
The organophosphorus compound majority is liquid, and when a large amount of cooperation, foam property reduces, or oozes out, and worries to shift to problems such as housing.In addition, adopt resin molding and resin foam all-in-one-piece packing ring, for example, in the fire retardancy test of UL94 regulation, shrink as the resin molding of base material, can not suppress test piece and curl in foam side, the result is that existence does not meet the problem of HBF specification.
Metal hydroxides such as aluminium hydroxide, magnesium hydroxide, above-mentioned carrying capacity of environment and the influence of human body etc. almost do not had can be used as safe packing ring, but for example, in order to form packing ring, must in resin foam, cooperate in a large number with the anti-flammability that meets the HBF specification.Yet, adopt the mechanical foaming method, when when foam raw material cooperates the powder body, tackify takes place, when particularly making low density resin foam, tackify is remarkable, adopts the resin foam of mechanical foaming method, be difficult to form the fine pore structure that had originally, have problems such as the shaggy so-called pore of foam is coarse.
The present invention relates to having in view of above-mentioned existing situation proposes: fire retardant do not ooze out, soft and be difficult to abrade, polyurethane foam that aesthetic appearance is good; And, polyurethane foam laminate that the anti-flammability of resin film layer is good and manufacture method thereof, and adopt that this polyurethane foam laminate constitutes, anti-flammability and the good packing ring of sealing.
Be used to solve the means of problem
The present invention relates to following content.
1. polyurethane foam laminate, it is characterized in that, be that the foam raw material that contains polyisocyanates, polyalcohol and fire retardant is being mixed with gas, generate gas-liquid mixture, then, this gas-liquid mixture is supplied with on the resin molding, secondly, heat this gas-liquid mixture, this foam raw material is reacted and in the polyurethane foam laminate of resin film layer that having of obtaining comprises this resin molding and the froth bed of the polyurethane foam that comprises generation
The above-mentioned fire retardant that contains in the above-mentioned foam raw material contains metal hydroxides powder and liquid combustion inhibitor, and when above-mentioned polyalcohol was 100 mass parts, this metal hydroxides powder was 20～60 mass parts, and this liquid combustion inhibitor is 5～20 mass parts, and,
The density of above-mentioned froth bed is 100～280kg/m
3
2. according to the polyurethane foam laminate described in above-mentioned 1, wherein, above-mentioned liquid combustion inhibitor is a phosphorus type flame retardant.
3. according to the polyurethane foam laminate described in above-mentioned 1, wherein, the average grain diameter of above-mentioned metal hydroxides powder is 10～100 μ m.
4. according to the polyurethane foam laminate described in above-mentioned 1, wherein, above-mentioned resin film layer contains PETG, and the thickness of this resin film layer is 25～125 μ m.
5. according to the polyurethane foam laminate described in above-mentioned 1, wherein, the average pore diameter of above-mentioned froth bed is 50～300 μ m.
6. according to the polyurethane foam laminate described in above-mentioned 1, wherein, above-mentioned froth bed with above-mentioned resin film layer on have the top layer on the face of face opposition side of lamination.
7. according to the polyurethane foam laminate described in above-mentioned 1, wherein, the loading of compressing at 40% o'clock is 0.002～0.02MPa.
8. according to the polyurethane foam laminate described in above-mentioned 1, wherein, in 50% o'clock compression residual deformations of 70 ℃ of compressions of temperature below 10.0%.
9. the manufacture method of polyurethane foam laminate; It is characterized in that; The foam raw material that contains polyisocyanates, polyalcohol and fire retardant is mixed with gas; Generate gas-liquid mixture; Then; This gas-liquid mixture is supplied with on the resin molding; Secondly; Heat this gas-liquid mixture; This foam raw material is reacted; Having obtained having the resin film layer that comprises this resin molding solidifies in the manufacture method of polyurethane foam laminate of froth bed of the polyurethane foam that generates with comprising by the reaction of this foam raw material
The above-mentioned fire retardant that contains in the above-mentioned foam raw material contains metal hydroxides powder and liquid combustion inhibitor, and when above-mentioned polyalcohol was 100 mass parts, this metal hydroxides powder was 20～60 mass parts, and this liquid combustion inhibitor is 5～20 mass parts, and,
The density of above-mentioned froth bed is 100～280kg/m
3
10. packing ring is characterized in that, adopts any one described polyurethane foam laminate in above-mentioned 1 to 8.
11. according to the packing ring described in above-mentioned 10, thickness is 0.4～1.5mm.
The invention effect
According to polyurethane foam laminate of the present invention owing to contain the metal hydroxides powder and the liquid combustion inhibitor of ormal weight respectively as fire retardant, have fire retardant do not ooze out, soft and be difficult to abrade, froth bed and resin film layer that aesthetic appearance is good.And, with generally, as good in flexibility, be fit in the instrument that uses under the severe rugged environments such as high-temperature atmosphere, encapsulant with packing ring configuration, that anti-flammability is good on the febrifacient instrument etc. etc.
When above-mentioned liquid combustion inhibitor was phosphorus type flame retardant, by the combination of this phosphorus type flame retardant and metal hydroxides powder, fire retardant did not ooze to the froth bed surface, had the density of regulation and had the soft foam layer, and anti-flammability is good.
Above-mentioned resin film layer contains PETG, and when the thickness of this resin film layer was 25～125 μ m, the shape stability of polyurethane foam laminate was good.And, when this polyurethane foam laminate when the packing ring, can reach complete to the sealing of the periphery of 2 members constituting Instrument shell etc.That is, the adaptation of above-mentioned periphery and above-mentioned resin film layer is good.
When the average pore diameter of above-mentioned froth bed was 50～300 μ m, the compression residual deformation in the froth bed was little, when using as packing ring, can obtain long-term good sealing etc.
In addition, above-mentioned froth bed with resin film layer on when having the top layer on the face of opposing face of face of lamination, the sealing of the periphery of 2 members constituting Instrument shell etc. is reached complete.That is, same with the adaptation in the resin film layer side, but the froth bed side also driving fit on above-mentioned periphery, during as the packing rings such as housing of mobile phone etc. etc., can obtain better sealing etc.
