JP2019130819A - Laminate substrate and exterior - Google Patents

Abstract

To provide a laminate substrate used as a resin substrate that has impact resistance, weather resistance and rigidity in a balanced manner and achieves cost reduction and weight saving, and an exterior including the laminate substrate and having excellent reliability.SOLUTION: A laminate substrate 1 has a laminate 4 having: an intermediate layer 2 containing polyester resin and polyolefin resin; and two coating layers 3 put on both sides of the intermediate layer 2 as the outermost layers and contain polycarbonate resin and ultraviolet absorber.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated substrate and an exterior.

  In recent years, polycarbonate-based resins have been used as outdoor panels (resin substrates) provided in exterior parts such as roof members provided in carports, garages, storerooms, and window members provided in solariums, balconies, terraces, gates, doors, fences, etc. A polycarbonate plate contained as a main material has been proposed (see, for example, Patent Document 1).

  However, although this carbonate plate is excellent in impact resistance, weather resistance, and lightweight properties, it has a drawback of being inferior in rigidity and cost.

  Moreover, when a polycarbonate substrate excellent in these characteristics is applied to an outdoor panel provided in the exterior, it can be said that, among these characteristics, the impact resistance and the weather resistance are excessive performance. Therefore, there is a demand for the development of an outdoor panel (resin substrate) that has an excellent balance of impact resistance, weather resistance, and rigidity, and that is reduced in cost and weight.

  In addition, development of such a resin substrate is requested | required similarly about the partition panel etc. with which not only an outdoor panel but an indoor partition is provided.

WO2016 / 024531 WO2014 / 088105

  An object of the present invention is to provide a multilayer substrate that is used as a resin substrate that has an excellent balance of impact resistance, weather resistance, and rigidity, and that is reduced in cost and weight, and reliability provided with such a multilayer substrate. Is to provide an excellent exterior.

Such an object is achieved by the present invention described in the following (1) to (11).
(1) An intermediate layer containing a polyester resin and a polyolefin resin;
A laminated substrate comprising: a laminated body having two coating layers each including a polycarbonate-based resin and an ultraviolet absorber, which are laminated as outermost layers on both sides of the intermediate layer.

  (2) The multilayer substrate according to (1), wherein the intermediate layer has a specific gravity of 1.21 or more and 1.34 or less.

  (3) The multilayer substrate according to (1) or (2), wherein the content of the polyolefin resin in the intermediate layer is 1.0 wt% or more and 30.0 wt% or less.

  (4) The multilayer substrate according to any one of (1) to (3), wherein the intermediate layer has a crystallinity of 30% or more and 80% or less.

  (5) The multilayer substrate according to any one of (1) to (4), wherein the intermediate layer further includes a filler.

  (6) The multilayer substrate according to any one of (1) to (5), wherein the intermediate layer further includes a polycarbonate-based resin.

  (7) The laminated substrate according to any one of (1) to (6), wherein the polyester-based resin is a polyethylene terephthalate resin.

  (8) In the laminated substrate, the degree of yellowing measured in accordance with JIS K 5600 after irradiating the coating layer with ultraviolet rays for 3000 hours is 3.0 [ΔYI] or less (1) to ( 7) The multilayer substrate according to any one of the above.

  (9) The multilayer substrate according to any one of (1) to (8), wherein the multilayer substrate has a flexural modulus of 1500 MPa or more.

  (10) The multilayer substrate according to any one of (1) to (9), wherein the multilayer substrate is an outdoor panel used outdoors.

  (11) An exterior comprising the laminated substrate according to (10) as the outdoor panel.

  According to the present invention, the laminated substrate can be excellent in balance of impact resistance, weather resistance and rigidity, and can be reduced in cost and weight. Therefore, when such a laminated substrate is applied to an outdoor panel (resin substrate) included in the exterior, the exterior can have excellent reliability.

It is a longitudinal cross-sectional view which shows embodiment of the laminated substrate of this invention. It is a side view of the multilayer substrate manufacturing apparatus which manufactures the multilayer substrate shown in FIG. 1 using a coextrusion method.

  Hereinafter, the multilayer substrate and the exterior of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

  The laminated substrate 1 of the present invention includes an intermediate layer 2 containing a polyester-based resin and a polyolefin-based resin, and a polycarbonate-based resin and an ultraviolet absorber laminated as outermost layers on both sides of the intermediate layer, respectively. It is characterized by being comprised by the laminated body 4 which has two coating layers 3 containing these.

  In this way, the laminated substrate 1 (resin substrate) is composed of the laminated body 4 having the intermediate layer 2 and the two covering layers 3 laminated as the outermost layers on both sides of the intermediate layer 2, respectively. By making the intermediate layer 2 contain a polyester-based resin and a polyolefin-based resin, and the coating layer 3 contains a polycarbonate-based resin and an ultraviolet absorber, the laminated substrate 1 is made to have impact resistance and weather resistance. In addition, it is possible to achieve an excellent balance of rigidity characteristics, and to achieve cost reduction and weight reduction. Therefore, when the laminated substrate 1 is applied to an outdoor panel (resin substrate) provided in the exterior, the exterior can have excellent reliability.

