JPH1052901A - Manufacture of synthetic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the surface unevenness of a laminate smaller by a method wherein glass fiber layers adhered with liquid isocyanate, hot melt films and surfacing materials are laminated on both the sides of a rigid polyurethane foam having open cells in the order named and then pressed with heated molds. SOLUTION: On the top surface of a rigid polyurethane foam 11 having open cells, a predetermined amount of glass fiber chops 22A are sprayed so as to provide a glass fiber layer 22. Then, polymeric MDI 34 and its solvent solution 39 are sprayed onto the layer 22. After that, onto the glass fiber layer 22, a hot melt film 36 is laminated. Then, a surfacing material 32 is laminated onto the film 36. Next, a laminated matter, in which the above-mentioned respective members are laminated top one another, is fed with a conveyor 50 to the position of a cutter 53 so as to be cut to a predetermined length. The cut laminate 10A is arranged between a mold 57 consisting of a bottom mold 55 and a to mold 56 so as to be hot-pressed, resulting in shaping the laminate 10A into the shapes of molding surfaces and, at the same time, the polymeric MDIs 33 and 34 harden so as to fix the shape of the laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a synthetic resin laminate.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a synthetic resin laminate used for an automobile interior material such as an automobile ceiling material and a door trim or other products, a soft or semi-rigid material such as urethane impregnated with a thermosetting adhesive has been used. On both sides of the foam, a glass fiber layer and a surface material (one constitutes the front side surface and the other side constitutes the back side surface) are laminated, and pressed into a desired shape with a heating mold, thereby reacting and curing. 2. Description of the Related Art There is known a method of performing bonding and shaping of each member to obtain a synthetic resin laminate.

However, in the method for producing a synthetic resin laminate, since a soft or semi-rigid foam is used and reaction-cured in a mold, strict condition control is required at the time of production. In addition, since continuous production is performed, there are many points that are troublesome for switching and the like, and the equipment is also dedicated, thus lacking versatility. Therefore, there were many restrictions on production.

In recent years, a two-component (two components of a polyol component and an isocyanate component) polyurethane adhesive has been sprayed on both sides of a one-layer rigid polyurethane foam made of open cells, a glass fiber layer, a hot melt film, and the like. A method has been proposed in which the two-component polyurethane adhesive is reactively hardened by laminating a surface material and pressing with a heating mold, thereby bonding and fixing each member. In this method, as a rigid polyurethane,
The branch density is about 1.8 to 2.1, and the glass transition point is 130.
A low temperature of about 150 ° C. is used. Further, the hard polyurethane having a low branch density and a low glass transition point is obtained by converting a polyol as one of the molding materials into a polyurethane having a hydroxyl value of 1 or less.
It is obtained by setting it as low as about 60 to 180. According to this method, since a rigid foam is used, the resulting synthetic resin laminate has excellent shape fixability and rigidity, and is suitable as a ceiling material in automobiles and the like.

[0005]

However, in the production method using the open-celled rigid foam, there are the following problems since a two-pack adhesive composed of a polyol component and an isocyanate component is used. .

First, as a first problem, when two liquids (two components) are mixed by an adhesive applicator and sprayed on a glass fiber layer, the mixed liquid scatters around and then hardens.
There is a problem that the maintenance and maintenance of the work place becomes troublesome.

As a second problem, the polyol component and the isocyanate component have a large difference in viscosity.
The discharge ratio of both components tends to fluctuate, and heating and temperature control are required to keep the ratio constant. This makes the structure and maintenance of the adhesive applicator complicated and increases the price of the adhesive coater. In addition, a gun for two-liquid spray application requires a structure that can withstand high discharge pressure in addition to a piping for two-liquid supply, a two-liquid mixing / stirring device, and a cleaning device. The weight is too heavy, and the application work is burdensome, and there is a problem that the tire is easily fatigued.

A third problem is that the two-component polyurethane adhesive is expensive. In particular, there is an extremely strong desire to lower the price of synthetic resin laminates used in fields where price competition is severe.