When 40% o'clock loading of compression is 0.002～0.02MPa in the polyurethane foam laminate of the present invention, very soft.And, to this polyurethane foam laminate adopt blanking die in addition stamping-out etc. process, when making the packing ring etc. of housing such as mobile phone etc., it is injured that froth bed does not take place, or processing component periphery etc. does not produce defective.In addition, polyurethane foam laminate of the present invention during as packing ring etc., can obtain good sealing etc.
In addition, polyurethane foam laminate of the present invention, when 70 ℃ of temperature, the compression residual deformation in 50% when compression 10.0% when following, as the packing ring of the housing of mobile phone etc. etc. etc., when using under severe rugged environments such as special high temperature, good sealing etc. can more long-term maintenance.
When the average pore diameter of above-mentioned froth bed is 50～300 μ m, can make polyurethane foam laminate with good rerum naturas such as the compression residual deformation are little.
According to the manufacture method of polyurethane foam laminate of the present invention, can make and have that fire retardant does not ooze out, not produce pore coarse, have the froth bed and the resin film layer of good appearance, the polyurethane foam laminate that anti-flammability is good.
In addition, compare with equal, the common soft dull and stereotyped polyurethane foam of density that adopts water or blowing agent manufacturing, the average pore diameter of froth bed is little.
When the average grain diameter of the metal hydroxides powder that contains in the above-mentioned foam raw material is 10～100 μ m, the inexcessive tackify of foam raw material and gas-liquid mixture, processing ease.In addition, adopt this foam raw material and gas, when generating gas-liquid mixture, both mixing are easy, can the limit suppress the sedimentation of metal hydroxides powder, and the gas-liquid mixture of homogeneous is effectively modulated on the limit.
When above-mentioned resin molding contains PETG, because this resin molding has full intensity, hear resistance etc., when the heat air liquid mixture, also be difficult for elongation, can stablize the good polyurethane foam laminate of adaptation of making froth bed and resin film layer.
According to packing ring of the present invention, anti-flammability, flexibility and sealing are good, and froth bed is difficult to scratch, and the operation when waiting configuration between housing members such as mobile phone is also easy.In addition, mobile phone etc. are in the slimming tendency, and when adopting existing packing ring to finish instrument, housing member bends.Yet, when adopting packing ring of the present invention, warpage can not taken place, the instrument that can obtain having good sealing.
In addition, when the thickness of packing ring was 0.4～1.5mm, operation was easy when waiting configuration between the housing member of miniature instruments such as mobile phone.In addition, when this disposes, needn't the excess compression packing ring.Therefore can long term maintenance good sealing etc.
Description of drawings
Fig. 1 is the ideograph that is used to illustrate polyurethane foam laminate of the present invention manufacturing process.
Fig. 2 is the stereogram that comprises one of the packing ring example of froth bed and resin film layer.
The specific embodiment
Describe the present invention below in detail.
1. polyurethane foam laminate and manufacture method thereof
Polyurethane foam laminate of the present invention, be to have the foam raw material that contains polyisocyanates, polyalcohol and fire retardant is mixed with gas, generate gas-liquid mixture, then, the gas-liquid mixture that obtains is supplied with on the resin molding, secondly, heat this gas-liquid mixture, make the foam raw material reaction and the layered product of the resin film layer that resin molding constituted that obtains and the froth bed of the polyurethane foam formation of generation.And the fire retardant that contains in the above-mentioned foam raw material contains metal hydroxides and liquid combustion inhibitor, and its content when polyalcohol is 100 mass parts, contains 20～60 mass parts and 5～20 mass parts respectively.In addition, the density of the froth bed of formation is 100～280kg/m
3
1-1. foam raw material
Above-mentioned foam raw material is the composition that contains polyisocyanates, polyalcohol and fire retardant, contains following other compositions as required.
Above-mentioned polyisocyanates is not particularly limited, the polyisocyanates that uses in the time of can adopting existing polyurethane foam to make.As this polyisocyanates, usually, can use 4,4 '-methyl diphenylene diisocyanate (MDI), thick MDI, toluene di-isocyanate(TDI) etc.In addition, can also use 1,6-hexamethylene diisocyanate, 1, the 5-naphthalene diisocyanate, to phenylene vulcabond, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate ,-the fragrant same clan or the polyisocyanates of aliphatic category, the polyisocyanates of prepolymer type etc. such as XDI, hexamethylene diisocyanate, hydrogenation MDI, IPDI.Above-mentioned polyisocyanates also can be more than 2 kinds and usefulness, but majority is only used a kind.
Cooperate polyisocyanates, make isocyanate index preferably reach 0.8～1.2, especially preferably reach 0.9～1.1.
Above-mentioned polyalcohol is not particularly limited, and can use the polyalcohol that uses in the existing polyurethane foam manufacturing.As this polyalcohol, can use polyester ether polylol that PPG, PEPA, PPG and PEPA copolymerization form etc.In addition, in order to obtain froth bed that has sufficient tensile strength etc. etc., also can and use polymer polyatomic alcohol.This polymer polyatomic alcohol, for example, alefinically unsaturated compounds such as glycerol polymerization acrylonitrile, styrene, methyl methacrylate are converted into solid constituent on PPG, preferred 10～40 quality %, the more preferably polyalcohol of 15～30 quality %.
The mean molecule quantity of above-mentioned polyalcohol preferred 400～5000, more preferably 800～4000.
Above-mentioned polyalcohol both can also can more than 2 kinds and be used only with a kind.
As above-mentioned fire retardant, can and use metal hydroxides powder and liquid combustion inhibitor.
As above-mentioned metal hydroxides powder, can enumerate the powder that contains aluminium hydroxide, magnesium hydroxide, calcium hydroxide etc.The metal hydroxides powder both can also can more than 2 kinds and be used only with a kind.Among these, the aluminium-hydroxide powder that has 3 hydroxyls, decomposition points to be low to moderate about 200 ℃ is preferred.When adopting this aluminium-hydroxide powder, by with liquid combustion inhibitor and usefulness, can give good especially anti-flammability.
In addition, the average grain diameter of metal hydroxides powder, preferred 10～100 μ m, special preferred 25～75 μ m.When the average grain diameter of metal hydroxides powder is 10～100 μ m, the inexcessive tackify of foam raw material and gas-liquid mixture, processing ease.In addition, adopt this foam raw material and gas, when generating gas-liquid mixture, both mixing are easy, and the limit suppresses the sedimentation of metal hydroxides powder, and the gas-liquid mixture of homogeneous can be effectively modulated on the limit.Also have, above-mentioned average grain diameter is the value that adopts particle size distribution device to measure.