  The laminated substrate 1 includes, for example, a roof member provided in a carport, a garage, a storeroom, a bicycle parking lot, and an exterior panel provided in an exterior such as a window member provided in a solarium, balcony, terrace, gate, door, fence, etc. It can be applied to the window member provided in the vending machine, the window member provided in the showcase, the showroom, etc., the partition material (partition panel) provided in the interior (indoor) partition, etc., but the characteristics of the multilayer substrate 1, that is, the multilayer substrate No. 1 is suitably applied to the outdoor panel provided in the exterior from the viewpoint that it is excellent in the balance of the characteristics of impact resistance, weather resistance and rigidity, and is reduced in cost and weight. Therefore, below, the case where the multilayer substrate 1 is applied to an outdoor panel included in the exterior will be described as an example.

<Laminated substrate 1>
FIG. 1 is a longitudinal sectional view showing an embodiment of a laminated substrate of the present invention. Hereinafter, for convenience of explanation, the upper side of FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  As described above, the laminated substrate 1 includes an intermediate layer 2 containing a polyester resin and a polyolefin resin, and a polycarbonate resin and an ultraviolet absorber that are laminated as outermost layers on both sides of the intermediate layer, respectively. It is comprised with the laminated body 4 which has the two coating layers 3 containing an agent.

  Hereinafter, each layer of the intermediate layer 2 and the covering layer 3 included in the multilayer substrate 1 (laminate 4) will be sequentially described.

<Intermediate layer>
The intermediate layer 2 is a main layer of the multilayer substrate 1 and includes a polyester-based resin and a polyolefin-based resin, whereby the multilayer substrate 1 has an excellent balance of impact resistance, weather resistance, and rigidity characteristics. It is for. In addition, since the polyester-based resin and the polyolefin-based resin are included, the cost of the multilayer substrate 1 can be reduced as compared with the case where the intermediate layer 2 is formed of a polycarbonate-based resin alone.

  Examples of the polyester resin include polyethylene terephthalate resin (PET), polycyclohexane terephthalate resin (PCT), polybutylene terephthalate resin (PBT), polyethylene naphthalate resin (PEN), polycyclohexanedimethylene terephthalate resin, polypropylene terephthalate resin, and the like. Of these, one or a combination of two or more can be used. In addition, when using in combination of 2 or more types of these, these polyester-type resin may be these blend bodies, and may be a copolymer. Among these, the polyester resin is particularly preferably a polyethylene terephthalate resin (PET). Since the cured product of the polyethylene terephthalate resin is rich in mechanical strength among the polyester-based resins, the crystallization of the multilayer substrate 1 can be increased by including the intermediate layer 2 in the polyethylene terephthalate resin. The bending elasticity of the laminated substrate 1 can be improved.

  The content of the polyester resin in the mid layer 2 is preferably 30.0% by weight or more and 90.0% by weight or less, and more preferably 40.0% by weight or more and 80.0% by weight or less. Thereby, impact resistance and rigidity can be improved.

  Examples of the polyolefin resin include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, Homopolymers of α-olefins such as 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, Examples include at least two types of α-olefin copolymers, copolymers of α-olefins and other monomers, and a mixture of two or more of these polyolefin resins.

  The other monomer is copolymerizable with an α-olefin, such as an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or an unsaturated carboxylic acid such as acrylic acid ester or methacrylic acid ester. Acid esters, polybasic unsaturated carboxylic acids such as maleic acid, acid anhydrides of polybasic unsaturated carboxylic acids, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, dicyclo Conjugated dienes such as pentadiene, dicyclopentadiene, 1,4-hexadiene, 1,9-decadiene, cyclooctadiene, norbornadiene, methylene norbornene, ethylidene norbornene, 7-methyl-1,6-octadiene Etc.

  Specific examples of such polyolefin resins include low density polyethylene (LDPE), low density linear polyethylene (LLDPE), polyethylene such as high density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene, One or a mixture of two or more of block polypropylene, polypropylene such as random polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-styrene copolymer Is mentioned. The polyolefin resin is particularly preferably polypropylene. Since the cured polypropylene is low in specific gravity and has a relatively high elastic modulus among polyolefin resins, the intermediate layer 2 contains polypropylene, so that the hardness of the laminated substrate 1 is reduced, that is, the laminated resin is laminated. The weight of the multilayer substrate 1 can be reduced while suppressing the rigidity of the substrate 1 from being lowered.

  The content of the polyolefin resin in the mid layer 2 is preferably 1.0% by weight or more and 30.0% by weight or less, and more preferably 5.0% by weight or more and 25.0% by weight or less. Thereby, weight reduction of the multilayer substrate 1 can be achieved while suppressing a decrease in the rigidity of the multilayer substrate 1.

  The intermediate layer 2 including the polyester resin and the polyolefin resin as described above has a specific gravity of preferably 1.21 or more and 1.34 or less, more preferably 1.21 or more and 1.28 or less. Here, the polycarbonate-based resin has a specific gravity of about 1.2 and is classified as a light resin material. Therefore, by setting the specific gravity of the intermediate layer 2 within the above range, the intermediate layer 2 As a result, it can be said that the multilayer substrate 1 is lightened.

  The intermediate layer 2 preferably further contains a polycarbonate resin in addition to the polyester resin and the polyolefin resin. Thereby, the intensity | strength of the intermediate | middle layer 2 can be made more excellent. That is, the impact resistance of the intermediate layer 2 can be improved.

