JPH11157039A - Manufacture of sheet laminate and production equipment therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method of manufacturing a highly rigid thermoplastic resin sheet laminate, in which a plurality of the thermoplastic resin sheets are made into an integral body without so much lowering the mechanical strength of the thermoplastic resin sheet and ply separation is hard to develop. SOLUTION: In order to obtain a sheet laminate 6A through the bundling of a plurality of thermoplastic resin sheets 6 onto a laminated matter and their integration, the resin sheets are immersed before their bundling in a liquid composition 2a, which has an affinity for the thermoplastic resin and includes a compound having a polymerizable unsaturated bond, a liquid composition 2a, which has an affinity for the thermoplastic resin and includes a compound having a volatility, a liquid composition 2a, which has an affinity for the thermoplastic resin and includes multifunctional active hydrogen compound and polyisocyanate, a liquid, which includes a compound having a polymerizable unsaturated bond and turns to be self-bonding properties after polymerization, or a liquid composition 2a, which includes a compound having a polymerizable unsaturated bond and a self-adhesive polymeric matter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for manufacturing a rigid sheet laminate which can be suitably used for structural materials such as civil engineering materials, for example. The present invention relates to a method and apparatus for manufacturing a sheet laminate capable of increasing the bonding strength between thermoplastic resin sheets and the rigidity of the sheet laminate by immersing a thermoplastic resin sheet in a specific liquid composition or the like and then integrating the same in a die. .

[0002]

2. Description of the Related Art Steel materials have been mainly used for structural materials such as civil engineering materials because of their high mechanical strength. In recent years, in order to reduce the weight of this type of structural material, a composite material obtained by reinforcing a synthetic resin with glass fibers, so-called FRP, has been used. However, F
The structural material using RP has a problem that it is difficult to recycle it because it contains glass fiber.

[0003] On the other hand, it is known that, when a crystalline thermoplastic resin is highly stretched, the strength and rigidity in the stretching direction according to the orientation of molecules are remarkably improved. Although a normal high-magnification stretched resin is obtained in a fibrous form, a method for obtaining a sheet-like form has recently been proposed (eg, Japanese Patent Publication No. 3-67490).

[0004] Since the above-described high-magnification stretched resin has a high rigidity comparable to that of glass fiber, it is considered that if a plurality of high-magnification stretched resin sheets can be laminated in a good adhesion state, it can be sufficiently used as a structural material. .

[0005] However, the resin sheet surface in a highly stretched state has poor adhesion, and even when laminated, it is difficult for the resin sheets to adhere well. To solve such a problem, JP-A-9-174773 discloses a multilayer sheet obtained by laminating a crosslinkable polyolefin resin sheet and a non-crosslinkable polyolefin resin sheet. To obtain a polyolefin laminate sheet with increased mechanical strength by applying a fiber structure to the entire sheet by stretching and then performing a crosslinking treatment and applying heat treatment while applying tension at a temperature equal to or higher than the melting point of the polyolefin resin. Has been proposed.

However, in Japanese Patent Application Laid-Open No. 9-174773, it is considered that since the step of obtaining the reinforced polyolefin sheet includes a step of finally performing a heat treatment at a temperature higher than the melting point of the polyolefin resin, the molecular orientation is relaxed. However, there is a problem that a reduction in rigidity cannot be avoided.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method and an apparatus for manufacturing a sheet laminate made of a thermoplastic resin having high rigidity, which solves the above-mentioned disadvantages of the prior art.

[0008]

The invention according to claim 1 is a method of manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are integrated. Prior to supplying the plastic resin sheet to the die, the sheet is immersed in a liquid composition containing a compound having an affinity for the thermoplastic resin and having a polymerizable unsaturated bond.

The invention according to claim 2 is a method for manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are formed into a die. Prior to the supply, the resin is immersed in a volatile compound or a liquid composition containing the compound which has an affinity for the thermoplastic resin.

According to a third aspect of the present invention, there is provided a method for manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are bonded to a die. Prior to supply, the composition is immersed in a liquid composition containing one of a polyfunctional isocyanate and a polyfunctional isocyanate having an affinity for a thermoplastic resin, and then a liquid composition containing the other. Or a liquid compound containing the active hydrogen compound and polyisocyanate.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are formed in a die. Prior to the supply, it is characterized by being immersed in a liquid composition containing a compound having an affinity for a thermoplastic resin and having a polymerizable unsaturated bond and exhibiting tackiness after polymerization.

[0012] The invention according to claim 5 is a method for manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated and integrated by a die, and the plurality of thermoplastic resin sheets are laminated on a die. Prior to supply, a compound having an affinity for a thermoplastic resin and having a polymerizable unsaturated bond,
It is characterized by being immersed in a liquid composition containing an adhesive polymer.

