JP2005219363A - Method and apparatus for producing glass fiber-reinforced rigid polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing glass fiber-reinforced rigid polyurethane foam in which it is difficult to be glass fiber-reinforced rigid polyurethane foam having a thin foamed layer when foaming is finished, and the reinforcing fibers are distributed uniformly in the thickness direction to produce a product high in uniformity. <P>SOLUTION: The method has a glass fiber mat supply process for supplying a glass fiber mat 6 onto a lower surface material 11L supplied from a lower surface material supply apparatus, an original solution supply process for supplying a rigid polyurethane foam foamed original solution composition 5 onto the supplied glass fiber mat 6, and an upper surface material supply process for continuously supplying an upper surface material 11U from an upper surface material supply apparatus onto its upper surface supplied with the original solution. By a press means 1 arranged between the glass fiber mat supply process and the original solution supply process, the glass fiber mat 6 supplied onto the lower surface material 11L is supplied to the downstream side while being pressed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing glass fiber-reinforced rigid polyurethane foam and a manufacturing apparatus therefor, and more particularly, heat insulation panels for ultra-low temperatures, in particular, heat insulation of a storage facility for storing LNG, liquefied helium, liquefied nitrogen and other low-boiling substances, particularly LNG. The present invention relates to a method for producing a glass fiber reinforced rigid polyurethane foam that can be used as a heat insulating panel suitable for the present invention, and an apparatus for producing a glass fiber reinforced rigid polyurethane foam suitable for carrying out this method.

  A rigid polyurethane foam reinforced with glass fibers that can be suitably used as an insulation material for ultra-low temperatures (hereinafter sometimes abbreviated as “RPUF”) generally has a glass fiber mat placed on the bottom material. Then, a foaming stock solution composition for forming a rigid polyurethane foam is supplied and impregnated, and then a top material is supplied, followed by nipping with a nip roll, reaction, and foaming.

A technique for producing a glass fiber reinforced rigid polyurethane foam by supplying a plurality of glass fiber mats during production is known (Patent Document 1). Patent Document 1 discloses a technique for lifting a glass fiber mat as foaming proceeds to reduce non-uniformity of glass fibers.
JP 2001-150558 A

  According to the method for producing a glass fiber reinforced rigid polyurethane foam disclosed in Patent Document 1, a glass fiber mat such as a continuous strand mat is supplied by unwinding a commercial product as it is from a roll-shaped raw material. The binder that binds the intersections of the yarns dissolves in the foaming stock solution composition, or the binding is released to some extent by nipping with a nip roll, and in the thickness direction due to the progress of foaming and curing of the foaming stock solution composition In many cases, foaming hardening of the foaming stock composition proceeds while the intersections of the yarns are bonded with a binder.

  Therefore, the supplied glass fiber mat is lifted as the foaming progresses, and a plurality of glass fiber mats exist uniformly in the thickness direction of the obtained glass fiber reinforced rigid polyurethane foam. The glass fibers constituting the fiber mat do not spread uniformly in the thickness direction, and in the formed glass fiber reinforced rigid polyurethane foam, portions with high and low glass fiber concentration are generated between the layers of the glass fiber mat and the like. There is a problem that the property is not sufficient and the strength is likely to vary. Not only the surface of the supplied glass fiber mat has irregularities, but when the foaming stock solution composition is supplied, it tends to accumulate in the recesses and becomes thin in the projections, and at the end of foaming, the foam layer in the projections The thin glass fiber reinforced rigid polyurethane foam is finished, and a non-uniform product in the thickness direction is completed.

  Therefore, the problem to be solved by the present invention is, in view of the above-mentioned problems of the prior art, difficult to become a thin glass fiber reinforced rigid polyurethane foam with a foamed layer at the end of foaming, the reinforcing fibers are uniformly distributed in the thickness direction, It is an object of the present invention to provide a method for manufacturing a glass fiber reinforced rigid polyurethane foam capable of manufacturing a highly uniform product and a manufacturing apparatus therefor.

  The above object can be achieved by the invention described in the claims. That is, the characteristic configuration of the method for producing a glass fiber reinforced rigid polyurethane foam according to the present invention includes a glass fiber mat supplying step of supplying a glass fiber mat onto the lower surface material supplied from the lower surface material supply device, and the supplied glass. A stock solution supplying step of supplying a rigid polyurethane foam foam stock solution composition onto the fiber mat, and a top surface material supplying step of continuously supplying the top material from the top material supply device to the top surface supplied with the stock solution. In the method having, the pressing means disposed between the glass fiber mat supply step and the stock solution supply step is to feed the glass fiber mat supplied onto the lower surface material to the downstream side while pressing. .