  The polycarbonate resin is not particularly limited, and various types can be used, and among them, an aromatic polycarbonate resin is preferable. The aromatic polycarbonate-based resin has an aromatic ring in its main chain, whereby the strength of the intermediate layer 2 can be further improved.

  This aromatic polycarbonate resin is synthesized by, for example, an interfacial polycondensation reaction between bisphenol and phosgene, a transesterification reaction between bisphenol and diphenyl carbonate, or the like.

  Examples of the bisphenol include bisphenol A and bisphenol (modified bisphenol) that is the origin of the repeating unit of the polycarbonate represented by the following formula (1A).

（式（１Ａ）中、Ｘは、炭素数１〜１８のアルキル基、芳香族基または環状脂肪族基であり、ＲａおよびＲｂは、それぞれ独立して、炭素数１〜１２のアルキル基であり、ｍおよびｎは、それぞれ０〜４の整数であり、ｐは、繰り返し単位の数である。）

(In the formula (1A), X is an alkyl group having 1 to 18 carbon atoms, an aromatic group or a cyclic aliphatic group, and Ra and Rb are each independently an alkyl group having 1 to 12 carbon atoms. , M and n are each an integer of 0 to 4, and p is the number of repeating units.)

  Specific examples of the bisphenol that is the origin of the repeating unit of the polycarbonate represented by the formula (1A) include 4,4 ′-(pentane-2,2-diyl) diphenol, 4,4 ′-( Pentane-3,3-diyl) diphenol, 4,4 ′-(butane-2,2-diyl) diphenol, 1,1 ′-(cyclohexanediyl) diphenol, 2-cyclohexyl-1,4-bis ( 4-hydroxyphenyl) benzene, 2,3-biscyclohexyl-1,4-bis (4-hydroxyphenyl) benzene, 1,1′-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2′- Bis (4-hydroxy-3-methylphenyl) propane and the like can be mentioned, and one or more of these can be used in combination.

  In particular, the polycarbonate-based resin is preferably composed mainly of a bisphenol-type polycarbonate-based resin having a skeleton derived from bisphenol. By using such a bisphenol-type polycarbonate resin, the intermediate layer 2 exhibits even better strength.

  The content of the polycarbonate resin in the intermediate layer 2 is not particularly limited, but is preferably 1.0% by weight or more and 20.0% by weight or less, and is preferably 1.0% by weight or more and 15.0% by weight or less. It is more preferable that By setting the content of the polycarbonate resin within the above range, the effect obtained by adding the polycarbonate resin to the mid layer 2 can be more remarkably exhibited. Moreover, if it is content in this range, the cost increase by adding polycarbonate-type resin can be suppressed in a tolerance | permissible_range.

  Furthermore, the crystallinity of the resin material contained in the intermediate layer 2 is preferably 1% or more and 80% or less, and more preferably 30% or more and 80% or less. By setting the crystallinity within the above range, the flexural elasticity of the intermediate layer 2 can be improved, so that the impact resistance of the multilayer substrate 1 can be improved.

The degree of crystallinity [%] of the resin material in the intermediate layer 2 is defined as ΔHm as the total endotherm when the intermediate layer 2 is melted, and ΔHc as the total amount of heat generated when the resin material is crystallized in the intermediate layer 2. When the total heat of fusion of the 100% crystal is ΔHm ⁰ , it can be calculated using the following formula (1).
Crystallinity [%] = (ΔHm−ΔHc) / ΔHm ⁰ × 100 (1)

  Moreover, the intermediate | middle layer 2 may contain various additives, such as an inorganic filler, antioxidant, a coloring agent, a plasticizer, a ultraviolet absorber, a heat ray absorber other than the various resin materials mentioned above, for example. Although it is good, it is particularly preferable that it contains an inorganic filler. Thereby, the hardness of the laminated substrate 1 can be set higher, that is, the laminated substrate 1 can be provided with more excellent rigidity.

  Examples of the inorganic filler include titanium oxide, zirconium oxide, silica, calcium carbonate, boron carbide, clay, mica, talc, wollastonite, glass beads, milled carbon, graphite, and the like. Alternatively, two or more kinds can be used in combination. Among these, talc is particularly preferable in that it is excellent in the crystallization promoting action of the polyester resin.

  The average particle size of the inorganic filler is not particularly limited, but is preferably about 0.01 μm or more and 10.0 μm or less, and more preferably about 0.1 μm or more and 5.0 μm or less. By setting the average particle diameter of the inorganic filler within the above range, the inorganic filler can be more uniformly dispersed in the intermediate layer 2.

  In addition, the average particle diameter of an inorganic filler can be measured, for example with a particle size distribution meter (the product made by HORIBA, LA-500).

  The average thickness of the mid layer 2 is preferably 0.4 mm or more and 15 mm or less, and more preferably 1 mm or more and 10 mm or less. When the thickness of the intermediate layer 2 is less than the lower limit, depending on the type and content of the polyester resin and the polyolefin resin, the mechanical strength of the laminated substrate 1 may be reduced. If the thickness exceeds the upper limit, the moldability of the laminated substrate 1 may be lowered depending on the types and contents of the polyester resin and the polyolefin resin.