The invention according to claim 6 is characterized in that a polyolefin sheet obtained by stretching a polyolefin is used as the thermoplastic resin sheet. The invention according to claim 7 is an apparatus for manufacturing a sheet laminate,
A supply unit that supplies a plurality of thermoplastic resin sheets, and a dipping tank that is disposed downstream of the thermoplastic resin sheet supply unit and stores a liquid composition in which the thermoplastic resin sheet is dipped, and A die for converging and integrating a plurality of thermoplastic resin sheets drawn out from the immersion tank, and a take-up unit for taking out the sheet laminate integrated by the die, the liquid composition comprising: a) a liquid composition containing a compound having an affinity for a thermoplastic resin and having a polymerizable unsaturated bond, and (b) a volatile compound having an affinity for the thermoplastic resin and containing the compound. A liquid composition, (c) a liquid composition having an affinity for a thermoplastic resin and containing a polyfunctional active hydrogen compound and a polyisocyanate, (d) containing a compound having a polymerizable unsaturated bond, and sticking after polymerization. Liquid Composition, characterized in that it is a one selected from (e) a compound having a polymerizable unsaturated bond, the group consisting of liquid composition containing a tacky polymer.

Hereinafter, the present invention will be described in detail. An outline of a method for manufacturing a sheet laminate according to the present invention (the inventions described in claims 1 to 6) will be described with reference to FIG.

FIG. 1 is a diagram showing a schematic configuration of an apparatus for manufacturing a sheet laminate according to the present invention. As is clear from FIG. 1, the apparatus for manufacturing a sheet laminate according to the present invention includes a supply unit 1, a dip tank 2, a forming unit 4 having a die 3, and a take-up unit 5 from upstream to downstream.

The supply section 1 supplies a plurality of thermoplastic resin sheets. In the structural example shown in FIG. 1, the supply section 1 has a plurality of reels 1a around which the thermoplastic resin sheets are wound.
The thermoplastic resin sheet 6 is fed out from each reel 1a. At the start of production, the thermoplastic resin sheet 6 is unwound from each reel 1a, pulled out toward the downstream side of the molding line shown in FIG.
The reel 1a is rotated by taking out each of the thermoplastic resin sheets 6, and the thermoplastic resin sheet 6 is continuously fed out.

The take-up section 5 is constituted by a take-up machine having an appropriate structure as long as it can take out a plurality of thermoplastic resin sheets 6 in an initial state and can take up the formed sheet laminate after the start of molding. can do.

In the structural example shown in FIG. 1, the take-up section 5 is constituted by a press-type take-up machine. That is, this take-up machine has an endless belt 5c stretched between the rollers 5a and 5b and an endless belt 5f stretched between the rollers 5d and 5e, and the rollers 5a, 5b, 5d and 5e.
, The sheet laminate is pressed and held between the endless belts 5c and 5f, and can be pulled in the direction of the arrow shown in the figure.

The immersion tank 2 is provided for immersing a plurality of thermoplastic resin sheets 6 fed from the supply section 1 in a liquid composition described below. That is, the immersion tank 2
Inside, a liquid composition 2a described later is stored, and guide rolls 2b and 2c for immersing the thermoplastic resin sheet 6 in the liquid composition 2a, at least the lower surface of which is immersed in the liquid composition 2a. It is arranged to be. By adjusting the distance between the guide rolls 2b and 2c, the time during which the thermoplastic resin sheet 6 is immersed in the liquid composition 2a can be adjusted.

A guide roll 7 and a deaeration roll 8 are arranged downstream of the immersion tank 2. The guide roll 7 and the deaeration roll 8 are configured to be rotatable, and are supplied to the forming section 4 via these rolls 7 and 8 in a state where a plurality of thermoplastic resin sheets 6 are stacked.

In the forming section 4, the die 3 is provided at the former stage, and the heating furnace 4a and the cooling furnace 4b are arranged at the latter stage. The die 3 is provided for converging and integrating a plurality of thermoplastic resin sheets 6 by applying pressure. In this case, it is not necessary to heat in the die 3, but in order to enhance the integration of the plurality of thermoplastic resin sheets 6, the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet is −50 ° C. or more, It is preferable to perform convergence and integration at a temperature within the range of the melting temperature or lower.

Although the structure of the die 3 is not particularly limited, for example, as shown in a cross-sectional view of FIG. 2, a recess for accommodating a structure in which a plurality of thermoplastic resin sheets 6 are laminated is formed. An upper and lower split die including a lower die 3a and an upper die 3b having a downwardly protruding portion that can enter the recess of the lower die 3a can be suitably used. In this case, by forming the clearance between the lower mold 3a and the upper mold 3b to be small on the downstream side, the die 3 is converged and integrated as the plurality of thermoplastic resin sheets 6 pass. It can be configured as follows.