  According to this configuration, the surface unevenness of the moving glass fiber mat can be leveled, the unevenness as in the prior art occurs, and the foaming stock solution composition is locally thinned or thickened. Not only can the occurrence be prevented, but also the glass fiber mat is not only pressed but also fed downstream, so that it is possible to avoid the accumulation of stress inside the glass fiber mat, after the presser means Also in this step, the reinforcing fibers are uniformly distributed in the thickness direction, and a product with high uniformity can be manufactured as a whole.

  As a result, a glass fiber reinforced rigid polyurethane foam with a thin foam layer at the end of foaming is unlikely, and a method for producing a glass fiber reinforced rigid polyurethane foam capable of producing a highly uniform product in which reinforcing fibers are uniformly distributed in the thickness direction is provided. We were able to.

  It is preferable that feeding to the downstream side while pressing the glass fiber mat on the lower surface material is performed by a rotation driving unit that rotates the pressing unit.

  According to this configuration, the glass fiber mat can be reliably fed downstream. In particular, if a pressing roller is used as the pressing means and a rotating roller separate from the pressing roller is used as the rotation driving means, the end face in the width direction is flexible when manufacturing a glass fiber reinforced rigid polyurethane foam. Even in the case of covering with a material, pressing and rotation of the pressing roller can be smoothly operated over the entire width direction.

  It is preferable that the stock solution supplying means for supplying the rigid polyurethane foam foam stock solution composition in the stock solution supplying step and the supply position of the top material supplied from the top material supply device are relatively movable.

  According to this structure, it can be made to penetrate evenly into the glass fiber mat according to the characteristics of the supplied rigid polyurethane foam foam concentrate solution, for example, the viscosity, and a product with higher uniformity can be produced.

  In addition, the characteristic configuration of the glass fiber reinforced rigid polyurethane foam manufacturing apparatus according to the present invention includes a lower surface material supply device for supplying a lower surface material, and a glass fiber mat supplied on the lower surface material supplied from the lower surface material supply device. A glass fiber mat supply device, a raw solution supply means for supplying a hard polyurethane foam foam concentrate solution to the glass fiber mat, and a continuous top surface of the rigid polyurethane foam foam concentrate solution supplied by the concentrate supply means. And an upper surface material supply device for supplying an upper surface material, wherein a pressing means is disposed between the glass fiber mat supply device and the stock solution supply means, and the glass supplied onto the lower surface material. It exists in feeding downstream, pressing a fiber mat.

  According to this configuration, it is difficult to become a glass fiber reinforced rigid polyurethane foam with a thin foam layer at the end of foaming, and the production of glass fiber reinforced rigid polyurethane foam capable of producing a highly uniform product in which reinforcing fibers are uniformly distributed in the thickness direction. An apparatus can be provided.

  It is preferable that a rotation driving means for rotating the pressing means and feeding the glass fiber mat to the downstream side is provided in the pressing means.

  According to this configuration, the glass fiber mat can be reliably fed downstream.

  It is preferable that the stock solution supply unit and the supply position of the upper surface material supplied from the upper surface material supply device can be moved relative to each other.

  According to this configuration, it is possible to produce a product with more uniform characteristics of the rigid polyurethane foam foam concentrate solution to be supplied.

  Embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 shows a schematic overall configuration of a manufacturing apparatus suitable for carrying out the present invention and a schematic configuration of a manufacturing method using this manufacturing apparatus. In this example, flexible face materials are used for both the upper and lower double-sided materials, and three layers of glass fiber mats are supplied.

  That is, the lower surface material 11L is supplied from the lower surface material supply device 10L onto the conveyors 7 and 8 (lower surface material supply process), and three glass fiber mat supply devices 6a, 6b, The glass fiber mat 6 is unwound by the unwinding roller 4 equipped with a number of discs from 6c and is continuously unwound from the original fabric and supplied and placed (glass fiber mat supply step), which is a stock solution supply means. After supplying the rigid polyurethane foam foam stock solution composition 5 (hereinafter sometimes referred to as foam stock solution composition) supplied from the head 3 of the foaming machine by a casting method (stock solution supplying step), the upper surface material 11U is squeezed from above. It is continuously supplied from the upper surface material supply apparatus 10U via the roller 22 to form a sandwich (upper surface material supply process), and hard by the nip roll 15 After re urethane foam frothing liquid was sufficiently impregnated into the glass fiber mat (nipping step), sent to the heating oven 19 provided with a conveyor 17, by foaming and curing to produce a (foaming step) glass fiber reinforced rigid polyurethane foam B.