  Further, for the purpose of improving the adhesion with the coating layer 3, the intermediate layer 2 is subjected to surface roughening treatment by sandblasting or solvent treatment, or corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment. Surface oxidation treatment such as ozone / ultraviolet irradiation treatment and electron beam irradiation treatment may be performed.

  In addition, as the intermediate | middle layer 2, the thing of the single layer structure obtained by the resin composition containing a polyester-type resin and polyolefin resin, and the resin composition containing at least one of a polyester-type resin and polyolefin-type resin are used. A multilayer structure in which two or more obtained single-layer films are laminated can be used.

  Further, in the case of a multilayer structure, each layer constituting the multilayer structure may be composed of the same material as long as it includes at least one of a polyester resin and a polyolefin resin. For example, a structure in which two second layers made of a polyolefin resin are laminated on both surfaces of a first layer made of a polyester resin may be used. Further, each layer may have a different thickness or the same thickness.

<Coat layer>
As shown in FIG. 1, the coating layer 3 (coat layer) is laminated as an outermost layer on both the front surface (one surface) and the lower surface (the other surface) of the intermediate layer 2, and is composed of a polycarbonate resin and an ultraviolet ray. It contains an absorbent and is provided for imparting excellent weather resistance and scratch resistance to the laminated substrate 1.

  Thus, when the coating layer 3 contains the polycarbonate resin and the ultraviolet absorber, the surface hardness of the coating layer 3 is increased, and excellent weather resistance and further excellent scratch resistance are imparted to the laminated substrate 1. Can be granted.

  Although it does not specifically limit as polycarbonate-type resin, For example, the thing similar to the thing quoted by the said intermediate | middle layer 2 can be used.

  The content of the polycarbonate resin in the coating layer 3 is preferably 80.0 wt% or more and 98.0 wt% or less, and more preferably 85.0 wt% or more and 95.0 wt% or less. . Thereby, the weather resistance and scratch resistance of the coating layer 3 can be improved reliably.

  The ultraviolet absorber absorbs ultraviolet rays in the coating layer 3 to change or deteriorate the polycarbonate resin contained in the coating layer 3 and further the polyester resin and polyolefin resin contained in the intermediate layer 2. In order to suppress and improve the weather resistance of the coating layer 3 and further the weather resistance of the intermediate layer 2, it is contained in the coating layer 3.

  The ultraviolet absorber is not particularly limited, and examples thereof include triazine-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers, and one or a combination of these can be used. .

  Further, the content of the ultraviolet absorber in the coating layer 3 is not particularly limited, but is preferably 0.1 wt% or more and 20.0 wt% or less, and is 1.0 wt% or more and 10.0 wt% or less. More preferably. If the content of the ultraviolet absorber in the coating layer 3 is less than the lower limit, the weather resistance of the coating layer 3 may be lowered depending on the type of the ultraviolet absorber. Further, even if the content of the ultraviolet absorber in the coating layer 3 exceeds the upper limit, no further improvement in weather resistance is observed, and the hardness of the coating layer 3 may be lowered depending on the type of the ultraviolet absorber. There is.

  Such a coating layer 3 preferably further contains a heat ray absorbent in addition to the polycarbonate resin and the ultraviolet absorbent. Thereby, the heat resistance of the coating layer 3 can be improved.

  Examples of the heat ray absorbent include carbon black, carbon powder, tin oxide, indium oxide, zinc oxide, ITO, ATO, and the like, and one or more of these can be used in combination. .

  Further, the content of the heat ray absorbent in the coating layer 3 is not particularly limited, but is preferably 0.1 wt% or more and 15.0 wt% or less, and is 1.0 wt% or more and 7.5 wt% or less. More preferably. If the content of the heat ray absorbent in the covering layer 3 is less than the lower limit, the heat resistance of the covering layer 3 may be lowered depending on the type of the heat ray absorbent. Moreover, even if content of the heat ray absorber in the coating layer 3 exceeds the said upper limit, the further heat resistance improvement is not seen, and depending on the kind of heat ray absorber, there exists a possibility that the hardness of the coating layer 3 may fall. There is.

  In addition, the coating layer 3 may further contain other materials in addition to the polycarbonate resin, the ultraviolet absorber, and the heat ray absorber described above.

  Examples of other materials include, but are not limited to, plasticizers, colorants, sensitizers, stabilizers, surfactants, antioxidants, anti-reduction agents, antistatic agents, surface conditioners, and hydrophilic additives. These can be used, and one or more of these can be used in combination.

  The average thickness of the coating layer 3 is not particularly limited, but is preferably 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 30 μm or less. When the thickness of the coating layer 3 is less than the lower limit value, the weather resistance of the multilayer substrate 1 may be lowered depending on the type of the ultraviolet absorber included in the coating layer 3. On the other hand, when the thickness of the coating layer 3 exceeds the upper limit, when the laminated substrate 1 is thermoformed to have a curved portion, there is a possibility that a crack may occur in the curved portion.

  Furthermore, when the thickness of the intermediate layer 2 is A [mm] and the thickness of the coating layer 3 is B [mm], A / B preferably satisfies the relationship of 300 to 15000, preferably 1500 or more. It is more preferable to satisfy the relationship of 10,000 or less. As a result, in the multilayer substrate 1, the intermediate layer 2 exhibits the function as the main layer, the multilayer substrate 1 exhibits the excellent impact resistance and rigidity, and the covering layer 3 exhibits the function as the outermost layer. Thus, the laminated substrate 1 can exhibit excellent weather resistance, and the cost and weight of the laminated substrate 1 can be reduced.