[0009] In addition, as a fourth problem, small irregularities are likely to be generated on the product surface.
There was a problem that the appearance was impaired. The present inventors have also conducted intensive studies on this point, and found that the hard polyurethane has a cause. That is, conventionally,
In order to prevent cracking even when pressing into complex shapes,
Although a rigid polyurethane having a low branch density and a low glass transition point was used as the rigid polyurethane, the rigid polyurethane having a low branch density and a low glass transition point is soft and brittle as compared with a normal rigid polyurethane, so it is press-molded. In that case, irregularities are likely to occur.

Therefore, the present invention is to provide a method for manufacturing a synthetic resin laminate having sufficient shape fixability and rigidity with good working environment, easily and inexpensively, and with less surface irregularities. Is what you do.

[0011]

That is, the present invention provides:
On both sides of the rigid polyurethane foam composed of open cells, a glass fiber layer, a hot melt film and a surface material to which liquid isocyanate is adhered are laminated and pressed into a desired shape by a heating mold, thereby bonding and forming the respective members. The present invention relates to a method for producing a synthetic resin laminate, wherein a fixed synthetic resin laminate is obtained.

The rigid polyurethane foam is not particularly limited, and any known rigid polyurethane foam having open cells can be used, and those having a density according to the use of the synthetic resin laminate can be selected. The closed cell rate of the rigid polyurethane foam is preferably 10% or less because the thermoformability and the permeability of liquid isocyanate are improved and the adhesiveness is excellent. On the other hand, when the closed cell rate is 40% or more, the flatness of the flat surface is poor such that the air bubbles are hardly swelled or crushed due to a rise in temperature during thermoforming, so that they do not follow. In particular, in addition to the two layers of the product front side foam layer and the product back side foam layer, the branch density and the glass transition point of the product front side foam layer are made higher than the product back side foam layer, and the surface foam layer is formed. Is preferably close to the substantial thermoforming temperature. Further, it is preferable that the product front side foam layer is formed of a polyether polyol having a higher hydroxyl value than the product back side foam layer, or that the product front side foam layer is thinner than the product back side foam layer. The synthetic resin laminate using the rigid polyurethane foam having such a configuration has an extremely good appearance by suppressing the occurrence of small irregularities that may be formed on the surface.

The liquid isocyanate is generally used as an adhesive, and any liquid isocyanate can be used without any particular limitation. For example, aromatic TDI
(Toluene diisocyanate), polymeric MDI
(4,4'diphenylmethane diisocyanate), ND
I (1,5-naphthalenediisocyanate), TODI
(Tolidine diisocyanate), PPDI (paraphenylene diisocyanate), XDI (xylylene diisocyanate), TMXDI (tetramethyl xylene diisocyanate) and modified products thereof.
Preferably, polymeric MDI, or TDI, M
The use of modified forms of DI and mixtures thereof is suitable.

These modified products are subjected to various modifications to a single isocyanate in order to reduce the vapor pressure, change the viscosity, the number of functional groups, the reactivity, and impart other adhesive properties and operability. That is, various types of modified TDI, modified MDI, and the like, which are referred to as prepolymers, such as urethane-modified, allophanate-modified, buret-modified, or carbimide / uretonimine-modified.

Of these, more preferred is 3
It is a liquid isocyanate of up to 300 cp and is excellent in spray applicability, permeability and the like. Conversely, those having a viscosity higher than 1000 cp are inferior in reactivity and workability. In particular, among these, polymeric MDI and carbodiimide-modified MDI have low vapor pressure and good affinity with glass fiber,
Suitable for reactivity / adhesion and workability because it wets glass fiber well. The type of the liquid isocyanate is appropriately selected and used depending on the adhesiveness, rigidity, reactivity, workability, and the like of the laminate. In addition, polymeric MDI is also called crude MDI or crude MDI.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the accompanying drawings. FIG. 1 is a partial cross-sectional view showing an example of a synthetic resin laminate product obtained by carrying out the present invention, FIG. 2 is a diagram showing an outline of equipment for one embodiment of a production method of the present invention, and FIG. FIG. 4 is a partial cross-sectional view of a synthetic resin laminate obtained according to an example, and FIG. 4 is a cross-sectional view illustrating a production example of a rigid polyurethane foam used for the synthetic resin laminate.