In addition, above-mentioned liquid combustion inhibitor is not particularly limited, and is the fire retardant of liquid in the time of 25 ℃ preferably.When adopting this liquid combustion inhibitor, the viscosity of foam raw material is reduced.And the mixing efficiency of foam raw material and gas improves, and can form the gas-liquid mixture of homogeneous.Its result can form the froth bed dispersed good, homogeneous of fire retardant.
As above-mentioned liquid combustion inhibitor, what halogen atoms such as chloride atom, bromine atoms were arranged contains the fire retardant and the non-halogen containing flame-retardant of Halogen not.From the viewpoint of carrying capacity of environment, non-halogen containing flame-retardant is preferred.As non-halogen containing flame-retardant, phosphorus type flame retardant is preferred, as this phosphorus type flame retardant, can enumerate organic phosphorus compounds such as phosphoric acid ester fire retardant, polyphosphoric acid based flame retardant.Wherein, the phosphoric acid ester fire retardant is preferred.Also have, these organic phosphorus compounds both can also can more than 2 kinds and be used only with a kind.
As the phosphoric acid ester fire retardant, can enumerate trimethyl phosphate, triethyl phosphate, tributyl phosphate, three iso-butyl ester of phosphoric acid, triphenyl phosphate, tricresyl phosphate, three-xylyl phosphate, tolyl diphenyl phosphate, tolyl two-2,6-xylyl phosphate etc.
By adopting, can form polyurethane foam laminate with the good froth bed of anti-flammability with above-mentioned 2 kinds of foam raw materials that fire retardant is a certain content.
The content of the metal hydroxides powder that contains in the above-mentioned foam raw material is 20～60 mass parts, preferred 30～60 mass parts, special preferred 30～50 mass parts when polyalcohol is 100 mass parts.When the content of metal hydroxides powder is 20～60 mass parts, because foam raw material and gas-liquid mixture excessive tackify, can form repressed froth beds such as pore is coarse.The content of this metal hydroxides powder, usually rerum natura limits such as loading and compression residual deformation are set during the compression of limit investigation polyurethane foam laminate.
In addition, the content of the liquid combustion inhibitor that contains in the above-mentioned foam raw material when polyalcohol is 100 mass parts, is 5～20 mass parts, preferred 7～18 mass parts, special preferred 10～15 mass parts.When the content of liquid combustion inhibitor was 5～20 mass parts, the tackify that can form foam raw material and gas-liquid mixture was fully suppressed, the froth bed that liquid combustion inhibitor does not ooze out.In addition, anti-flammability and flexibility etc. are also fully kept.The content of this liquid combustion inhibitor, usually rerum natura limits such as loading and compression residual deformation are set during the compression of limit investigation polyurethane foam laminate.
Except that polyisocyanates, polyalcohol and fire retardant, also can contain catalyst, surfactant, crosslinking agent etc. in the above-mentioned foam raw material.
As above-mentioned catalyst; can enumerate ス タ Na ス オ Network ト エ one ト; the dibutyl tin diacetate esters; organo-tin compounds such as dibutyltin dilaurate; organic zinc compounds such as zinc octoate; pentanedione closes nickel; diacetyl acetone closes organic nickel compounds such as nickel; pentanedione closes organoiron compounds such as iron; the alkoxide of alkali metal such as sodium acetate or alkaline-earth metal; metallic catalysts such as phenates; triethylamine; triethylenediamine; N-methylmorpholine dimethylaminomethyl phenol; imidazoles; 1, tertiary amine catalysts such as 8-diazacyclo [5.4.0] endecatylene; acylate etc.Wherein, organo-tin compound is preferred.Also have, catalyst both can also can more than 2 kinds and be used only with a kind.
The content of the catalyst that contains in the above-mentioned foam raw material also depends on the formation condition of its kind, froth bed etc., when polyalcohol is 100 mass parts, and preferred 0.05～2.0 mass parts, special preferred 0.05～1.0 mass parts.
As above-mentioned surfactant, can adopt silicone based surfactant usually.As this silicone based surfactant, can enumerate dimethyl silica alkyl compound, polyethers dimethyl silica alkyl compound, phenyl methyl siloxane compound etc.These both can also can more than 2 kinds and be used only with a kind.In addition, these compounds also can be the compound with organic functional base.In the present invention, polyethers dimethyl silica alkyl compound is preferred, and the block interpolymers of dimethyl polysiloxane and polyethers is special preferred the use.
The content of the surfactant that contains in the above-mentioned foam raw material also depends on its kind, desirable foam property etc., when polyalcohol is 100 mass parts, and preferred 2.0～10 mass parts, special preferred 3.0～8.0 mass parts.
As above-mentioned crosslinking agent, can enumerate with ethylene glycol, trimethylolpropane etc. as initator, with 6-caprolactone carry out chain elongation the high crosslinking agent of 3 functional polyethers polyalcohol equimolecular quantitys of oligoesters, molecular weight about 400～700 or ethylene glycol, diethylene glycol (DEG), propane diols, DPG, 1, short-chain diol class crosslinking agents such as 4-butanediol, glycerine, trimethylolpropane.When adopting high molecular weight crosslinked dose, can form foam than soft.In addition, when adopting short-chain diol class crosslinking agent, because the ratio of hard segment has the tendency that uprises, so consider that it is preferred that this point is set use level.Crosslinking agent both can also can more than 2 kinds and be used only with a kind.
The content of the crosslinking agent that contains in the above-mentioned foam raw material also depends on its kind, desirable foam property etc., when polyalcohol is 100 mass parts, and preferred 1.0～10 mass parts, special preferred 2.0～5.0 mass parts.
In the above-mentioned foam raw material, can cooperate the general additive that uses in polyurethane foam is made such as ultra-violet absorber, antioxidant, organic and inorganic filler, colouring agent as required in right amount.
1-2. the manufacture method of polyurethane foam laminate
The production of raw material for use of polyurethane foam laminate of the present invention is, contains the foam raw material with above-mentioned formation and the gas-liquid mixture and the resin molding of gas.
Gas with above-mentioned foam raw material mixes is not particularly limited, and can adopt nitrogen, inert gas, dry air etc.Wherein, nitrogen is preferred.