  The two coating layers 3 formed on both the upper surface and the lower surface of the intermediate layer 2 are not particularly limited as long as each of them includes a polycarbonate resin and an ultraviolet absorber as described above. These may be the same or different. The two coating layers 3 may have the same thickness or different thicknesses.

  By making the laminated substrate 1 to have the above-described configuration, it is possible to achieve a good balance of impact resistance, weather resistance, and rigidity characteristics. Specifically, the following indicators are used. Is preferably satisfied.

  That is, it is preferable that the laminated substrate 1 has a DuPont impact at a weight of 1 kg at 25 ° C. of 50 cm or more and less than 150 cm, more preferably 75 cm or more and less than 150 cm, measured in accordance with JIS K 5600-5-3. preferable. Thereby, it can be said that the multilayer substrate 1 has sufficient impact resistance, and as a result, the multilayer substrate 1 can be suitably applied to an outdoor panel included in the exterior.

  In the multilayer substrate 1, the yellowing degree of the intermediate layer 2 measured according to JIS K 5600 after the coating layer was irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer was 3.0 [ ΔYI] or less is preferable, and 2.0 [ΔYI] or less is more preferable. As a result, it can be said that the multilayer substrate 1 has more excellent weather resistance, and as a result, deterioration of the appearance of the multilayer substrate 1 is more accurately suppressed or prevented. It can be suitably applied to an outdoor panel provided.

  Further, the laminated substrate 1 has a flexural modulus measured at 25 ° C. of preferably 1500 MPa or more, more preferably 3000 MPa or more and 3600 MPa or less, measured in accordance with JIS K 6911. Thereby, it can be said that the multilayer substrate 1 has sufficient rigidity, and as a result, the multilayer substrate 1 can be suitably applied to an outdoor panel included in the exterior.

  Furthermore, it is preferable that the laminated substrate 1 has a Vicat softening temperature of 100 ° C. or higher, and more preferably 140 ° C. or higher. Thereby, it can be said that the laminated substrate 1 has more excellent heat resistance. As a result, even if the laminated substrate 1 is heated during use, the laminated substrate 1 is warped or deformed. Therefore, the multilayer substrate 1 can be suitably applied to an outdoor panel provided in the exterior.

<The manufacturing method of the laminated substrate 1>
The laminated substrate 1 having the above-described configuration can be manufactured using, for example, a coextrusion method, a press method, a casting method, an injection method, and the like. In the following, the laminated substrate 1 is manufactured using a coextrusion method. The case will be described as an example.

First, the laminated substrate manufacturing apparatus to which the coextrusion method is applied will be described.
FIG. 2 is a side view of a multilayer substrate manufacturing apparatus for manufacturing the multilayer substrate of the present invention by applying a coextrusion method. In the following description, the upper side in FIG. 2 is referred to as “upper” and the lower side is referred to as “lower”.

  A laminated substrate manufacturing apparatus 500 shown in FIG. 2 includes a sheet supply unit 700 and a sheet forming unit 800.

  The sheet supply unit 700 includes an extruder 210, an extruder 220, a T-die 600, and a two-type three-layer distribution type distributor 230, and a pipe 212 connected to the molten resin discharge unit 211 of the extruder 210. A distributor 230 is connected to a pipe 212 connected to the molten resin discharge part 221 of the extruder 220, and a T die 600 is connected to the distributor 230 via the pipe 212.

  In the sheet supply unit 700 having such a configuration, the resin composition (constituent material) constituting the intermediate layer 2 is accommodated in the extruder 210, and the resin (constituent material) constituting the coating layer 3 is accommodated in the extruder 220. . A resin composition (A) constituting the intermediate layer 2 in a molten state or a softened state and a resin (B) constituting the coating layer 3 in a molten state or a softened state are two-type three-layer distribution type distributors 230, when the distributor 230 is operated, the molten sheet or sheet in which the resin (B), the resin composition (A), and the resin (B) are laminated in this order. 150 is supplied to the sheet forming unit 800 via the distributor 230, the pipe 212, and the T die 600 (the opening 601 that the die has). Thus, by setting it as the structure which obtains the molten sheet 150 by a coextrusion method, the thickness of the formed molten sheet 150 can be stabilized.

  The sheet forming unit 800 includes a touch roll 110, a cooling roll 120, and a rear cooling roll 130. These rolls are configured to rotate independently by respective motors (drive means) (not shown), and the molten sheet 150 is cooled by the rotation of these rolls, whereby the laminated substrate 1 is continuously formed. It is to be sent out. By continuously feeding the melted or softened molten sheet 150 to the sheet forming portion 800, the first surface 15 and the second surface 13 of the molten sheet 150 are flattened, and the molten sheet 150 has a desired thickness. Is set to

  Further, the molten sheet 150 that has passed between the cooling roll 120 and the touch roll 110 is further supplied between the cooling roll 120 and the subsequent cooling roll 130, whereby the molten sheet 150 is cooled. A laminated substrate 1 in which the coating layer 3, the intermediate layer 2, and the coating layer 3 are laminated in this order is formed.