A laminated synthetic resin product 10 shown in FIG. 1 is used for an automobile ceiling material. Glass fiber layers 21 and 22 and surface materials 31 and 32 are laminated on both surfaces of a rigid polyurethane foam 11 composed of open cells. It is adhered and shaped into a predetermined shape. The rigid polyurethane foam 11 is bonded to the glass fiber layers 21 and 22 by bonding the glass fiber layers 21 and 22 with each other.
22 by curing the polymeric MDIs 33, 34 attached to the glass fiber layers 21, 22 and the surface material 3.
Bonding with glass fiber layers 21 and 22 and surface material 3
Hot melt film 35, 3 provided between 1, 32
6 is made by welding.

The rigid polyurethane foam 11 composed of the open cells constitutes the base material of the synthetic resin laminate 10 and may be a known one. In this example, a rigid polyurethane foam was obtained using a polyether-based polyol having a hydroxyl value of 172 mgKOH / g. The foam has a physical property value of a polyether-based material having a density of 25 to 38 kg / m ³ , a branch density of 2.0, and a glass transition point of 145 ° C. Further, the thickness of the rigid polyurethane foam 11 composed of the open cells is determined to be appropriate according to the use of the synthetic resin laminate 10.

The glass fiber layers 21 and 22 are used to increase the rigidity of the synthetic resin laminate 10 and are formed by stacking glass fiber chops (cut long glass fibers) into layers. Made of glass fiber mat. The weight of the glass fiber layers 21 and 22 is appropriately determined according to the rigidity required for the synthetic resin laminate 10 and the like.

The polymeric MDIs 33, 34 are solidified by the reaction with water in the presence of heat and a catalyst, and are cured to bond the open-celled rigid polyurethane foam 11 and the glass fiber layers 21, 22 to each other. Also,
The polymeric MDIs 33 and 34 also have the function of fixing the shape of the synthetic resin laminate 10 by the curing. The viscosity of the polymeric MDIs 33 and 34 is 200
cp / 25 ° C., and can be easily attached to the glass fiber layers 21 and 22 by spraying or the like when the synthetic resin laminate 10 is manufactured.

The hot melt films 35 and 36 are melted by heating to exhibit adhesiveness, and are made of EVA (ethylene vinyl acetate copolymer), EAA (ethyl acryl acetate), PE (polyethylene), PP (polypropylene). Known materials such as a polyolefin-based hot melt film and a polyamide-based hot melt film are used. The surface materials 31 and 32 are made of the synthetic resin laminate 10.
Is provided for internal protection and decorativeness, etc., one 31 constitutes the back surface of the synthetic resin laminate and the other 32 constitutes the front surface. The material of the surface materials 31 and 32 is appropriately selected from a single material such as a nonwoven fabric, a knit fabric, or a PVC leather sheet, or a material in which a knit fabric or a PVC leather sheet is laminated on a foam. Of course, it is not necessary to form both surface members 31 and 32 from the same material.

Next, an example of manufacturing the synthetic resin laminate 10 by the manufacturing method of the present invention will be described. In addition,
In the following example, an example in which each member is continuously laminated using a conveyor is described. However, in the present invention, members cut in advance to predetermined dimensions may be sequentially laminated without using a conveyor.

First, in this example, as shown in FIG. 2, the surface material 31 serving as the back surface of the synthetic resin laminated product and the hot melt film 35 disposed on the upper surface thereof are stacked by a conveyor 50 in a stacked state. Supply continuously in one direction. Then, a glass fiber chop 21A cut to a predetermined size is sprayed on the hot melt film 35 at a predetermined position on the conveyor 50 and is deposited to a predetermined weight to form the glass fiber layer 21. A glass fiber mat may be laminated on the hot melt film 35 instead of the glass fiber chop 21A.

