JPH04325241A - Flame-retarded weather-resistant shock-resistant resin laminated board - Google Patents

Abstract

PURPOSE:To provide a resin laminated sheet having excellent transparency, flame retardancy, heat resistance, shock resistance and weather resistance and proper for exterior application, particularly a roof material. CONSTITUTION:A resin laminated board is manufactured by forming coating resin layers composed of a 100 pts.wt. acrylic resin and a 0.5-5 pts.wt. benzotriazole group ultraviolet absorbing agent on one surface of both surfaces of a flame-retarded resin layer consisting of a 90-50 pts.wt. after-chlorinated vinyl chloride resin, a 20 pts.wt. vinyl chloride resin, the 50-5 pts.wt. acrylic resin, a 1-20 pts.wt. chlorinated polyethylene (the 100 pts.wt. above-mentioned substances in total) and the 0.1-0.5 pts.wt. benzotriazole group ultraviolet absorbing agent in thickness of 10-100mu.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant, weather-resistant and impact-resistant resin laminate. More specifically, the present invention relates to a resin laminate that is excellent in flame retardancy, heat resistance, transparency, weather resistance, and impact resistance, and is suitable for exterior use, particularly as a roofing material for carports, sunrooms, and the like.

0002

2. Description of the Related Art Acrylic resin plates have been widely used as transparent resin materials for signboards, exteriors, optical parts, and the like. Although this acrylic resin board has excellent transparency and weather resistance, its flame retardancy itself is low, making it unsuitable for use in exteriors and nameplates for electrical equipment, where demand for flame retardancy has increased in recent years. Not necessarily appropriate. In order to improve flame retardancy, attempts have been made to add flame retardants such as organic phosphorus compounds, but it is necessary to add a fairly large amount of flame retardants to achieve the UL standard "V-2". Therefore, the transparency, weather resistance, and heat resistance of the resin plate are significantly reduced. moreover,
It is very difficult to achieve flame retardancy of "V-1" or better.

[0003] As transparent flame-retardant resin materials, vinyl chloride resins and flame-retardant polycarbonates are known. However, these have poor weather resistance, and furthermore, the latter have the problem of being expensive. Therefore, a transparent material that improves the weather resistance of polyvinyl chloride by laminating a plate-shaped molded polyvinyl chloride resin and an acrylic film,
This is proposed in Japanese Unexamined Patent Publication No. 3-28252. However, since the core material of such a laminate is mainly made of polyvinyl chloride, it lacks heat resistance, and when used outdoors, particularly in the summer, there is a problem that it tends to sag or wave due to thermal deformation.

Furthermore, in order to improve heat resistance, a plate in which an acrylic resin sheet containing an ultraviolet absorber is laminated on a post-chlorinated vinyl chloride resin sheet is disclosed in Japanese Patent Laid-Open No. 1-12.
This is proposed in Japanese Patent No. 7338. However, since the core material of such laminates is post-chlorinated vinyl chloride resin, they tend to be thermally colored during sheet molding, have poor transparency, and have insufficient weather resistance. There is.

[0005] Post-chlorinated vinyl chloride resins improve their heat resistance as their chlorine content increases, but they also become brittle, so they are generally blended with an elastomer component such as MBS as an impact modifier. However, when MBS is added, the weather resistance and flame retardance of the resin are reduced, making it difficult to produce a flame retardant resin laminate for outdoor use.

[0006]

[Problems to be Solved by the Invention] The present invention provides a good balance of excellent flame retardancy, heat resistance, transparency, weather resistance, and impact resistance, which has not been achieved with conventional transparent resin plates as described above. The present invention aims to provide a resin laminate suitable for exterior use, particularly as roofing material for carports, sunrooms, etc.

[0007]

[Means for Solving the Problems] The present invention provides (1) a polymerization degree of 500 to 800 before chlorination, and a chlorine content of 60
-68% by weight of post-chlorinated vinyl chloride resin 95-50
parts by weight, (2) 20 parts by weight or less of a vinyl chloride resin, which is a vinyl chloride homopolymer or a vinyl chloride copolymer consisting of 80% by weight or more of vinyl chloride and has a degree of polymerization of 400 to 1100; 3) Methyl methacrylate 68~
94.8% by weight, 5 to 30% by weight of alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms, and 0.2 to 2% by weight of alkyl acrylate or acrylonitrile whose alkyl group has 1 to 4 carbon atoms, 50 to 5 parts by weight of an acrylic resin having a reduced viscosity of 0.4 to 0.8 dl/g measured at 23°C in chloroform (
Here, the total of 1, 2 and 3 is 100 parts by weight), (4)
A flame retardant material comprising 1 to 20 parts by weight of chlorinated polyethylene having a chlorine content of 30 to 45% by weight, and (5) 0.1 to 0.5 parts by weight of at least one type of benzotriazole ultraviolet absorber. (6) 68 to 94.8% by weight of methyl methacrylate on one or both sides of the resin layer (A);
5 to 30% by weight of alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms and an alkyl group whose carbon number is 1 to 30% by weight
100 parts by weight of an acrylic resin consisting of 0.2 to 2% by weight of alkyl acrylate or acrylonitrile of 4 and having a reduced viscosity of 0.4 to 0.8 dl/g measured at 23°C in chloroform, and ( 7) At least one type of benzotriazole ultraviolet absorber 0.5
The coating resin layer (B) consisting of 10 to 10 parts by weight of
This invention relates to a flame-retardant, weather-resistant and impact-resistant resin laminate provided with a thickness of 0μ.