  The cooling roll 120 is a roll having a smooth outer peripheral surface, and includes cooling means for cooling the molten sheet 150 in a molten state supplied from the T die 600. By pressing the molten sheet 150 against the cooling roll 120, the first surface 15 is flattened and the molten sheet 150 is cooled.

  The touch roll 110 is a roll having a smooth outer peripheral surface, and is disposed opposite to the cooling roll 120. By supplying the molten sheet 150 between the touch roll 110 and the cooling roll 120, the second surface 13 of the molten sheet 150 is flattened.

  The rear cooling roll 130 is a roll having a smooth outer peripheral surface, and includes a cooling unit that cools the molten sheet 150, and is disposed downstream of the touch roll 110 and the cooling roll 120. By supplying the molten sheet 150 to such a subsequent cooling roll 130, the molten sheet 150 can be cooled more reliably and the laminated substrate 1 can be obtained.

  In the present embodiment, the case where the cooling roll 120 has the cooling means and the touch roll 110 does not have the cooling means has been described. However, the present invention is not limited to this case, and at least one of the cooling roll 120 and the touch roll 110 is used. As long as one has a cooling means, the touch roll 110 may have a cooling means, the cooling roll 120 may not have a cooling means, and both the cooling roll 120 and the touch roll 110 may be cooled. You may have a means.

  The multilayer substrate 1 is manufactured by the multilayer substrate manufacturing method using the multilayer substrate manufacturing apparatus 500 as described above.

  The method for manufacturing a laminated substrate includes an extrusion process for extruding a molten or softened molten sheet 150 formed into a belt-like sheet, and planarizing the first surface 15 and the second surface 13 of the molten sheet 150. 1 and a cooling step for cooling the molded molten sheet 150 in a molten state or a softened state.

Hereinafter, each process for manufacturing the multilayer substrate 1 will be described in detail.
[A] First, the molten or softened molten sheet 150 formed into a belt-like sheet is extruded (extrusion process).

  In this extrusion process, the resin composition (constituent material) constituting the intermediate layer 2 is accommodated in the extruder 210, and the resin (constituent material) constituting the coating layer 3 is accommodated in the extruder 220. A resin composition (A) constituting the intermediate layer 2 in a molten state or a softened state and a resin (B) constituting the coating layer 3 in a molten state or a softened state are two-type three-layer distribution type distributors 230, when the distributor 230 is operated, the molten sheet or sheet in which the resin (B), the resin composition (A), and the resin (B) are laminated in this order. 150 is pushed out from the opening 601 of the T-die 600 through the distributor 230 and the pipe 212. As a result, the molten or softened molten sheet 150 formed into a belt-like sheet is continuously fed out.

  In other words, the molten sheet 150 in a molten state or a softened state is formed by coextrusion so as to be extruded from the opening 601.

  [B] Next, the first surface 15 and the second surface 13 of the molten sheet 150 are flattened, and the molten sheet 150 is set to a predetermined thickness so that the coating layer 3 is in a molten state or a softened state. Then, the laminated substrate 1 in which the intermediate layer 2 and the covering layer 3 are laminated in this order is formed (molding step).

  This forming step is performed by supplying a molten sheet 150 between the touch roll 110 and the cooling roll 120.

  At this time, the outer peripheral surface of the cooling roll 120 and the outer peripheral surface of the touch roll 110 are each in the form of a roll having smoothness. Therefore, the first surface 15 and the second surface 13 of the molten sheet 150 are each flattened by being pressed against the outer peripheral surface having smoothness.

  Further, the separation distance between the outer peripheral surface of the cooling roll 120 and the outer peripheral surface of the touch roll 110 is set to the thickness of the laminated substrate 1 to be formed, and this separation distance is set to a predetermined size as desired. A molten sheet 150 having a thickness of 5 mm can be obtained.

  Thus, in this step [B], the cooling roll 120 and the touch roll 110 are used to flatten the first surface 15 and the second surface 13 and to set the thickness of the molten sheet 150, respectively. It is done.

  [C] Next, the molten sheet 150 in the molten state or the softened state in which the first surface 15 and the second surface 13 are flattened and made porous is cooled (cooling step).

  Thereby, the laminated substrate 1 which consists of the laminated body 4 in which the coating layer 3, the intermediate | middle layer 2, and the coating layer 3 were laminated | stacked in this order is formed.

  This cooling step is performed by supplying the molten sheet 150 between the cooling roll 120 and the rear cooling roll 130.

  Thereby, until the 1st surface 15 of the fusion | melting sheet 150 contact | abuts the cooling roll 120 to the cooling roll 120 and the cooling roll 120 rotates 180 degrees, and the back | latter stage cooling roll 130 rotates 90 degrees. The second surface 13 of the molten sheet 150 contacts.

  Here, in this embodiment, since both the cooling roll 120 and the rear cooling roll 130 are provided with cooling means, the contact (contact) of the molten sheet 150 with the rolls 120 and 130 as described above. The molten sheet 150 in which the first surface 15 and the second surface 13 are flattened is cooled. As a result, the first surface 15 and the second surface 13 are planarized, and the laminated substrate 1 is obtained.

  In the present embodiment, the molten sheet 150 is cooled in a state where the first surface 15 and the second surface 13 of the molten sheet 150 are alternately in contact with the respective cooling rolls 120 and 130. Therefore, it is possible to reliably prevent the molten sheet 150 from being cooled in a state where the first surface 15 or the second surface 13 is warped.