Next, polymeric MDI 33 is sprayed on the glass fiber layer 21. Furthermore, in this example, in order to accelerate the reaction curing of polymeric MDI,
The catalyst solution 38 is sprayed on the glass fiber layer 21. The catalyst solution 38 of this example is dimethylethanolamine /
60 g of a 5% aqueous solution of triethylenediamine = 6/10
/ M ² . The catalyst solution to be sprayed here is
A 4% aqueous solution of dimethylethanolamine alone may be used.
Polymeric M sprayed on the glass fiber layer 21
The DI 33 and the catalyst solution 38 adhere to the surface and inside of the glass fiber layer 21 and are held by the glass fiber layer 21.

Since the above-mentioned polymeric MDI is composed of one liquid, it is not necessary to adjust the viscosity of each liquid as compared with a two-part polyurethane adhesive, and the structure of the coating machine used is simplified. Therefore, maintenance of the apparatus is easy, and equipment costs are low. Furthermore, since polymeric MDI initiates a curing reaction by heating with catalyst water, even if it scatters around, it hardly cures as it is, and there is little risk of impairing the working environment. In addition, Polymeric MD
I is cheaper than a two-component polyurethane adhesive, and such a synthetic resin laminate can be manufactured at low cost.

Thereafter, a rigid polyurethane foam 11 having a plate-like shape and having open cells cut into a predetermined size is supplied from the side of the conveyor 50 to the upper surface of the glass fiber layer 21 and laminated. The size of the open-celled rigid polyurethane foam 11 is as follows:
The size depends on the size of the target synthetic resin laminate. The foam 11 of this embodiment is a polyether-based foam having a density of 25 to 38 kg / m ³ and a thickness of about 7 mm.

The open-celled rigid polyurethane foam 1
First, a predetermined amount of a glass fiber chop 22A is sprayed on the upper surface of 1 to provide a glass fiber layer 22. The glass fiber chops 22A to be sprayed here may be of the same type, size and amount as the glass fiber chops 21A previously sprayed, or may be different. Of course, a glass fiber mat may be used.

Next, the glass fiber layer 22 is sprayed with a polymeric MDI 34 and a catalyst solution 39 thereof. The catalyst solution 39 is the same as the catalyst solution 38 described above,
The spray amount of the polymeric MDI 34 and the catalyst solution 39 is determined as appropriate. Here, the sprayed polymeric MDI 34 and catalyst solution 39 are permeated and held in the surface of the glass fiber layer 22 and in the glass fiber layer 22.

Thereafter, a hot melt film 36 is laminated on the glass fiber layer 22, and the surface material 3 is further placed thereon.
2 are laminated. The hot melt film 36 and the surface material 32 may be the same as or different from the previously used hot melt film 35 or the surface material 31, respectively.
They are appropriately selected according to the physical properties required for the intended synthetic resin laminate, the intended use, and the like.

Then, a laminate in which the above members are laminated is
The sheet is fed to the position of a cutting tool such as a cutter 53 by the conveyer 50, and cut into a predetermined size there. At this time, in this embodiment, since the rigid foam 11 of the open cells has a predetermined size in advance, other members, that is, the surface materials 31, 32, etc., are cut at positions that are ends of the rigid foam 11. .

Thereafter, the cut laminate 10A is
It is arranged between a heating mold 57 composed of a lower mold 55 and an upper mold 56 and is heated and pressed. The lower mold 55 and the upper mold 56 have a mold surface (inner surface) shape adapted to the outer surface of the synthetic resin laminate, and a heater and a heat medium pipe are disposed inside. It can be heated to a predetermined temperature.
In this example, the mold surface temperature is 130 ° C. and the pressing pressure is 2.5 k
g / cm ² , and the press time is 30 to 45 seconds.

By this press, the laminate 10A is shaped into a mold surface shape, and the polymeric MDIs 33, 34 adhered and held on the glass fiber layers 21, 22 are hard foamed with the glass fiber layers 21, 22 and open cells. And the glass fiber layers 21 and 22 and the open-celled rigid polyurethane foam 1 by the heat of the mold surface.
The curing reaction is started between 1 and within the glass fiber layers 21 and 22. The polymeric MDIs 33 and 34 are quickly cured by the presence of the catalyst solution attached to the glass fiber layers 21 and 22 to bond the glass fiber layers 21 and 22 to the rigid polyurethane foam 11 and to form them. Perform fixing.