  The glass fiber reinforced rigid polyurethane foam production apparatus of the present embodiment is, as shown in an enlarged view in FIG. 2, after the glass fiber mat 6 is supplied on the lower surface material 11L, the foaming stock solution composition from the head 3 of the foaming machine. Before the glass fiber mat 6 is pressed by the pressing roller 1 which is a pressing means, and the surface thereof is smoothed. By doing so, the unevenness of the surface of the supplied glass fiber mat 6 is reduced, and the foaming stock solution composition is effectively prevented from being easily accumulated in the concave portion and becoming thin in the convex portion. A product having a uniform direction is formed. However, the unevenness on the surface of the glass fiber mat 6 does not need to be completely smooth, and when the foaming stock composition is supplied, it is difficult to accumulate deeply in the concave portion and to be in a thin state in the convex portion with respect to the supply amount. If it is.

  Further, the presser roller 1 is rotationally driven by a rubber roller 2 which is a rotary drive means via a drive source (not shown) at two positions above and below the presser roller. The presser roller 1 is a rubber roller. Since the press roller 1 is rotationally driven by 2, the presser roller 1 not only simply presses the glass fiber mat 6 from above, but also provides a function of feeding downstream. Therefore, the internal stress of the glass fiber mat is reduced, and a product having a uniform thickness after foaming can be reliably manufactured.

  The rotational drive means is not limited to rubber, but is preferably made of a material having a high frictional resistance such as rubber. However, the rotation driving means is not necessarily a separate roller from the pressing roller 1, and a driving system that directly rotates the pressing roller 1 itself may be employed. Further, the surface of the presser roller 1 may be provided with a number of irregularities such as fine lateral grooves and dimple patterns so that the supplied foaming stock solution composition can easily flow on the surface.

  In addition, it is preferable that the manufacturing apparatus of the glass fiber reinforced rigid polyurethane foam of the present embodiment is configured such that the head 3 of the foaming machine can be moved back and forth toward the upper surface material supply side. In such a case, even if the viscosity of the foamed undiluted solution composition 5 varies, the permeability to the glass fiber mat 6 can be maintained in a preferable state, which is convenient for producing a uniform product. . That is, when the viscosity of the foaming stock solution composition 5 is high, the permeability to the glass fiber mat 6 is not good, so that the distance L between the foaming machine head 3 and the ironing roller 22 is increased. When the head 3 is retracted from the upper surface material supply side, the foamed undiluted liquid composition 5 can sufficiently penetrate into the glass fiber mat 6 and a glass fiber reinforced rigid polyurethane foam having high uniformity in the thickness direction can be produced. it can.

  No. 20 is a glass fiber mat lifting device, and this device is not always necessary. However, through this process, the glass fibers are more uniformly distributed in the thickness direction, which is convenient.

  Next, the RPUF used in this embodiment will be described. This RPUF is formed by using a rigid polyurethane foam stock solution having excellent low-temperature insulation performance. The rigid polyurethane foam stock solution uses a component containing an active hydrogen-containing compound, a foaming agent, a catalyst, etc. (polyol component) and a component mainly composed of a polyisocyanate compound (isocyanate component), and a polyol using a foaming machine. The component and the isocyanate component are mixed and used for forming a glass fiber reinforced rigid polyurethane foam as a foamed stock solution composition.

  As the polyisocyanate compound constituting the isocyanate component, any polyisocyanate compound known in the technical field of polyurethane can be used. Specifically, 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, Aromatic diisocyanate compounds such as 2,6-toluene diisocyanate and naphthalene diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated m-xylylene diisocyanate (HXDI) , Cycloaliphatic diisocyanates such as norbornane diisocyanate, crude MDI (44V-10, 44V-20, etc. (manufactured by Bayer)), uretonimine-containing MDI (liquid MDI) Millionate MTL; polyfunctional isocyanates of Nippon Polyurethane Industry) and the like.

  Said polyisocyanate compound may be used independently and may use 2 or more types together. Among the above polyisocyanate compounds, it is preferable to use crude MDI because it is easy to handle, fast in reaction, excellent in physical properties of the resulting RPUF, and low in cost.