As mentioned above, in this process [C], each cooling roll 120 and 130 provided with a cooling means is used in order to cool the fusion sheet 150. FIG.
The laminated substrate 1 is manufactured through the above processes.

  Although the multilayer substrate and the exterior of the present invention have been described above, the present invention is not limited to this, and each part constituting the multilayer substrate and the exterior is replaced with an arbitrary configuration that can exhibit the same function. can do. Moreover, arbitrary components may be added.

  The laminated substrate may be one in which at least one other layer such as a bonding layer (adhesive layer) is interposed between the intermediate layer and the covering layer.

  Hereinafter, based on an Example, this invention is demonstrated more concretely. In addition, this invention is not limited at all by these Examples.

1. Formation of laminated substrate [Example 1]
[1] First, polyethylene terephthalate (manufactured by INDORAMA, “S1”) and polypropylene (manufactured by Sumitomo Chemical, “FH1016”) are 90% by weight and 10% by weight, respectively. In addition, an intermediate layer forming material was prepared by preparing by stirring and mixing.

  Moreover, each content of bisphenol A type polycarbonate (Mitsubishi Engineer Plastics, "H3000") and tribromophenoxytriazine (Daiichi Kogyo Seiyaku Co., Ltd., "SR-245") as an ultraviolet absorber. Was prepared by stirring and mixing so as to be 90% by weight and 10% by weight, thereby preparing a coating layer forming material.

  [2] Next, the prepared intermediate layer forming material and coating layer forming material are respectively stored in the single-screw extruder 210 and the single-screw extruder 220 provided in the multilayer substrate manufacturing apparatus 500 shown in FIG. Thereafter, the single-screw extruder 210 and the single-screw extruder 220 were supplied to the distributor 230 under the condition that the rotation speed of the single-screw extruder 210 was 50 rpm. The distributor 230 supplies the T-die 600 with the distribution material distributed in the order of the coating layer forming material, the intermediate layer forming material, and the coating layer forming material, and then from the opening 601 of the T die 600. Then, the sheet was extruded into the sheet forming section 800 as a molten sheet.

  Then, the distribution in the form of a sheet extruded from the opening 601 is sandwiched between the touch roll 110 and the cooling roll 120 and between the cooling roll 120 and the subsequent cooling roll 130, thereby flattening and It cooled and the laminated substrate of Example 1 comprised by the laminated body provided with an intermediate | middle layer and the coating layer which coat | covers both the upper surface and lower surface of this intermediate | middle layer was obtained.

  The distribution ratio of the coating layer forming material, the intermediate layer forming material, and the coating layer forming material in the distribution formed by the distributor 230 is 5: 90: 5, and the conveyance speed in the sheet forming unit 800 is 2 m. Under the condition of / min, a multilayer substrate of Example 1 including an intermediate layer having an average thickness of 3.0 mm, a specific gravity of 1.30, and a coating layer having an average thickness of 0.01 mm was obtained.

[Examples 2 to 6]
In the step [1], an example was obtained in the same manner as in the example 1, except that the contents of polyethylene terephthalate and polypropylene contained in the intermediate layer forming material were changed as shown in Table 1, respectively. 2 to 6 laminated substrates were obtained.

[Example 7]
In the step [1], the intermediate layer forming material further includes a bisphenol A type polycarbonate (manufactured by Mitsubishi Engineer Plastics, "H3000"), and includes polyethylene terephthalate, polypropylene and A laminated substrate of Example 7 was obtained in the same manner as in Example 1 except that the content of bisphenol A-type polycarbonate was as shown in Table 1.

[Example 8]
In the step [1], the intermediate layer forming material further includes talc (manufactured by Nippon Talc Co., Ltd., “P-3”), and contains polyethylene terephthalate, polypropylene, and talc contained in the intermediate layer forming material. A laminated substrate of Example 8 was obtained in the same manner as in Example 1 except that the amounts were as shown in Table 1.

[Example 9]
In the step [1], the intermediate layer forming material further includes bisphenol A type polycarbonate (Mitsubishi Engineer Plastics, “H3000”) and talc (Nippon Talc, “P-3”). In the same manner as in Example 1 except that the contents of polyethylene terephthalate, polypropylene, bisphenol A type polycarbonate and talc contained in the intermediate layer forming material are as shown in Table 1, respectively. 9 laminated substrates were obtained.

[Comparative Example 1]
In step [1], the preparation of the coating layer forming material was omitted, and a single layer intermediate layer was prepared as a laminated substrate of Comparative Example 1.

[Comparative Example 2]
Lamination of Comparative Example 2 in the same manner as in Example 1 except that, in the step [1], the intermediate layer forming material includes polyethylene terephthalate (manufactured by INDORAMA, “S1”) alone. A substrate was obtained.

[Comparative Example 3]
Lamination of Comparative Example 3 in the same manner as in Example 1 except that in the step [1], the intermediate layer forming material includes polypropylene ("FH1016", manufactured by Sumitomo Chemical Co., Ltd.) alone. A substrate was obtained.

[Comparative Example 4]
In the step [1], except that the coating layer forming material contains bisphenol A type polycarbonate (manufactured by Mitsubishi Engineer Plastics Co., Ltd., “H3000”) in the same manner as in Example 1, A laminated substrate of Comparative Example 4 was obtained.