Among the present invention,, adopt that mixer 11 stirs etc., form gas-liquid mixture 21a above-mentioned foam raw material and gas.Then, supply with this gas-liquid mixture 21a and make and be coated on the resin molding 22a, secondly, on the surface of the gas-liquid mixture 21a of curtain coating, square from it side is supplied with processing release paper (or the demoulding with the resin molding of having handled) 3.And, make this laminated state former state, by roll-coater 12 etc., adjust the thickness of the uncured layer 21b that constitutes by gas-liquid mixture 21a.Also have, no matter whether use processing release paper 3, when using this processing release paper 3, the thickness adjustment of uncured layer 21b is easy, and the surface of the froth bed 21 that can obtain after heat treatment (processing release paper 3 sides) go up and form the top layer.By these operations, the one side side (following) that can obtain uncured layer 21b has resin molding 22a (forming resin film layer 22), another side side (top) lamination 3 stratotype laminates of processing release paper 3.
Then, this laminate adopts annealing device to heat.Thus, foam raw material is reacted, uncured layer 21b is solidified, can obtain forming the polyurethane foam laminate 2 of froth bed 21.In this polyurethane foam laminate 2, froth bed 21 engages securely with resin film layer 22.Resulting polyurethane foam laminate 2, also can after processing release paper 3 is peeled off, be reeled as 2 stratotype layered products in formation roll bodies of upward reeling such as paper tubes as shown in Figure 1 with the 3-tier architecture former state, forms roll body.In addition, also can on manufacturing line, be cut into the size of regulation, make sheet.Secondly, also can, bale packing stacked this sheet.At this moment, both can 3 layers of former state stacked, also can be used as 2 stratotype layered products and come stacked.
Manufacture method to polyurethane foam laminate is specifically described below.
As mentioned above, the production of raw material for use of polyurethane foam laminate is gas-liquid mixture 21a and the resin molding 22a that adopts foam raw material and gas to obtain.
The compound method of above-mentioned foam raw material is not particularly limited, but preferably polyisocyanates, the method for mixing with the mixture of the polyalcohol that does not contain polyisocyanates, fire retardant, catalyst etc. (below be called " the 1st mixture ").Also have, the additive of Pei Heing is generally comprised within the 1st mixture as required.
The modulator approach of above-mentioned gas-liquid mixture 21a, be not particularly limited, the volume ratio of foam raw material and gas, when both amount to 100 volume %, foam raw material and gas are mixed, preferably reach 5～30 volume % and 70～95 volume %, more preferably 8～25 volume % and 75～92 volume % respectively.Adopt this mixing ratio, can modulate be suitable for forming froth bed with above-mentioned specific density gas-liquid mixture 21a.In addition, the mixer 11 that uses in the mixing of foam raw material and gas is not particularly limited, and preferably adopts AUX (オ one Network ス) mixer, ホ バ one ト mixer etc.Adopt these mixers 11, can evenly mix foam raw material with gas, the control of alveolation is easy, and being can be used as more by the homogeneous gas-liquid mixture 21a of alveolation, the mixture of homogeneous generates.
Also have, the method that foam raw material mixes with gas, preferably in the chamber of mixing usefulness etc., be blown in the foam raw material of depositing in advance gas method and, past this indoor method of supplying with foam raw material and gas simultaneously.At this moment, foam raw material also can be toward this indoor polyisocyanates and above-mentioned the 1st mixture supplied with respectively.
Adopt the froth bed of above-mentioned gas-liquid mixture, preferably adopt the mechanical foaming method to form.According to this method, the volume of the volume of the gas-liquid mixture of use and the polyurethane foam that obtains much at one.Therefore, the density of polyurethane foam can promptly, be adjusted the gas import volume of above-mentioned foam raw material by the composition of gas-liquid mixture.
For the density that makes foam reaches setting, be used for the gas combined amount that gas-liquid mixture forms, can be by following such decision.
At first, obtain the weighted average of the density (true specific gravity) of each contained in the foam raw material of definite quality composition, with it as foam raw material gross density (ρ).Then, with the quality of above-mentioned density (ρ), calculate the cumulative volume of foam raw material except that used foam raw material.
Secondly, from the cumulative volume of foam raw material and foam density (target density), obtain the gas volume amount that imports foam raw material as target.Use it in the actual manufacturing, can form polyurethane foam with desired density.
Above-mentioned resin molding 22a, only otherwise cause distortion when froth bed forms, rotten etc. can and be not particularly limited.In addition, as the support material of supporting froth bed, the material that preferably has tensile strength, tearing strength, hear resistance etc.As this resin molding 22a, can adopt plastic film usually.As synthetic resin, can enumerate mylar such as PETG, polybutylene terephthalate (PBT), polyurethane resin, vistanexes such as polyethylene, polypropylene, polyamide etc.Wherein, from the viewpoint of intensity, hear resistance etc., mylar, polyurethane resin and polyamide are preferred.In addition, have the polyurethane foam laminate of the present invention of the resin molding that contains these resins, when being used as the packing ring of 2 members of sealing, can obtain good adaptation and sealing.In the present invention, for above-mentioned resin molding 22a, mylar is preferred, and PETG is special preferred.
The thickness of above-mentioned resin molding 22a (being the thickness that constitutes the resin film layer 22 of polyurethane foam laminate) is not particularly limited yet.Preferred thickness more than 25 μ m, more preferably 25～125 μ m, especially preferred 25～100 μ m, preferred especially 30～70 μ m.When this thickness more than 25 μ m, when making continuously as shown in Figure 1, also fully tolerate the tension stress of froth bed 11 at forming direction, make the stable possibility that creates of polyurethane foam laminate.In addition, when above-mentioned resin molding 22a is a PETG, and its thickness is when being 25～125 μ m, and shape stability is good.In addition, the polyurethane foam laminate of this formation when when the packing ring, does not excessively form upright and outspokenly, and the operation during insertion toward between housing members such as mobile phone is easy, can obtain good sealing etc.
Above-mentioned gas-liquid mixture 21a is supplied with the surface of above-mentioned resin molding 22a, and then, to the surface of the gas-liquid mixture 21a of curtain coating, square from it side is supplied with processing release paper 3, forms laminate.Secondly,, heat, the foam raw material that contains among the uncured layer 21b is reacted, form froth bed 21 with the annealing device 13 that is set in set point of temperature this 3 stratotype laminate.