The post-chlorinated vinyl chloride resin (1) constituting the flame-retardant resin layer (A) of the present invention is one obtained by post-chlorinating a polyvinyl chloride resin. Here, post-chlorination methods include dissolving polyvinyl chloride resin in a solvent such as chloroform and reacting it with chlorine, or suspending polyvinyl chloride resin particles in water and blowing chlorine gas while exposing it to light or radicals. Examples include a method of reacting using a generator, and any method may be used. In addition, the degree of polymerization of the polyvinyl chloride resin before chlorination is preferably 500 to 800, preferably 600 to 700. If the degree of polymerization is less than 500, the mechanical strength of the flame-retardant resin layer will be low, and if the degree of polymerization is more than 800, the melt viscosity during molding of the flame-retardant resin layer will be high, resulting in Since the temperature has to be raised, the resin undergoes severe thermal decomposition and thermal coloring, resulting in products with inferior appearance and transparency. Further, as the post-chlorinated vinyl chloride resin (1), one having a chlorine content of 60 to 68% by weight, preferably 62 to 66% by weight is used. Here, if the chlorine content is less than 60% by weight, the heat resistance of the flame-retardant resin layer will be insufficient, and if it exceeds 68% by weight, the melt viscosity during molding of the flame-retardant resin layer will be insufficient. Since the molding temperature has to be raised, thermal decomposition and thermal coloring of the resin are severe, resulting in products with inferior appearance and transparency.

[0009] As the post-chlorinated vinyl chloride resin (1) of the present invention, a mixture of two or more resins having the above-mentioned pre-chlorination polymerization degree and chlorine content may be used. In particular, it is recommended to mainly use resins with a high degree of polymerization and high chlorine content, and also use a small amount of resins with a low degree of polymerization and low chlorine content to improve moldability without significantly reducing the mechanical strength of the resin. This is a useful method.

The vinyl chloride resin (2) constituting the flame-retardant resin layer (A) of the present invention is selected from vinyl chloride homopolymers and vinyl chloride copolymers containing 80% by weight or more of vinyl chloride. It will be done. Monomers copolymerized with vinyl chloride include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate acrylate, maleate, etc.
It is also possible to use a mixture of more than one type of homopolymer or copolymer. The degree of polymerization of vinyl chloride resin (2) is 400
~1100 are used. Here, the degree of polymerization is 4
If the degree of polymerization is less than 00, the mechanical strength of the flame-retardant resin layer will decrease, and if the degree of polymerization exceeds 1100, moldability will decrease, which is undesirable.

The acrylic resin (3) constituting the flame retardant resin layer (A) of the present invention is methyl methacrylate 68-9
4.8% by weight, 5 to 30% by weight of alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms, and 0.2 to 30% of alkyl acrylate or acrylonitrile whose alkyl group has 1 to 4 carbon atoms. It is obtained by polymerizing a monomer mixture consisting of 2% by weight. As the polymerization method, any known method such as suspension polymerization, emulsion polymerization, mercury polymerization, or solution polymerization may be used. Examples of alkyl methacrylates whose alkyl group has 2 to 18 carbon atoms include ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Examples include methacrylate, and ethyl methacrylate and n-butyl methacrylate are preferably used. Examples of the alkyl acrylate in which the alkyl group has 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like, with methyl acrylate being preferably used.

Regarding the monomer composition constituting the acrylic resin (3), if the alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms is less than 5% by weight, the acrylic resin (3) and the post-chlorine Since the compatibility with vinyl chloride resin (1) and vinyl chloride resin (2) is low, the transparency of the flame-retardant resin layer decreases, and on the other hand, if it exceeds 30% by weight, acrylic resin (3) This is not preferable because it lowers the glass transition temperature of the resin and reduces the heat resistance of the coating resin layer. Also,
If the alkyl methacrylate whose alkyl group has 1 to 4 carbon atoms is less than 0.2% by weight, the acrylic resin (3) will lack heat decomposition resistance, resulting in surface defects when forming a flame-retardant resin layer. On the other hand, if the amount exceeds 2% by weight, the compatibility of the acrylic resin (3) with the post-chlorinated vinyl chloride resin (1) and the vinyl chloride resin (2) becomes low, resulting in poor flame retardancy. The transparency of the resin layer decreases, making it difficult to obtain a good laminate. Further, if the amount of acrylonitrile exceeds 2% by weight, the resin tends to decompose and become colored during heat processing, which is not preferable.