  As the active hydrogen group-containing compound which is the main component of the polyol component, a compound generally known as a polyol compound can be used. In particular, aliphatic polyols, aromatic polyols, amine polyols and the like exemplified below are known as polyols for rigid polyurethane foams.

  The aliphatic polyol is a polyfunctional active hydrogen compound, that is, an aliphatic or alicyclic polyfunctional active hydrogen compound as a polyol initiator, an alkylene oxide, specifically, propylene oxide (PO), ethylene oxide (EO), styrene. Examples thereof include polyfunctional oligomers obtained by ring-opening addition polymerization of one or more cyclic ethers such as oxide (SO) and tetrahydrofuran.

  Examples of the polyol initiator include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and neopentyl glycol, and triols such as trimethylolpropane and glycerin. And tetrafunctional alcohols such as pentaerythritol, polyhydric alcohols such as sorbitol and sucrose, and water.

  A polyol compound obtained by ring-opening polymerization of lactones such as ε-caprolactone together with alkylene oxide or together with alkylene oxide can also be used.

  Amine-based polyols include, as a polyol initiator, at least one kind of primary or secondary amine such as alkylene oxide, specifically propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran, or the like. It is a polyfunctional polyol compound obtained by ring-opening addition polymerization.

  Examples of the initiator include amines such as ethylenediamine, toluenediamine, and diphenylmethanediamine, and alkanolamines such as monoethanolamine and diethanolamine.

  Examples of the aromatic polyol include a method of adding the above-mentioned alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, an ester of an aromatic polycarboxylic acid and a polyhydric alcohol, and the like.

  Specific examples of the polyol compound obtained by adding the above-described alkylene oxide to a polyfunctional active hydrogen compound include compounds obtained by ring-opening addition of at least one of PO, EO, and SO to hydroquinone, bisphenol A, and the like. The

  Specific examples of esters of aromatic polycarboxylic acids and polyhydric alcohols include ester polyols having a hydroxyl group terminal between terephthalic acid, phthalic acid, isophthalic acid, and the like, and ethylene glycol, diethylene glycol, and the like.

  The polyol compound preferably has a hydroxyl value of 200 to 600 mgKOH / g and an average functional group number of 2 to 6.

  The above polyol compounds may be used alone, or two or more of them may be used in combination to form RPUF having more preferable characteristics.

  In the production of the rigid polyurethane foam, catalysts, flame retardants, foaming agents, colorants, antioxidants and the like well known to those skilled in the art can be used.

  As a blowing agent, a fluorocarbon compound having a small ozone layer depletion coefficient, for example, a fluorine-containing compound such as HFC-134a, HFC-245fa, and HFC-365mfc, an aliphatic or alicyclic hydrocarbon such as cyclopentane and n-pentane, and the like Water can be used. In particular, the use of HFC-245fa and HFC-365mfc is preferable because of its excellent low-temperature heat insulation performance.

  Catalysts include metals such as triethylenediamine, N-methylmorpholine, N, N, N ′, N′-hexamethylethylenediamine, tertiary amines such as DBU, dibutyltin dilaurate, dibutyltin diacetate, and tin octylate. A system catalyst is illustrated as a urethanization reaction catalyst. In addition, when water is used as one component of the blowing agent, the organotin catalyst is hydrolyzed and deteriorated, and therefore a tertiary amine catalyst is preferably used.

  The use of a catalyst that forms an isocyanurate bond that contributes to improvement in flame retardancy in the structure of the polyurethane molecule is also preferred, and examples thereof include potassium acetate and potassium octylate. Some of the above-mentioned tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes isocyanurate bond formation and a catalyst that promotes urethane bond formation may be used in combination.

  Furthermore, a flame retardant may be added, and examples of suitable flame retardants include metal compounds such as halogen-containing compounds, organic phosphate esters, antimony trioxide, and aluminum hydroxide.

  These flame retardants may deteriorate the physical properties of the rigid polyurethane foam obtained when, for example, an excessive amount of organophosphate is added, and foam foaming behavior when an excessive amount of metal compound powder such as antimony trioxide is added. Therefore, the amount of addition is preferably limited to a range that does not cause such a problem.

  A plasticizer may be used as necessary. Such a plasticizer is also preferably one that contributes to flame retardancy. Halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like can be used. β-chloroethyl) phosphate (TCEP, manufactured by Daihachi Chemical), tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethylmethylphosphonate, etc. can be exemplified. One or more of these can be used. The addition amount of the plasticizer is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyol component. If this range is exceeded, problems such as insufficient plasticizing effect and a decrease in physical properties of the foam may occur.