Alternatively, a plurality of thermoplastic resin sheets 6 may be bundled and integrated by externally pressing the upper mold 3b and the lower mold 3a so that they are close to each other. As described above, a plurality of thermoplastic resin sheets 6 are bundled and integrated by passing through the die 3 to form a sheet laminate 6A. Here, the sheet laminate 6A may contain an uncured liquid composition described below. Therefore, a heating furnace 4a shown in FIG. 1 is disposed downstream of the die 3 to complete the curing.

However, if the die 3 itself is heated, the heating furnace 4a may be omitted. Furthermore, since the heating furnace 4a is used to complete the curing of the uncured liquid composition, when the liquid composition does not include the uncured processing liquid, the heating furnace 4a is It may be omitted.

As the heating furnace 4a, an appropriate heating furnace such as a normal hot-air heating furnace can be used. Also,
When the heating furnace 4a is used, as shown in FIG. 1, it is desirable to arrange a cooling furnace 4b at a subsequent stage to cool the sheet laminate 6A. Regarding the structure of the cooling furnace 4b, an appropriate structure such as a cool air blowing furnace can be used.

By heating or pressing the thermoplastic resin sheet to a temperature higher than the melting temperature, a plurality of thermoplastic resin sheets can be integrated by self-adhesion. However, like a stretched thermoplastic resin sheet,
When a thermoplastic resin sheet whose elastic modulus is significantly increased by molecular orientation is integrated, heating above the melting temperature of the resin will reduce the molecular orientation. Therefore, even if a sheet laminate is obtained, desired high rigidity cannot be realized. If the pressure is excessively high, the friction between the thermoplastic resin sheet and the die increases, and it becomes difficult to pull out the sheet laminate.

Accordingly, in the present invention, when a plurality of thermoplastic resin sheets are bundled and integrated, the immersion tank is not heated to a temperature higher than the melting temperature, and the integration is performed under as gentle a pressure as possible. 2 a specific liquid composition 2 as a processing liquid
a is stored, and the treatment with the liquid composition is performed.

In each of the first to fifth aspects of the present invention, the above-mentioned specific liquid composition is used as the liquid composition. That is, in the invention described in claim 1, a liquid composition containing a compound having an affinity for a thermoplastic resin and having a polymerizable unsaturated bond is used. In this case, since the compound having an affinity for the thermoplastic resin differs depending on the type of the thermoplastic resin to be used, a compound having a polymerizable unsaturated bond according to the type of the thermoplastic resin is used.

For example, when a polyolefin sheet is used as the thermoplastic resin sheet, the compound having an affinity for polyolefin and having a polymerizable unsaturated bond may be a compound having an unsaturated terminal such as 1-hexene or 1-heptene. Aliphatic hydrocarbon having a bond; aromatic or alicyclic hydrocarbon containing a vinyl group such as styrene, vinyltoluene, α-methylstyrene, divinylbenzene, and vinylcyclohexene; methyl vinyl ketone, ethyl vinyl ether, vinyl acetate, acrolein, and acrylic Organic compounds having a vinyl group or (meth) acrylic group, such as methyl acrylate, ethyl acrylate and methyl methacrylate, having 7 or less carbon atoms can be exemplified.
These compounds may be used alone, or two or more kinds may be used in combination, and may be used as a mixture with a compound having a polymerizable unsaturated bond other than those described above.

In addition to the compound having a polymerizable unsaturated bond, a polymerization catalyst may be contained in the liquid composition. As the polymerization catalyst, a catalyst that performs an organic chain reaction is preferable, and examples thereof include a peroxide having an O—O bond in a molecule and an azo compound having a C—N = N bond. it can.

In the invention described in claim 2, as the liquid composition, one having an affinity for the thermoplastic resin and containing a volatile compound or the compound itself is used. In this case, the above compound is selected depending on the type of the thermoplastic resin to be used. For example, when a polyolefin is used as the thermoplastic resin, a volatile compound having an affinity for the polyolefin is used.
Examples of such a compound include aliphatic hydrocarbons having 8 or less carbon atoms such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene, xylene, styrene and vinyltoluene; cyclohexane and the like. Alicyclic hydrocarbons; examples thereof include chlorides having 3 or less carbon atoms, such as carbon tetrachloride, dichloroethane, and trichloroethane. These compounds may be used alone or in combination of two or more.