The heating means of above-mentioned 3 stratotype laminates are not particularly limited, and can suitably select according to the kind of annealing device 13 etc.
Heating-up temperature is solidified for making the foam raw material that contains among the uncured layer 21b, can suitably select according to the kind of polyalcohol and polyisocyanates etc.This heating-up temperature, preferred 120 ℃～200 ℃, more preferably 140 ℃～180 ℃, preferred especially 150 ℃～170 ℃.
In addition, heat time heating time, preferred 1～10 minute, more preferably 1～5 minute.
As above-mentioned annealing device 13, can enumerate heating furnace, far-infrared radiation device etc.When adopting heating furnace, utilize the thermal source that is fixed in the device, the limit makes 3 stratotype laminates static or mobile, and heat-treat on the limit.At this moment, also can supply with hot blast.Also have, when making polyurethane foam laminate continuously, the limit is moved 3 stratotype laminates in heating furnace, and heat on the limit is preferred.
To the heating of above-mentioned 3 stratotype laminates,, or carry out from both sides in any side of resin molding side and processing release paper side.In the present invention, for it is all evenly heated, more effective formation is the froth bed 21 of homogeneous more, and it is preferred heating from the both sides of 3 stratotype laminates.
The manufacture method of polyurethane foam laminate of the present invention, during for manufacturing system shown in Figure 1, the modulation of gas-liquid mixture 21a, gas-liquid mixture 21a on resin molding 22a supply and, supply above uncured layer 21b such as processing release paper, adopt the thickness adjustment of roll-coater etc. and to the heating of 3 stratotype laminates, can carry out continuously, can make polyurethane foam laminate continuously.That is, adopt the gas-liquid mixture 21a of mixer 11 modulation, sent continuously, upward supply with continuously to the resin molding 22a that moves with the feed speed of regulation, to the surface of the gas-liquid mixture 21a of curtain coating, processing release paper 3 is supplied to the speed identical with resin molding 22a, adjusts thickness with roll-coater 12.Then, the annealing device 13 of 3 stratotype laminates importing with roll-coater 12 disposed adjacent, for example heating furnace.When adopting heating furnace, can import 3 stratotype laminates from the one peristome usually, use the translational speed identical or approximate with resin molding 22a, move in the heating furnace, derive from another peristome and also can.Thus, can make polyurethane foam laminate with processing release paper 3.Then, as required, remove processing release paper 3, make the polyurethane foam laminate that comprises froth bed 21 and resin film layer 22.
Also have, in the manufacture method of polyurethane foam laminate of the present invention, can on the two sides of resin film layer 22, form froth bed 21.As this method, can enumerate froth bed 21 and heat simultaneously in the method that forms on each single face and after forming uncured layer 21b on the two sides of resin molding 22a, form the method for froth bed 21 simultaneously.
Polyurethane foam laminate of the present invention as mentioned above, can be unworthy of Heshui and blowing agent in foam raw material, adopt the mechanical foaming method to make.In addition, also can be in foam raw material hydrous water and/or blowing agent, adopt so-called chemical blowing process to make.At this moment, as water, can adopt ion exchange water, running water, distilled water etc.The consumption of water is not particularly limited, and when polyalcohol is 100 mass parts, is generally 0.1～0.5 mass parts, special preferred 0.2～0.4 mass parts.In addition, blowing agent is not particularly limited, and can adopt hydrocarbon, substitute fluon etc.The consumption of this blowing agent is not particularly limited yet.Therefore, when employing has cooperated the chemical blowing process of the foam raw material of water and/or blowing agent to replace the mechanical foaming method, but the bubblement stable maintenance of gas-liquid mixture, it is coarse etc. also not produce pore, can easily form the froth bed with desirable density and thickness.Its result can make the polyurethane foam laminate of the froth bed with good rerum natura.
1-3. the rerum natura of polyurethane foam laminate
Polyurethane foam laminate of the present invention is the binding element that adopts that said method is made, froth bed 21 and resin film layer 22.The density of above-mentioned froth bed is 100～280kg/m
3, preferred 120～260kg/m
3, preferred especially 150～240kg/m
3
The density of above-mentioned froth bed is that the quality of layered product is deducted quality after the resin film layer quality, removes and calculate with the volume of froth bed.Also have, the volume of froth bed is calculated like that by following.That is, from layered product, for example, cut rectangle, make test piece, the size in length and breadth of this test piece is measured with slide calliper rule etc.Then, after the gross thickness of test piece is measured with amesdial thickness meter etc., deduct the thickness of resin film layer, obtain the thickness of froth bed.And, from above-mentioned in length and breadth size and the thickness of froth bed, can be regarded as out the volume of froth bed.
In the past, only the complexed metal hydroxide powder as fire retardant, form for example 280kg/m of density
3During following low density foam layer, it is coarse etc. to produce pore, and can not form can be for practical polyurethane foam laminate.But, according to manufacture method of the present invention,, can form repressed, the soft froth bed of unfavorable condition such as have above-mentioned specific density, pore is coarse by metal hydroxides and liquid combustion inhibitor and usefulness, and, can form the good polyurethane foam laminate of anti-flammability.
In addition, formed in the polyurethane resin portion of froth bed, contained metal hydroxides powder and liquid combustion inhibitor as fire retardant, these do not ooze out and keep.In addition, in aftermentioned purposes etc., even when waiting load by compression, do not ooze out too.The content of metal hydroxides powder and liquid combustion inhibitor, relative polyurethane 100 mass parts are respectively preferred 20～60 mass parts and 5～20 mass parts, more preferably 20～40 mass parts and 5～10 mass parts.
In the polyurethane foam laminate that the method for employing the invention described above is made, compare, can have the little froth bed of pore diameter with the soft dull and stereotyped polyurethane foam that adopts known in the past chemical blowing manufactured.That is, the average pore diameter in the above-mentioned froth bed, preferred 50～350 μ m, special preferred 50～250 μ m.When the pore diameter of froth bed is in above-mentioned scope, can form polyurethane foam laminate with good rerum naturas such as the compression residual deformation are little.When using as the packing ring of 2 members of sealing with the little polyurethane foam laminate of compression residual deformation, in the polyurethane foam laminate resin film layer side surface and froth bed side surface both, can on 2 members, can be obtained good sealing etc. by abundant driving fit.
Above-mentioned average pore diameter is observed for 200 times the section amplification of froth bed with scanning electron microscope, and the aggregate value of pore diameter is removed and calculated with the number of pore.