  As the stock solution for forming the rigid polyurethane foam, a commercially available stock solution using a component selected from the above-described components can be used. Specifically, Soflan R115-90F, Soflan R115-90H, etc. (Toyo Tire & Rubber) Kogyo Co., Ltd.) and the like are exemplified.

The glass fiber material used to reinforce the RPUF is preferably a glass fiber having a large aspect ratio. As a suitable material, a glass long fiber mat-like product, specifically, a chop strand mat, a continuous strand mat, etc. Is exemplified. It is preferable to use a continuous strand mat because it is excellent in impregnation property of RPUF foaming stock solution and reinforcing property of foam.
[Another embodiment]
(1) As the face material used in the present invention, various flexible face materials, high-rigid face materials and the like can be used. Specific examples of the highly rigid breathable plate-like face material include gypsum board, woody plywood, and calcium silicate board. Examples of the flexible face material include flexible face materials such as paper face materials, resin-laminated paper face materials, aluminum sheets, steel plates, resin films, etc., which can be used without limitation, but the physical strength of the sheet itself is good. It is equipped with an aluminum sheet, glass cloth, and resin coating layer for reasons such as that it does not corrode even when condensed water is generated when used in highly heat-insulating applications, and has good reaction adhesive strength with rigid polyurethane foam. The use of composite materials is preferred. Since such an aluminum sheet composite face material does not have any organic compound permeability, the glass fiber reinforced rigid polyurethane foam obtained by using the aluminum sheet composite face material is particularly suitable as a heat insulating material for an LNG storage tank.

When a releasable face material such as release paper or release film is used, the skin surface of the glass fiber reinforced polyurethane foam formed by peeling and removing the releasable face material is adhered to another rigid polyurethane foam. Is possible.
(2) In the said embodiment, although the example which makes the glass fiber mat 6 3 layers was shown, the number of layers is not limited to this, It can change suitably according to a use, a specification, etc.
(3) In the above embodiment, the example in which the head 3 of the foaming machine is movable back and forth toward the upper surface material supply side is shown. You may be comprised so that relative movement is possible. Moreover, both the head 3 and the ironing roller 22 of these foaming machines may be movable.

Schematic overall configuration diagram of a manufacturing apparatus for glass fiber reinforced rigid polyurethane foam according to the present invention The principal part expansion perspective view of the manufacturing apparatus of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pressing means 2 Rotation drive means 3 Stock solution supply means 6 Glass fiber mat 11L Lower surface material 11U Upper surface material

Claims (4)

A glass fiber mat supplying step of supplying a glass fiber mat onto the lower surface material supplied from the lower surface material supply device, a stock solution supplying step of supplying a rigid polyurethane foam foaming stock solution composition onto the supplied glass fiber mat, and An upper surface material supply step of continuously supplying the upper surface material from the upper surface material supply device to the upper surface supplied with the stock solution,
The glass fiber is fed to the downstream side while pressing the glass fiber mat supplied onto the lower surface material by a pressing means disposed between the glass fiber mat supply step and the stock solution supply step. Method for producing reinforced rigid polyurethane foam. The method for producing a glass fiber reinforced rigid polyurethane foam according to claim 1, wherein the sheet is fed downstream while pressing the glass fiber mat on the lower surface material by a rotation driving means for rotating the pressing means. The stock solution supplying means for supplying the rigid polyurethane foam foam stock solution composition in the stock solution supplying step and the supply position of the top material supplied from the top material supply device are capable of relative movement. Manufacturing method of glass fiber reinforced rigid polyurethane foam. A lower surface material supply device for supplying a lower surface material, a glass fiber mat supply device for supplying a glass fiber mat onto the lower surface material supplied from the lower surface material supply device, and a rigid polyurethane foam foam concentrate solution composition on the glass fiber mat A glass fiber reinforced hard polyurethane comprising: a stock solution supplying means for supplying a top surface material supply device for continuously supplying a top surface material to the top surface of the hard polyurethane foam foam stock solution composition supplied by the stock solution supplying means. In foam manufacturing equipment,
A presser is disposed between the glass fiber mat supply device and the undiluted solution supply means, and the glass fiber mat supplied onto the lower surface material is pressed and fed downstream. Equipment for manufacturing fiber reinforced rigid polyurethane foam.

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