2. Evaluation The laminated substrate of each Example and each comparative example was evaluated by the following method.
<Bending modulus test>
In accordance with JIS K 6911, using the Shimadzu Autograph (manufactured by Shimadzu Corporation, “AG-20kNXDplus”), the flexural modulus of the laminated substrate of each example and each comparative example was measured at room temperature (25 ° C.). It was measured.
And based on the measured bending elastic modulus, it evaluated as follows.

A: The flexural modulus is 3000 MPa or more.
◯: The flexural modulus is 1500 MPa or more and less than 3000 MPa.
X: The bending elastic modulus is less than 1500 MPa.

<DuPont impact test>
In accordance with JIS K 5600-5-3, using a DuPont impact tester ("IM-4530", manufactured by Ueshima Seisakusho Co., Ltd.), the DuPont impact of the laminated substrates of each Example and each Comparative Example under the condition of 25 ° C. Was measured.

<Heat resistance (Vicat softening temperature) test>
Based on JIS K 7206: 1999, the Vicat softening temperature of the laminated substrate of each Example and each Comparative Example was measured using AUTO HDT Tester (“6A-2” manufactured by Toyo Seiki Co., Ltd.).

<Weather resistance (yellowing degree) test>
About each laminated substrate of each example and each comparative example, each sample (width 60 mm, length 120 mm, thickness 4 mm) was softened by heating for 10 minutes in a hot air circulation oven set at 170 ° C. A curved surface was added to a wooden cylinder with a radius of 30 mm through a flannel cloth, and the sample was kept as it was until it was cooled to near room temperature, thereby performing single-curved surface molding to obtain a molded body.

  Next, the molded body obtained from the laminated substrate of each example and each comparative example was subjected to an acceleration test using a carbon arc sunshine weatherometer, and the appearance after 3000 hours of ultraviolet irradiation according to JIS K 5600. The yellowing degree (ΔYI) was evaluated as follows.

A: ΔYI is 2.0 or less and there is no change in appearance.
A: Appearance change is slightly observed when ΔYI is more than 2.0 and 3.0 or less.
X: Appearance change is clearly seen when ΔYI exceeds 3.0.

  The evaluation results of the laminated substrates of the examples and comparative examples obtained as described above are shown in Table 1 below.

  As shown in Table 1, in each example, the laminated substrate was formed of an intermediate layer containing a polyester-based resin and a polyolefin-based resin, and polycarbonate laminated as outermost layers on both sides of the intermediate layer. By comprising a laminate having two coating layers containing a resin and an ultraviolet absorber, this laminated substrate has an excellent balance of impact resistance, weather resistance and rigidity (flexural elasticity) characteristics, and It was possible to reduce the weight.

  On the other hand, in each comparative example, the formation of the coating layer in the laminated substrate is omitted, the addition of the polyester resin or the polyolefin resin to the intermediate layer is omitted, or the addition of the ultraviolet absorber to the coating layer is omitted. As a result, the results of obtaining a laminated substrate that cannot balance the characteristics of impact resistance, weather resistance, and rigidity (flexural elasticity) or that cannot be said to be lighter.

DESCRIPTION OF SYMBOLS 1 Laminated substrate 2 Intermediate | middle layer 3 Cover layer 4 Laminated body 13 2nd surface 15 1st surface 110 Touch roll 120 Cooling roll 130 Subsequent cooling roll 150 Molten sheet 210 Extruder 211 Molten resin discharge part 212 Piping 220 Extruder 221 Molten resin discharge Section 230 Distributor 500 Multilayer substrate manufacturing apparatus 600 T die 601 Opening section 700 Sheet supply section 800 Sheet forming section

Claims (11)

An intermediate layer containing a polyester resin and a polyolefin resin;
A laminated substrate comprising: a laminated body having two coating layers each including a polycarbonate-based resin and an ultraviolet absorber, which are laminated as outermost layers on both sides of the intermediate layer.   The multilayer substrate according to claim 1, wherein the intermediate layer has a specific gravity of 1.21 to 1.34.   The multilayer substrate according to claim 1 or 2, wherein the content of the polyolefin resin in the intermediate layer is 1.0 wt% or more and 30.0 wt% or less.   The laminated substrate according to any one of claims 1 to 3, wherein the intermediate layer has a crystallinity of 30% or more and 80% or less.   The multilayer substrate according to claim 1, wherein the intermediate layer further includes a filler.   The multilayer substrate according to claim 1, wherein the intermediate layer further includes a polycarbonate-based resin.   The laminated substrate according to any one of claims 1 to 6, wherein the polyester resin is a polyethylene terephthalate resin.   8. The laminated substrate according to any one of claims 1 to 7, wherein the yellowing degree measured in accordance with JIS K 5600 after the coating layer is irradiated with ultraviolet rays for 3000 hours is 3.0 [ΔYI] or less. The laminated substrate according to item.   The multilayer substrate according to any one of claims 1 to 8, wherein the multilayer substrate has a flexural modulus of 1500 MPa or more.   The multilayer substrate according to any one of claims 1 to 9, wherein the multilayer substrate is an outdoor panel used outdoors.   An exterior comprising the laminated substrate according to claim 10 as the outdoor panel.

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