The volatile compound may be mixed with another volatile solvent to form a liquid composition, or may be used alone. According to the third aspect of the present invention, as the liquid composition, a first liquid composition having an affinity for a thermoplastic resin and containing one of a polyfunctional active hydrogen compound and a polyisocyanate is used. Or a second liquid composition containing the other may be used sequentially,
Alternatively, a liquid composition containing both of these may be used.

In this case, the polyfunctional active hydrogen compound means a compound having two or more functional groups capable of reacting with polyisocyanate such as —OH, —NH ₂ , and —COOH. Hydrogen compounds have high polarity, so when used for low-polarity thermoplastic resins such as polyolefins, low-polarity binding groups such as long-chain aliphatic hydrocarbons and aromatic hydrocarbon alicyclic hydrocarbons Or having a small molecular size. Examples of such polyfunctional active hydrogen compounds include hexanediol, phthalic acid, cyclohexanedimethanol, and maleic acid. These polyfunctional active hydrogen compounds may be used alone or in combination of two or more.

Further, in addition to the polyfunctional active hydrogen compound,
Other active hydrogen compounds may be used as a mixture. When the polyisocyanate has an affinity for the thermoplastic resin, the affinity of the active hydrogen compound is not particularly problematic. In this case, any polyfunctional active hydrogen compound can be used without any particular limitation.

The polyisocyanate is represented by -N = C =
It refers to a compound having two or more functional groups of O. Since the polyisocyanate has a relatively high polarity, when it is used for a low-polarity thermoplastic resin such as a polyolefin, a long-chain aliphatic hydrocarbon is used. And those having a low-polarity binding group such as aromatic hydrocarbons and alicyclic hydrocarbons or having a small molecular size. Examples of such polyisocyanates include fatty acids such as toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, trans-1,4-cyclohexyl diisocyanate, and 1,6-hexamethylene diisocyanate. Group polyisocyanate and the like. These polyisocyanates may be used alone or in combination of two or more, and may be used in combination with other polyisocyanates other than those described above.

When the polyfunctional active hydrogen compound has an affinity for a thermoplastic resin, the affinity of the polyisocyanate does not cause any particular problem. In this case, the polyisocyanate is not limited to the above, and any polyisocyanate can be used.

The polyfunctional active hydrogen compound and the polyisocyanate are polymerized by a polyaddition reaction and cured. Although this reaction proceeds spontaneously, the curing time can be reduced by heating and adding a catalyst. Examples of such a catalyst include a basic substance, a tertiary amine, and an organotin compound. These may be used alone or in combination of two or more.

In the invention according to claim 4, a liquid composition having a polymerizable unsaturated bond and becoming sticky after polymerization is used as the liquid composition. Are aliphatic hydrocarbons having an unsaturated bond at the terminal such as 1-hexene and 1-heptene, styrene, vinyl toluene, α-methyl styrene, divinyl benzene, vinyl cyclohexene, methyl vinyl ketone, ethyl vinyl ether, vinyl acetate, acrolein And liquid organic compounds having a vinyl group at the terminal such as methyl acrylate, ethyl acrylate, and methyl methacrylate. These may be used alone or in combination of two or more, and may be used as a mixture with a compound having a polymerizable unsaturated bond other than those described above.

Of the above compounds, particularly preferred is n
It is a liquid organic compound having a vinyl group and an alkyl group having 4 or more carbon atoms at terminals, such as -butyl acrylate, 2-ethylhexyl acrylate, and n-butyl methacrylate. These organic compounds effectively exert the effect of increasing the tackiness even after the liquid composition is cured.

The above liquid composition can be cured by heating for a long time, but preferably, a polymerization catalyst may be added in order to accelerate the curing. As the polymerization catalyst, those which can conduct a chain reaction are suitable.
A peroxide having an O—O bond in the molecule, an azo compound having a C—N = N bond, or the like can be preferably used.

The above liquid composition preferably has a glass transition point after curing of 25 ° C. or lower, preferably 0 ° C. or lower.
If the glass transition point is too high, tackiness may not be exhibited. In particular, when the glass transition point of a homopolymer (homopolymer) measured at a sufficient degree of polymerization is higher than 25 ° C., it is preferable to use a mixture of the homopolymer with a component having a glass transition point of 25 ° C. or lower. For example, when styrene (glass transition point of homopolymer = 100 ° C.) is used as a component of the liquid composition, a low glass transition point such as n-butyl acrylate (glass transition point of homopolymer = −55 ° C.) is used. It is desirable to use a mixture with the components to be provided.