The thickness of above-mentioned froth bed can suitably be selected according to purpose, purposes etc., is generally 0.4～1.5mm.
In addition, the thickness of polyurethane foam laminate of the present invention is not particularly limited, and is generally 0.5～1.8mm, preferred especially 0.5～1.0mm.
Polyurethane foam laminate of the present invention as mentioned above, can form the layered product that has froth bed on the two sides of resin film layer.At this moment, density, average pore diameter and thickness in 2 froth beds, both can be identical mutually also can be different.
In addition, the face (with the opposing face of the face of lamination on the resin film layer) that exposes of the froth bed in the polyurethane foam laminate of the present invention goes up that to form the top layer be preferred.This has the polyurethane foam laminate on top layer, and when as packing ring, the sealing of the periphery of 2 members of formation Instrument shell etc. can reach complete.Above-mentioned top layer can observe obtaining confirming to the section of froth bed with electron microscope etc.
Loading when 40% of polyurethane foam laminate of the present invention compresses, preferred 0.002～0.02MPa, preferred especially 0.005～0.015MPa.Loading during this 40% compression is the 40%CLD that measures according to JIS K 6254.
In addition, in the polyurethane foam laminate,, preferred below 10.0%, preferred below 6.0% especially in 70 ℃ of temperature, the compression residual deformation in 50% when compression.Also have, lower limit is generally 0.3%.This compresses residual deformation, can measure according to JIS K 6401.
2. the purposes of polyurethane foam laminate
Polyurethane foam laminate of the present invention is to be useful polyurethane foam laminate in the purposes of packing ring etc.
Packing ring of the present invention can be made into the shape according to purpose, purposes etc.For example, packing ring 100 is as shown in Figure 2 processed polyurethane foam laminate of the present invention and is obtained, be have resin film layer 102 and with the ring spacer of the froth bed 101 of the surface engagement of this resin film layer 102, the surface of froth bed 101 (Fig. 2's is top) preferably has the top layer.Like this, the one side side of packing ring 100 is made of resin film layer 102 and forms the packing ring 100 of the froth bed 101 with top layer on the another side side, when when the sealing of the periphery of 2 members of the housing that constitutes instrument etc., adopting, can be from suppressing the intrusion of dust between 2 members.That is, can fully prevent the intrusion of the dust of two sides side (froth bed 101 sides, and resin film layer 102 sides) from packing ring 100.
The shape of packing ring of the present invention does not limit the peristome bigger than body part that have as shown in Figure 2, for example, stipulates the sheet (polyurethane foam laminate) of shape relatively, can have the peristome of small size yet.
The thickness of above-mentioned packing ring is not particularly limited, and is generally 0.4～1.5mm, preferred especially 1.0～1.5mm.When the thickness of packing ring was 0.4～1.5mm, then the limit produced the polyurethane foam laminate flexibility, and the limit obtains good sealing.
Obtain the method for the packing ring with circulus 100 shown in Figure 2, be not particularly limited, the method that can enumerate the method that adopts the blanking die stamping-out, cuts with cutting machine continuously etc.Wherein, blanking method is preferred.In addition, as mentioned above, because froth bed 101 low-density, and flexibility is good, therefore when stamping-out etc., can not abrade froth bed 101, or can not make and add Ministry of worker's periphery etc. and produce defective.
Packing ring of the present invention can be inserted between the housing member of electronic instrument and use.This electronic instrument is not particularly limited, and can enumerate portable electronic instruments such as mobile phone, digital camera, digital camera, portable type computer, pocket sound equipment, portable type game machine, guider etc.In these electronic instruments, particularly many people hold and the mobile phone that how when going out, carries, easily contact with the fiber of clothes etc., it is preferred using packing ring of the present invention.
The housing of electronic instrument, usually constitute by opposed in opposite directions a plurality of housing members, between housing member, insert packing ring, but in recent years, be accompanied by miniaturization, the high performance of electronic instrument, operation is not easily, need embed the ditch of packing ring and have good sealing packing ring on the housing member when need inserting.In addition, owing to make the wall of housing member thin, with original same member when connected to each other, warpage takes place housing member sometimes, so need have the packing ring of ten minutes flexibility.Under this situation, packing ring of the present invention is a low-density and very soft, also is being favourable aspect miniaturization, the particularly slimming of reply electronic instrument.
Embodiment
Below, specifically describe the present invention by embodiment.Also have, following " part " is not particularly limited, and is quality criteria.
The raw material that the manufacturing of polyurethane foam laminate is used such as following.
(1) PPG A
Adopt Sanyo to change into " GP-3000 " (trade name) that society makes.
(2) PPG B
Adopt Sanyo to change into " GP-600 " (trade name) that society makes.
(3) catalyst
ス タ Na ス オ Network ト エ one ト that adopts north of the city chemistry society to make.
(4) surfactant
The silicone based surfactant " L-5617 " (trade name) that adopts モ メ Application テ イ ヴ society to make.These goods are the block copolymer of dimethyl polysiloxane and polyethers.
(5) metal hydroxides powder
Adopt aluminium-hydroxide powder " Ha イ ジ ラ イ ト H-10 " (trade name) clear and that electrician society makes.
(6) phosphorus type flame retardant
The aliphatic condensed phosphoric acid esters " DAIGUA R D880 " (trade name) that adopts big eight chemical industry societies to make.These goods are light yellow transparent liquid in the time of 25 ℃.
(7) polyisocyanates
The thick MDI " C-1130 " (trade name) that adopts Japanese polyurethane society to make.Polyisocyanate-based content is 31%.
(8) resin molding
Adopt the PETG film of thickness 50 μ m.
Embodiment 1～4 and 6～15 and comparative example 1～7
The metal hydroxides powder and the phosphorus type flame retardant of the use level of record in 100 parts of PPGs (mass ratio with 90/10 uses PPG A and B), 0.1 part of catalyst, 5 parts of surfactants and the table 1～table 4 are mixed, stirred, modulated the 1st mixture.
Then, the polyisocyanates input that the 1st mixture and isocyanate index are reached 0.9～1.1 use level is configured in the indoor of AUX's mixer.Then, inject the nitrogen amount of the amount of the prescribed volume ratio that reaches table 1～table 4 record simultaneously, so that reach the target density of the froth bed of record in table 1～table 4.