The hot melt films 35 and 36 between the glass fiber layers 21 and 22 and the surface materials 31 and 32 are melted by the heat of the mold surface during the pressing, and the glass fiber layers 2 and 22 are melted.
1 and 22 and the surface materials 31 and 32 are adhered.

Thereafter, the laminated product 10B having been bonded and fixed in shape is pressed by a trimming mold 58, and the laminated product 1B is pressed.
Unnecessary portions around the periphery of 0B are cut off to obtain a desired synthetic resin laminate shown in FIG. Table 1 shows the materials and the like of Examples 1 to 6 in which the synthetic resin laminate was manufactured by changing the material and amount of the members used in the manufacturing method of the above-mentioned Example. In addition, Table 2 shows the physical property values for the above examples. The physical properties of the obtained synthetic resin laminate were sufficiently resistant to use as ceiling materials in automobiles.

[0035]

[Table 1]

[0036]

[Table 2]

Further, as described above, the rigid polyurethane foam has a two-layer structure composed of a product front-side foam layer and a product back-side foam layer, and has a branch density and a glass transition point of the product front-side foam layer. Higher than the foam layer on the back of the product not only improves the rigidity and brittleness of the synthetic resin laminate, but also is extremely effective in preventing the occurrence of fine irregularities that may be formed on the product surface. is there. FIG. 3 shows an example. Reference numeral 40 in the figure denotes a synthetic resin laminate,
49 is a surface material, 42 and 48 are hot melt films, 4
3, 47 are glass fiber layers, 44, 46 are polymeric M
DI and 45 are rigid polyurethane foams, and a product front side foam layer 45A and a product back side foam layer 45B are laminated via a hot melt film 45C. In this synthetic resin laminate, each layer is laminated and adhered as shown in the figure, and shaped into a predetermined shape.

There are various methods for increasing the branch density and the glass transition point of the product front-side foam layer 45A as compared with the product back-side foam layer 45B, but the product front-side foam layer 45A is replaced with the product back-side foam layer 45B. It is simple and reliable to form with a polyether polyol having a higher hydroxyl value. The hydroxyl value referred to here is an alkali required to neutralize acetic acid bound to an acetylated product obtained from 1 g of a sample, which is represented by the amount of potassium hydroxide.
It is considered that as this value increases, the reaction activity increases and the rigidity of the foam increases. Assuming that the hydroxyl value of the foam layer on the back side of the product is 160 to 230 mgKOH / g, the hydroxyl value of the foam layer on the front side of the product is 230 to 300 mgKOH / g.
About mgKOH / g is preferable. At this time, by making the product front-side foam layer 45A thinner than the product back-side foam layer 45B, it is possible to make it difficult to generate irregularities on the product surface without impairing the rigidity of the synthetic resin laminate. In this example, the thickness of the product front side foam layer 45A was 2 mm, and the thickness of the product back side foam layer 45B was 4 to 5 mm.

FIG. 4 shows an example of a method for producing a rigid polyurethane foam having two layers. In the figure, reference numeral 60 denotes a conveyor, 61 denotes a laminating machine, 62 denotes a heater thereof, and a product front side foam layer 45A is laminated via a hot melt film 45C to a product back side foam layer 45B moving on the conveyor 60. Then, the laminator machine 61 appropriately adjusted to the temperature.
By melting the hot melt film 45C in the inside, the product front side foam layer 45A and the product back side foam 45
B is integrally bonded. In this example, the conveyor speed was 2.0 m / min, the heater temperature was 180 ° C. to 200 ° C., and the rigid polyurethane foam was compressed to about 70 to 90% of its thickness by the laminator 61. The method of bonding the foam on the front side of the product and the foam on the back side of the product is not limited to the method using a hot-melt film shown in the drawings, and a polymer MDI is applied, and the applied surface is sprayed with water or the like to react. There is also a method in which both foams are joined by curing or spraying a polyethylene powder on the surface of one foam, and overlaying the other foam via a hot melt film thereon and heating.