According to a fifth aspect of the present invention, there is provided the compound having a polymerizable unsaturated bond used in the first aspect of the present invention,
A liquid composition containing a polymer having tackiness is used. The above adhesive polymer is preferably a polymer having a glass transition point of 25 ° C. or lower, more preferably 0 ° C. or lower, and a commercially available product other than a cured product obtained by polymerizing the components of the liquid composition. It may be an available polymer. Examples of such commercially available polymers include petroleum resins (in particular, CO-based petroleum resins are preferable), low molecular weight polystyrene (with a degree of polymerization of 30 or less), liquid rubber, terpene resins,
Rosin, rosin ester, xylene resin and the like can be mentioned.

Since the above adhesive polymer does not constitute a liquid composition by itself, it is necessary to dissolve it in a liquid composition containing a compound having a polymerizable unsaturated bond before use.

In order to obtain a highly rigid sheet laminate in the present invention, it is preferable to use a stretched sheet obtained by stretching a crystalline thermoplastic resin sheet at a high magnification as the thermoplastic resin sheet. Polyolefin, polyamide, polyester, polyoxymethylene, and the like are known as the crystalline thermoplastic resin, and a polyolefin that can be stretched at a high magnification is particularly preferable.

Specific examples of polyolefins include homopolymers such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, polypropylene, polybutene, and polypentene;
Butene copolymer, ethylene, propylene, butene as a copolymer such as ethylene-vinyl acetate copolymer,
Copolymers containing at least one of pentenes may be mentioned. Further, the above-mentioned polyolefins may be used alone, or two or more kinds may be used in combination, or may be used by mixing with other thermoplastic resins.

(Function) According to the first aspect of the present invention, the liquid composition has a high affinity for the thermoplastic resin, and the compound having a polymerizable unsaturated bond is polymerized and cured by heating, for example. After treating a plurality of thermoplastic resin sheets with the liquid composition, the thermoplastic resin sheets are firmly adhered to each other when they are bundled and integrated.

According to the second aspect of the present invention, the liquid composition or compound has a high affinity for the thermoplastic resin and has an effect of swelling the polymer chains constituting the thermoplastic resin. Therefore, it is possible to swell by immersing a plurality of thermoplastic resin sheets in the liquid composition, and when the swelled thermoplastic resin sheets are bundled and integrated, the heat of each thermoplastic resin sheet is increased. The polymer chains constituting the plastic resin are entangled with each other, and the self-adhesiveness is enhanced. In addition, the liquid composition and the compound itself have volatility and almost volatilize after molding, and therefore do not remain in the sheet laminate.

Similarly, in the present invention, the liquid composition has a high affinity for the thermoplastic resin and swells the polymer chains constituting the thermoplastic resin. Therefore, a plurality of swollen thermoplastic resin sheets are bundled and
Upon integration, the polymer chains constituting the thermoplastic resin are entangled with each other, and the self-adhesiveness is enhanced. In addition, since the liquid composition itself is cured by a polyaddition reaction between the polyfunctional active hydrogen compound and the polyisocyanate, it does not remain as a liquid component in the sheet laminate.

According to the fourth aspect of the present invention, since the liquid composition contains a compound having a polymerizable unsaturated bond and exhibits tackiness after polymerization, a plurality of thermoplastic resin sheets are used. When a sheet-like laminate is obtained by being bundled and integrated after treatment with the liquid composition, a plurality of thermoplastic resin sheets can be firmly adhered to each other by the above-mentioned adhesiveness.

In the invention according to claim 5, since the liquid composition contains a compound having a polymerizable unsaturated bond and a sticky polymer, a plurality of thermoplastic resin sheets are formed by the liquid composition. After processing, when a plurality of thermoplastic resin sheets are bundled and integrated, the plurality of thermoplastic resin sheets are firmly adhered to each other and integrated.

That is, in the production method according to each of the first to fifth aspects of the present invention, a plurality of thermoplastic resin sheets are immersed in the above-described specific liquid compositions and treated,
By converging and integrating, the thermoplastic resin sheets are firmly adhered to each other and integrated.

Therefore, even when a stretched sheet obtained by stretching a polyolefin is used as the thermoplastic resin sheet, the stretched sheets are firmly integrated with each other, and mechanically. A sheet laminate having high strength can be obtained.

In the apparatus for manufacturing a sheet laminate according to the invention of claim 7, in the forming line having the supply section, the immersion tank, the die and the take-off section, the immersion tank is provided in the immersion tank. The liquid composition according to the present invention is stored, and in the immersion tank, a plurality of thermoplastic resin sheets are treated prior to integration, so that a plurality of thermoplastic resin sheets are treated in the same manner as in each of the inventions according to claims 1 to 5. Focusing resin sheet on die
It is possible to obtain a sheet laminate in which the thermoplastic resin sheets are integrally joined to each other firmly.

[0054]

The present invention will be clarified by the following non-limiting examples.