Secondly, mentioned component is stirred, mixed, be modulated into the gas-liquid mixture of alveolation indoor.And, on the resin molding of this gas-liquid mixture supply with 5m/ minute speed transmission, on the surface of the gas-liquid mixture of curtain coating, square from it side, supply with processing release paper with the speed identical with resin molding, adopt roll-coater, be adjusted to specific thickness, form the uncured layer (with reference to Fig. 1) that constitutes by gas-liquid mixture.
Then, 3 layers of laminate that will comprise resin molding, uncured layer and processing release paper import and are heated to 160 ℃ heating furnace with far infra-red heater and heat (length of heating furnace is that 5m, heat time heating time are 1 minute).Secondly, peel off processing release paper, resin molding and froth bed are bonded into polyurethane foam laminate, on paper tube, reel from layered product.The thickness of polyurethane foam laminate is with amesdial thickness instrumentation fixed (table 1～table 4).
Embodiment 5
As PPG, except that only adopting 100 parts of PPG A,, obtain polyurethane foam laminate (table 1) with above-mentioned same.
Cut test piece from the polyurethane foam laminate of above-mentioned manufacturing, loading and compression residual deformation when measuring density, average pore diameter, 40% compression of froth bed, have or not and ooze out, have or not indentation and anti-flammability the outward appearance of assess foam layer.It the results are shown in table 1～table 4.
(1) density of froth bed
(50mm * 50mm), make test piece, the size in length and breadth of this test piece is correctly measured with slide calliper rule to cut square shape from the polyurethane foam laminate that obtains.Then, deduct thickness of resin film, obtain the thickness of froth bed from the thickness of layered product shown in each table.Then, adopt above-mentioned in length and breadth size and the thickness of froth bed, calculate the volume of froth bed.Secondly,, deduct resulting quality after the quality of resin film layer, remove, obtain the density of froth bed with above-mentioned volume of foam from the quality of test piece.
(2) average pore diameter
The section of the froth bed in the polyurethane foam laminate that obtains is used scanning electron microscope, amplifies 200 times and observes, and to 50 in image foaming pores, surveys size.Then, the total of these pore diameter obtains average pore diameter with the individual divisor of pore.
Loading during (3) 40% compressions
Measure according to JIS K 6254.Concrete is, polyurethane foam laminate is carried out stamping-out processing, obtains the circular test piece of diameter 50mm.Then, adopt and the compression clamp of this test piece, carry out concentric circles with test piece and contact, use compression test,, carry out 40% compression (reaching 60% preceding thickness of compression), measure the loading of this moment with 1mm/ minute speed in 23 ℃ of temperature with diameter.From the loading that obtains, loading (unit: MPa) when calculating 40% compression according to following formula.
The loading during 40% compression=[area (mm of loading (the N)/test piece during 40% compression
2)]
(4) compression residual deformation
Measure according to JIS K 6401.Concrete is, to polyurethane foam laminate, carries out stamping-out processing, obtains the test piece of 50mm * 50mm.Then, this test piece compression test, in 70 ℃ of compressions 50% of temperature, former state was placed 22 hours.Then, open compression after 30 minutes, is measured the thickness of test piece in 23 ℃ of placements.Adopt the thickness of compression test front and back, calculate the compression residual deformation according to following formula.
Compression residual deformation (%)=[thickness before (thickness after the thickness-opening before the compression)/compression] * 100
(5) outward appearance of froth bed
The surface of the froth bed of polyurethane foam laminate is observed with light microscope, the number of the major diameter pore that diameter (full-size) the 700 μ m that exist in counting 10cm is square are above, the outward appearance of assess foam layer." well " in the table means the major diameter pore less than 20, and " pore is coarse " means the major diameter pore and observe more than 20.
(6) have or not and ooze out
Polyurethane foam laminate is carried out machining, obtain the test piece of 50mm * 50mm.Then, (behind 60mm * 60mm * 0.1mm), use compression test, in 70 ℃ of compressions 50% of temperature, former state was placed 168 hours at mounting Copper Foil on the froth bed surface of this test piece.Secondly, open compression, the copper foil surface that perusal is peeled off (with the contact-making surface of froth bed) is estimated the exudative of phosphorus type flame retardant." nothing " in the table means copper foil surface and do not observe impurity, do not ooze out, and " the having " in the table means copper foil surface and observe impurity, oozes out.
(7) have or not indentation
Polyurethane foam laminate is carried out machining, obtain the circular test piece of diameter 50mm.Then, the froth bed of this test piece makes progress, and the disc that is placed on experimental rig is worn the central portion of putting above the platform.Then, the stainless steel pressing body from top contact diameter 50mm makes with test piece to become concentric circles, and pressing body is applied the 1.2kg loading.Secondly, put platform with the speed rotation (the symbol optional position of test piece edge portion on be accompanied by rotation translational speed reach 50mm/ minute) of test piece, when rotating 10 times, stop the rotation with 43 rev/mins wearing.Then, the froth bed of perusal test piece is estimated scratch property." zero " in the table means the froth bed surface and does not observe scratch, and " △ " means and observe the scratch of full-size less than 5mm, and " * " means and observe the above scratch of full-size 5mm.
(8) anti-flammability
Whether qualified with the fire-retardant benchmark HBF specification stipulated among the UL94, estimate anti-flammability.In the table " zero ", it is qualified to mean the HBF specification, and it is defective that " * " means the HBF specification.
Table 1
Annotate "-" expression undetermined.
Table 2
Annotate "-" expression undetermined.
Table 3
Annotate "-" expression undetermined.
Shown in table 1～table 3, adopt the content of relative polyalcohol to contain the polyurethane foam laminate of embodiment 1～15 of froth bed of the foam raw material density range that form, that have regulation of the metal hydroxides powder of ormal weight and phosphorus type flame retardant, it is very little and the compression residual deformation is also little to compress 40% o'clock loading.In addition, all among the embodiment, the outward appearance of froth bed is good, and phosphorus type flame retardant does not also ooze out and good.In addition, having or not during indentation estimates, among the lower a part of embodiment of the density of froth bed, can observe the minority indentation, but not have big problem, be the polyurethane foam laminate that in the purposes of packing ring etc., can fully use.In addition, in whole embodiment, the HBF specification is qualified, has good anti-flammability.