Table 3 shows the hydroxyl group, thickness, branch density, glass transition point, and flyability of each layer of Production Examples 1 to 3 in which rigid polyurethane foam layers were produced by changing the hydroxyl value and thickness of the two layers. It is. The method of measuring flyability is as follows. 25.4mm
Twelve cubic rigid polyurethane foams were placed in a cube (19
7mm cube) shaped wooden box with 19.05mm cube 2
Put together with 4 pieces and put the wooden box at a speed of 60 revolutions per minute for 600
After spinning, the weight percent of powdered foam relative to the total weight of the foam before testing is determined. (ASTM C-42
1-61)

[0041]

[Table 3]

Next, a glass fiber and a surface material are laminated on the obtained rigid polyurethane foam to obtain a synthetic resin laminate (Examples 7 to 9). Table 4 shows the configuration of each layer. In the table, one of the surface materials 49 is shown as a back surface material constituting the product back surface. Further, also in this synthetic resin laminate, each layer can be continuously laminated by the conveyor as shown in FIG. 2 and described, and is formed into a predetermined shape by an appropriate press device.

[0043]

[Table 4]

The synthetic resin laminate was thermoformed into a ceiling material, and its physical properties and appearance were examined. Table 5 shows the results. Note that the methods for measuring the physical properties and the like are the same as the examples shown in Table 2. The unevenness of the product appearance
Observation by visual inspection, Shiatsu buckling, press the surface of the laminate with a finger to observe whether a dent that does not return to the shape occurred,
Further, for the curved surface sagging, it is visually observed whether or not there is a portion where fine irregularities on the product surface are not clearly formed with high accuracy. As shown in the table, the synthetic resin laminate obtained by the production method of the present invention had physical properties and appearance satisfying as automotive ceiling materials.

[0045]

[Table 5]

In order to further clarify the effects of the present invention, the following comparative examples were carried out. [Comparative Example 1] In Production Example 1, the product backside foam layer had a hydroxyl value of 283 mgKOH / g and a branch density of 2.8 mmol.
/ G and a glass transition point of 182 ° C., except that the rigid polyurethane foam was formed in the same manner as in Production Example 1. Using the obtained foam, a synthetic resin laminate was formed in the same manner as in Example 7, and the appearance was observed. As a result, no irregularities and buckling were observed, but cracks were formed on the product curved surface sag and fine product curved surface. Had occurred.

Comparative Example 2 In Production Example 1, the product foam layer had a hydroxyl value of 183 mg KOH / g, a branch density of 1.9 mmol / g, a glass transition point of 137 ° C., and the product foam layer had a hydroxyl value of 283 mg KOH. / G, a branch density of 2.8 mmol / g, and a glass transition point of 182 ° C., except that a rigid polyurethane foam was formed in the same manner as in Production Example 1. Using the obtained foam, Example 7
A synthetic resin laminate was formed in the same manner as described above, and the appearance of the laminate was observed. As a result, irregularities, curved surface sagging, and fine cracks in the curved surface of the product were found to occur slightly on the product surface. He also buckled with his finger.

Comparative Example 3 The same procedure as in Production Example 1 was carried out except that the foam layer on the surface side of the product in Production Example 1 was replaced with one having a hydroxyl value of 183 mg KOH / g, a branch density of 1.9 mmol / g, and a glass transition point of 137 ° C. To form a rigid polyurethane foam. Using the obtained foam, a synthetic resin laminate was formed in the same manner as in Example 7, and the appearance of the laminate was observed. Buckled.

[0049]

As shown and described above, in the method for producing a synthetic resin laminate according to the present invention, liquid isocyanate is used as an adhesive between the open-celled rigid foam and the glass fiber. This has the effect of minimizing deterioration.