(Example 1) As a thermoplastic resin, high-density polyethylene (melting temperature 135 ° C, melt index M
I = 1 g / 10 min) was melt-kneaded at a temperature of 200 ° C. with a 30 mm twin screw extruder, extruded in a sheet shape with a T-die, cooled with a cooling roll, and had a thickness of 2.5 mm ×
An unstretched sheet having a width of 70 mm and a tensile modulus of 40 GPa was obtained.

The unstretched sheet was unwound with a roll at an unwinding speed of 1 m / min and passed through a heating furnace at 120 ° C.
Taking off with a roll at a take-up speed of 30 m / min
Double, thickness 0.15mm, width 40mm and tensile modulus 40
A GPa stretched sheet was obtained.

In the supply section 1 shown in FIG. 1, forty reels are arranged, and the stretched sheets are wound around the forty reels.
And pulled out to the take-up part 5. In the present example, in the manufacturing apparatus shown in FIG. 1, the thickness of the entrance of the die 3 is 60 mm, the thickness of the exit is 80 mm, the distance from the entrance to the exit is 1 m, and the die 3 is 120 mm. Heated to ° C. As the liquid composition 2a in the immersion tank 2, as a compound having a polymerizable unsaturated bond, 100 parts by weight of styrene and divinylbenzene 2
Parts by weight and a polymerization catalyst containing 1 part by weight of Trigonox 29A manufactured by Kayaku Akzo Co., Ltd. were used.

In the take-up section 5, the sheet laminate 6A was taken out at a take-up speed of 0.3 m / min while pressing. Shortly after the start of take-off, the integrated sheet laminate 6A was obtained continuously.

The sheet laminate 6 obtained as described above
When the flexural modulus of A was measured, it was 32 GPa,
It has been confirmed that a stretched sheet having a high rigidity that can maintain a strength of about 80% of the tensile modulus of the stretched sheet itself before lamination can be used as a structural material.

The interlayer shear strength (Inter-Lamina Share Strength), which is an index of adhesiveness, is 20 GPa, and peeling between sheets hardly occurs with some deformation, and good adhesiveness between sheets is obtained. That was confirmed.

(Comparative Example 1) In Example 1, immersion tank 2
The liquid composition 2a was not used, and the die temperature was 1
Molding was carried out in the same manner as in Example 1 except that the temperature was 35 ° C., and a sheet laminate was continuously obtained.

The sheet laminate obtained had a flexural modulus of 15
GPa, which was only about 40% of the tensile modulus of the stretched sheet itself, and the mechanical strength was inferior to that of Example 1. The interlayer shear strength, which is an index of adhesiveness, is 5 GPa.
When it was slightly lower than that of Example 1 and slightly deformed, peeling was observed between the stacked sheets.

Example 2 A sheet laminate was obtained using the same stretched sheet as used in Example 1 and using the manufacturing apparatus shown in FIG. However, toluene was used as the liquid composition 2a in the immersion tank 2, and the sheet laminate in the take-up machine was pressurized and taken up at a take-up speed of 0.15 m / min. Shortly after the start of the take-off, an integrated sheet laminate can be obtained continuously.

The flexural modulus of the sheet laminate is 25 GP.
a, the strength of the stretched sheet used was 60% of the tensile modulus of the stretched sheet itself, and it was confirmed that the stretched sheet had high rigidity as a structural material.

The interlayer shear strength, which is an index of adhesiveness, was 20 GPa, and peeling between the sheets was unlikely to occur with some deformation, and it was confirmed that the stretched sheets were bonded to each other with sufficient strength.

Comparative Example 2 A sheet laminate was obtained in the same manner as in Example 2, except that toluene was not used and the temperature of the die was 135 ° C. Was.

The bending elastic modulus of the obtained sheet laminate was 15
GPa, which was only about 40% of the tensile modulus of the stretched sheet used, and the rigidity of the sheet laminate was significantly inferior to Example 2. In addition, the interlayer shear strength, which is an index of adhesiveness, was 5 GPa, several steps lower than that of Example 2, and peeling occurred between the stretched sheets only by giving a slight deformation.

Example 3 A sheet laminate was obtained using the same stretched sheet used in Example 1 and using the manufacturing apparatus shown in FIG. However, as the liquid composition 2a in the immersion tank 2, 100 parts by weight of hexanediol as a polyfunctional active hydrogen compound, 149 parts by weight of toluene diisocyanate as a polyisocyanate, 0.1 part by weight of triethylenediamine as a polymerization catalyst, and tin octate Using a liquid composition consisting of 0.35 parts by weight, the sheet laminate in the take-up machine is pressed to reduce the take-up speed to 0.15 m.
/ Min. Shortly after the start of the take-off, an integrated sheet laminate can be obtained continuously.