On the other hand, as known from Table 4,, do not contain the comparative example 1 of phosphorus type flame retardant, the coarse and indentation of pore takes place even the density of froth bed is in the preferred range.In addition, the comparative example 2 of metal hydroxide-containing powder not, anti-flammability is defective.In addition, the comparative example 2 of metal hydroxide-containing powder and comparative example 3 do not compress residual deformation and significantly become big.In addition, though contain the metal hydroxides powder of ormal weight and the low excessively comparative example 4 and the comparative example 7 of density of phosphorus type flame retardant froth bed, the coarse and indentation of pore takes place.In addition, comparative example 5 and comparative example 6 be not though the rerum natura aspect has special problem, because the density of froth bed is too high, therefore for particularly can not supply with practical polyurethane foam laminate in the purposes of packing ring.
Also have, the present invention is not limited to above-mentioned specific embodiment, can form the embodiment of all changes within the scope of the invention according to purpose, purposes.For example, employing cooperates water, the so-called chemical blowing process of (polyalcohol is 100 parts) about 0.2～0.4 part also can make same polyurethane foam laminate in foam raw material.
Utilize possibility on the industry
The present invention can utilize in the various goods field of the intrusions such as the anti-sealing of needs and dust. In addition, in recent years, significantly requiring slimming, miniaturization and high performance, also requiring many people electronic instruments that hold and that how when going out, to carry such as value in the various electronic instrumentations of well-designed is higher, mobile phone, digital camera, guider, in the mobile phone of popularizing significantly, often carrying, be useful especially particularly.
Claims (11)
1. polyurethane foam laminate, it is characterized in that, be that the foam raw material that contains polyisocyanates, polyalcohol and fire retardant is being mixed with gas, generate gas-liquid mixture, then, this gas-liquid mixture is supplied with on the resin molding, secondly, heat this gas-liquid mixture, this foam raw material is reacted and in the polyurethane foam laminate of resin film layer that having of obtaining comprises this resin molding and the froth bed of the polyurethane foam that comprises generation
The above-mentioned fire retardant that contains in the above-mentioned foam raw material contains metal hydroxides powder and liquid combustion inhibitor, and when above-mentioned polyalcohol was 100 mass parts, this metal hydroxides powder was 20～60 mass parts, and this liquid combustion inhibitor is 5～20 mass parts, and,
The density of above-mentioned froth bed is 100～280kg/m
3
2. according to the polyurethane foam laminate described in the claim 1, wherein, above-mentioned liquid combustion inhibitor is a phosphorus type flame retardant.
3. according to the polyurethane foam laminate described in the claim 1, wherein, the average grain diameter of above-mentioned metal hydroxides powder is 10～100 μ m.
4. according to the polyurethane foam laminate described in the claim 1, wherein, above-mentioned resin film layer contains PETG, and the thickness of this resin film layer is 25～125 μ m.
5. according to the polyurethane foam laminate described in the claim 1, wherein, the average pore diameter of above-mentioned froth bed is 50～300 μ m.
6. according to the polyurethane foam laminate described in the claim 1, wherein, above-mentioned froth bed with above-mentioned resin film layer on have the top layer on the face of face opposition side of lamination.
7. according to the polyurethane foam laminate described in the claim 1, wherein, the loading of compressing at 40% o'clock is 0.002～0.02MPa.
8. according to the polyurethane foam laminate described in the claim 1, wherein, in 50% o'clock compression residual deformations of 70 ℃ of compressions of temperature below 10.0%.
9. the manufacture method of polyurethane foam laminate; It is characterized in that; The foam raw material that contains polyisocyanates, polyalcohol and fire retardant is mixed with gas; Generate gas-liquid mixture; Then; This gas-liquid mixture is supplied with on the resin molding; Secondly; Heat this gas-liquid mixture; This foam raw material is reacted; Obtain having the resin film layer that comprises this resin molding and comprised the manufacture method of polyurethane foam laminate of solidifying the froth bed of the polyurethane foam that generates by the reaction of this foam raw material
The above-mentioned fire retardant that contains in the above-mentioned foam raw material contains metal hydroxides powder and liquid combustion inhibitor, and when above-mentioned polyalcohol was 100 mass parts, this metal hydroxides powder was 20～60 mass parts, and this liquid combustion inhibitor is 5～20 mass parts, and,
The density of above-mentioned froth bed is 100～280kg/m
3
10. packing ring is characterized in that, any one described polyurethane foam laminate forms in the employing claim 1 to 8.
11. according to the packing ring described in the claim 10, its thickness is 0.4～1.5mm.
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| US9751241B2 (en) | 2013-06-13 | 2017-09-05 | Saint-Gobain Performance Plastics Corporation | Foam gasket and bonding tape based on polyurethane dispersions |
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| KR20220054802A (en) * | 2019-08-28 | 2022-05-03 | 세키스이가가쿠 고교가부시키가이샤 | Polyol-Containing Compositions, Expandable Polyurethane Compositions and Polyurethane Foams |
| CN116234687A (en) * | 2020-12-24 | 2023-06-06 | 井上株式会社 | Sheet and method for producing sheet |
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| JP2008006592A (en) * | 2006-06-27 | 2008-01-17 | Inoac Corp | Method for producing sheet-shaped product of polyurethane foam |
-
2010
- 2010-03-18 JP JP2010063234A patent/JP5479174B2/en active Active
- 2010-03-23 KR KR1020100025637A patent/KR20100106929A/en not_active Application Discontinuation
- 2010-03-24 CN CN201010143220.1A patent/CN101850639B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637108A (en) * | 2003-12-11 | 2005-07-13 | 井上株式会社 | Flame resistant sealing material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014100921A1 (en) * | 2012-12-31 | 2014-07-03 | Saint-Gobain Performance Plastics Corporation | Foam gasket and bonding tape based on polyurethane dispersions |
| US9751241B2 (en) | 2013-06-13 | 2017-09-05 | Saint-Gobain Performance Plastics Corporation | Foam gasket and bonding tape based on polyurethane dispersions |
| US9878471B2 (en) | 2013-06-13 | 2018-01-30 | Saint-Gobain Performance Plastics Corporation | Foam gasket and bonding tape based on polyurethane dispersions |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100106929A (en) | 2010-10-04 |
| CN101850639B (en) | 2014-10-01 |
| JP2010247532A (en) | 2010-11-04 |
| JP5479174B2 (en) | 2014-04-23 |
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