Further, since the adhesive used in the present invention is a liquid isocyanate and a catalyst solution (aqueous), both of them have low viscosity of liquid and excellent spray workability and excellent permeability to material members. Also reacts easily. In addition, since the reaction cured product is a urea bond, it is cross-linked in the molecule and has higher rigidity. In particular, in the case of polymeric MDI or carbodiimide-modified MDI, the affinity with glass fibers is very strong, and it easily penetrates into fine gaps between glass fibers only by spray application, so that adhesiveness and rigidity are further improved. A laminate is obtained.

On the other hand, the two-component polyurethane adhesive has a high viscosity, and the air
Due to the progress of the reaction hardening of the liquid, the reaction liquid (adhesive) cannot enter the small gap between the glass fibers. Therefore, in the conventional two-component polyurethane adhesive, the reaction liquid (adhesive) does not penetrate into small gaps between the glass fibers, and the rigidity as expected cannot be obtained. High rigidity can be obtained. The reason that such sufficient rigidity can be obtained is not only that the method of applying the adhesive is changed, but also that the reaction liquid (adhesive) can penetrate into minute gaps between glass fibers. Because he came up with

Further, according to the present invention, a coating machine used for spraying or coating a liquid isocyanate has a simple structure as compared with a coating machine for a two-component polyurethane adhesive. There is an advantage that maintenance is easy and equipment costs are low. Further, since the present invention produces a synthetic resin laminate using an open-celled rigid polyurethane foam, the rigid polyurethane foam has an advantage that a synthetic resin laminate having high rigidity and shape retention can be obtained. This is a manufacturing method suitable for interior materials such as ceiling materials.

In addition, the rigid polyurethane foam is made into two layers, a product front side foam layer and a product back side foam layer,
If the product front side foam layer is formed from a polyether polyol having a higher hydroxyl value than the product back side foam layer and the branch density and glass transition point of the product front side foam layer are higher than the product back side foam layer, the product Not only can the surface rigidity be further enhanced, but also the product shape can be sharply expressed without unevenness or curved surface sagging on the surface, and the appearance becomes extremely good.

Although the reason is not clear, as the branch density increases, the hardness of the foam increases, the brittleness is improved, and the pock disappears. Also, by increasing the glass transition point,
It is considered that since the temperature approaches the substantial thermoforming temperature, the heat deformability is improved, the ability to follow irregularities is increased, the effect of curved surface sagging is reduced, and the effect of improving thermoformability is exhibited.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing an example of a synthetic resin laminate obtained by carrying out the present invention.

FIG. 2 is a diagram showing an outline of equipment for one embodiment of the manufacturing method of the present invention.

FIG. 3 is a partial sectional view of a synthetic resin laminate obtained according to another example of the present invention.

FIG. 4 is a cross-sectional view showing a production example of a rigid polyurethane foam used for the synthetic resin laminate.

[Explanation of symbols]

10,40 Synthetic resin laminate 11,45 Open cell hard polyurethane foam 21,22,43,47 Glass fiber layer 31,32,41,49 Surface material 33,34,44,46 Polymeric MDI 35,36,42 , 45C, 48 Hot melt film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B32B 31/20 9349-4F B32B 31/20 // B29K 105: 04

Claims (4)

[Claims] 1. A hard polyurethane foam composed of open cells, a glass fiber layer to which liquid isocyanate is adhered, a hot melt film and a surface material laminated on both surfaces, and pressed into a desired shape by a heating mold to obtain each of the above. A method for producing a synthetic resin laminate, comprising obtaining a synthetic resin laminate in which members are adhered and the shape is fixed. 2. The product according to claim 1, wherein the rigid polyurethane foam comprises two layers, a product front side foam layer and a product back side foam layer, and a branch density and a glass transition point of the product front side foam layer are determined on the product back side foam layer. A method for manufacturing a synthetic resin laminate, wherein the height is higher than a body layer. 3. The method for producing a synthetic resin laminate according to claim 2, wherein the product front side foam layer is formed from a polyether polyol having a higher hydroxyl value than the product back side foam layer. 4. The method for producing a synthetic resin laminate according to claim 2, wherein the product front side foam layer is thinner than the product back side foam layer.