The sheet laminate had a flexural modulus of 25 GP.
a, the strength of the stretched sheet used was 60% of the tensile modulus of the stretched sheet itself, and it was confirmed that the stretched sheet had high rigidity as a structural material.

The interlayer shear strength, which is an index of adhesiveness, was 20 GPa. It was confirmed that peeling between the sheets hardly occurred with some deformation, and that the stretched sheets were bonded with sufficient strength.

Comparative Example 3 A sheet laminate was obtained in the same manner as in Example 3, except that toluene was not used and the temperature of the die was 135 ° C. Was.

The bending elastic modulus of the obtained sheet laminate was 15
GPa, which was only about 40% of the tensile modulus of the stretched sheet used, and the rigidity of the sheet laminate was significantly inferior to Example 3. Further, the interlayer shear strength, which is an index of adhesiveness, was 5 GPa, which was several steps lower than that of Example 3, and peeling occurred between the stretched sheets only by giving a slight deformation.

Example 4 Using the same stretched sheet as used in Example 1, a sheet laminate was obtained using the manufacturing apparatus shown in FIG. However, as the liquid composition 2a in the immersion tank 2, 50 parts by weight of styrene, 50 parts by weight of n-butyl acrylate, 2 parts by weight of divinylbenzene, and 1 part by weight of Trigonox 29A manufactured by Kazaku Akzo Co., Ltd. as a polymerization catalyst were used. Using the resulting liquid composition, the sheet laminate in the take-off machine was pressurized and taken off at a take-up speed of 0.15 m / min. Shortly after the start of the take-off, an integrated sheet laminate can be obtained continuously.

The sheet laminate has a flexural modulus of 25 GP.
a, the strength of the stretched sheet used was 60% of the tensile modulus of the stretched sheet itself, and it was confirmed that the stretched sheet had high rigidity as a structural material.

The interlayer shear strength, which is an index of adhesiveness, was 20 GPa. It was confirmed that peeling between the sheets was unlikely to occur with some deformation, and that the stretched sheets were bonded to each other with sufficient strength.

Example 5 A sheet laminate was obtained using the same stretched sheet used in Example 1 and using the manufacturing apparatus shown in FIG. Of course, as the liquid composition 2a in the immersion tank 2, 100 parts by weight of a liquid component composed of a styrene / n-butyl acrylate / n-butyl acrylate polymer, 2 parts by weight of divinylbenzene, and a product of Kayaku Akzo as a polymerization catalyst , One Trigonox 29A
Using the liquid composition consisting of parts by weight, the sheet laminate in the take-up machine was pressurized and taken up at a take-up speed of 0.15 m / min. Shortly after the start of the take-off, an integrated sheet laminate can be obtained continuously.

The sheet laminate has a flexural modulus of 25 GP.
a, the strength of the stretched sheet used was 60% of the tensile modulus of the stretched sheet itself, and it was confirmed that the stretched sheet had high rigidity as a structural material.

The interlayer shear strength, which is an index of adhesiveness, was 20 GPa. It was confirmed that peeling between the sheets did not easily occur with a slight deformation, and that the stretched sheets were bonded to each other with sufficient strength.

The component consisting of the styrene / n-butyl acrylate / n-butyl acrylate polymer is as follows:
It was prepared as follows. That is, 49.97 parts by weight of high-purity n-butyl acrylate and 0.03 parts by weight of azobisisobutyronitrile as a polymerization catalyst are charged into a polymerization vessel, and the mixture is slowly stirred at 60 ° C. under a nitrogen atmosphere. When the polymerization was completed and the polymerization conversion reached 50%, 50 parts by weight of styrene was added, and the mixture was immediately cooled to room temperature. The sticky liquid thus obtained was used as the above liquid composition.

Comparative Example 4 A sheet laminate was obtained in the same manner as in Example 2, except that toluene was not used and the temperature of the die was 135 ° C. Was.

The sheet laminate obtained had a flexural modulus of 15
GPa, which was only about 40% of the tensile modulus of the stretched sheet used, and the rigidity of the sheet laminate was significantly inferior to Example 2. In addition, the interlayer shear strength, which is an index of adhesiveness, was 5 GPa, several steps lower than that of Example 2, and peeling occurred between the stretched sheets only by giving a slight deformation.

[0082]

According to the first to fifth aspects of the present invention, when a plurality of thermoplastic resin sheets are bundled and integrated, the thermoplastic resin sheets are preliminarily immersed in the specific liquid compositions described above. Because the surface of the resin sheet is treated, the thermoplastic resin sheet swells due to convergence and integration,
Due to the curing and the development of adhesiveness of the liquid composition, it becomes possible to obtain a sheet laminate in which the thermoplastic resin sheets are firmly joined together and integrated.

Accordingly, since the step of heating the thermoplastic resin sheet to a temperature higher than the melting temperature is not required for integrating the plurality of thermoplastic resin sheets, the mechanical strength of the used thermoplastic resin sheet is significantly reduced. Therefore, a sheet laminate having high rigidity can be obtained.

In particular, when the stretched polyethylene sheet is used as the thermoplastic resin sheet as described in claim 6, the stretched sheet originally has low self-adhesiveness, but the stretched sheets are treated with the liquid composition to form a stretched sheet. Since they are adhered and integrated with sufficient adhesive strength, a sheet laminate having even higher rigidity can be provided, and a sheet laminate suitable for structural materials such as civil engineering materials can be provided.

In addition, since the sheet laminate obtained according to the present invention does not require a reinforcing material such as glass fiber, it is excellent in moldability and recyclability as compared with conventional fiber-reinforced composite materials.

In the apparatus for manufacturing a sheet laminate according to the present invention, the supply section, the immersion tank, the die, and the take-up section are arranged in this order, and the immersion tank is provided in the immersion tank. Since a specific liquid composition is stored, by treating a plurality of thermoplastic resin sheets with the liquid composition, a plurality of thermoplastic resin sheets are formed in the same manner as in the invention according to claims 1 to 5. It is possible to obtain an integrated sheet laminate in which the sheets are firmly adhered to each other.

[Brief description of the drawings]

FIG. 1 is a diagram showing a schematic configuration of an apparatus used in a method of manufacturing a sheet laminate according to the present invention.

FIG. 2 is a cross-sectional view for explaining a die used in the method for manufacturing a sheet laminate of the present invention.

[Description of Signs] 1 ... Supplying unit 2 ... Immersion tank 2a ... Liquid composition 3 ... Die 5 ... Taking-up unit 6 ... Thermoplastic resin sheet 6A ... Sheet laminate

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Koichi Kariya 2-2 Sekisui Kagaku Kogyo Co., Ltd.

Claims (7)

[Claims] 1. A method for manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are supplied to a die before being supplied to the die. A method for producing a sheet laminate, characterized by immersing in a liquid composition containing a compound having an affinity for a resin and having a polymerizable unsaturated bond. 2. A method for producing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are supplied to a die before being supplied to the die. A method for producing a sheet laminate, characterized by immersing in a volatile compound having affinity for a resin and a liquid composition containing the compound. 3. A method for producing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are thermoplastically mixed before being supplied to the die. The resin is immersed in a liquid composition containing one of an active hydrogen compound and a polyisocyanate having an affinity for a polyfunctional resin, and then immersed in a liquid composition containing the other one, or A method for producing a sheet laminate, wherein the method is immersed in a liquid composition containing a hydrogen compound and a polyisocyanate. 4. A method for manufacturing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated and integrated by a die, wherein the plurality of thermoplastic resin sheets are supplied to a die before being supplied to the die. A method for producing a sheet laminate, comprising: immersing in a liquid composition containing a compound having an affinity for a resin and having a polymerizable unsaturated bond, and exhibiting tackiness after polymerization. 5. A method for producing a sheet laminate in which a plurality of thermoplastic resin sheets are laminated by a die and integrated, wherein the plurality of thermoplastic resin sheets are supplied to a die before being supplied to the die. A method for producing a sheet laminate, comprising immersing in a liquid composition containing a compound having an affinity for a resin and having a polymerizable unsaturated bond, and an adhesive polymer. 6. The method for producing a sheet laminate according to claim 1, wherein a polyolefin sheet obtained by stretching a polyolefin is used as the thermoplastic resin sheet. 7. A supply part for supplying a plurality of thermoplastic resin sheets, and a liquid composition which is disposed downstream of the thermoplastic resin sheet supply part and in which the thermoplastic resin sheet is immersed is stored. An immersion tank, a die for converging and integrating a plurality of thermoplastic resin sheets drawn out from the immersion tank, and a take-up unit that takes out the sheet laminate integrated by the die, A liquid composition containing (a) a compound having an affinity for a thermoplastic resin and having a polymerizable unsaturated bond; and (b) a volatile compound having an affinity for the thermoplastic resin and having a affinity. Or a liquid composition containing the compound, (c) a liquid composition having an affinity for a thermoplastic resin and containing a polyfunctional active hydrogen compound and polyisocyanate, and (d) a compound having a polymerizable unsaturated bond. Including, after polymerization Sheet lamination, characterized in that it is a kind selected from the group consisting of a liquid composition that becomes sticky, a liquid composition containing (e) a compound having a polymerizable unsaturated bond, and a sticky polymer. Body manufacturing equipment.