[0013] The acrylic resin (3) also has a reduced viscosity of 0.4 to 0.0 when measured in chloroform at 23°C.
8 deciliter/g is used. here,
If the reduced viscosity is less than 0.4 deciliters/g, the mechanical strength of the flame-retardant resin layer will decrease, and if it exceeds 0.8 deciliters/g, the moldability will deteriorate, which is not preferable.

The flame-retardant resin layer (A) of the present invention comprises 95 to 50 parts by weight of the above-mentioned post-chlorinated vinyl chloride resin (1), 20 parts by weight or less of the vinyl chloride resin (2), and acrylic resin ( 3) 50 to 5 parts by weight (total of the above is 100 parts by weight)
obtained by mixing. If the post-chlorinated vinyl chloride resin (1) is less than 50 parts by weight, the flame retardant and heat resistance of the flame-retardant resin layer (A) will be poor, and if it exceeds 95 parts by weight, the transparency and coloring will be poor. Only products with inferior properties and processability can be obtained. Moreover, when the vinyl chloride resin (2) exceeds 20 parts by weight, the heat resistance of the flame-retardant resin layer (A) decreases, which is not preferable. Furthermore, if the acrylic resin (3) is less than 5 parts by weight, transparency, coloring processability, and weather resistance will be poor;
If the amount exceeds 1 part by weight, the flame retardance deteriorates, and neither can be used as a preferable flame-retardant resin layer (A).

The flame-retardant resin layer (A) of the present invention contains 1 to 20 parts by weight of chlorinated polyethylene (4) based on a total of 100 parts by weight of the above resins. As the chlorinated polyethylene, a soft one having a chlorine content of 30 to 45% by weight is used. If the chlorine content is outside this range,
The elastomeric properties of the polymer are reduced and it cannot be used as an effective impact modifier. Furthermore, if the amount of chlorinated polyethylene is less than 1 part by weight, the effect of improving impact resistance will be insufficient, and if it exceeds 20 parts by weight, the heat resistance of the flame-retardant resin layer (A) will be reduced. Neither is preferable.

The flame retardant resin layer (A) of the present invention contains 0.1 to 0.5 parts by weight of benzene based on a total of 100 parts by weight of the above resins (1), (2) and (3). Contains a triazole ultraviolet absorber (5). As the benzotriazole ultraviolet absorber, at least one type expressed by the following formula (1) is used.

[0017]

[Chemical formula 1]

For example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole 2-(3,5-di-t
-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,
Examples include 5-di-t-amyl-hydroxyphenyl)benzotriazole. In addition, in the present invention, 2
A mixture of more than one type of ultraviolet absorber may be used. If the amount of ultraviolet absorber added is less than 0.1 part by weight, the flame retardant resin layer (
The effect of improving weather resistance of A) is not sufficient, and if more than 5 parts by weight is added, the heat resistance decreases, and good results cannot be obtained in either case.

Further, the flame retardant resin layer (A) of the present invention includes:
In order to prevent thermal decomposition and thermal coloring during extrusion molding, it is preferable to incorporate a thermal stabilizer. As the heat stabilizer, those commonly used for vinyl chloride resins may be used, but when transparency of the resin composition is required as in the present invention, organotin stabilizers are preferably used. In particular, dibutyltin malate ester stabilizers and dibutyltin mercaptoester stabilizers have good compatibility with the acrylic resin (3) and are particularly preferably used. Examples include dibutyltin bisalkyl maleate, dibutyltin bisalkyl thioglycolate, dibutyltin bisalkyl β-
Examples include mercaptopropionate, and these may be used alone or in combination of two or more. It is preferable to mix 1 to 5 parts of these heat stabilizers with respect to 100 parts of the flame-retardant resin layer (A).

The flame retardant resin layer (A) of the present invention preferably contains higher fatty acid esters, higher fatty acid esters of glycerin, waxes, etc. as lubricants. In particular, glycerin monostearate has good compatibility with the acrylic resin (3) and has the advantage of not impairing the transparency of the flame-retardant resin layer. Furthermore, the flame-retardant resin layer (A) of the present invention may contain antioxidants, dyes, pigments, and the like. In particular, for exterior board materials, dyes and pigments are often mixed in to give the material a smoke color.

The coating resin layer (B) of the present invention is mainly composed of an acrylic resin (5), which contains 68 to 94.8% by weight of methyl methacrylate and a carbon number of an alkyl group. 5 to 30% by weight of an alkyl methacrylate having a carbon number of 2 to 18, and 0.2 to 2% by weight of an alkyl acrylate or acrylonitrile having an alkyl group having a carbon number of 1 to 4.
It is obtained by polymerizing a monomer mixture consisting of: Polymerization methods include suspension polymerization, emulsion polymerization,
Any known method such as mercury polymerization or solution polymerization can be used. Alkyl group has 2 to 1 carbon atoms
Examples of the alkyl methacrylate represented by No. 8 include ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. , ethyl methacrylate, and n-butyl methacrylate are preferably used. Examples of the alkyl acrylate in which the alkyl group has 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like, with methyl acrylate being preferably used.

Regarding the monomer composition constituting the acrylic resin (5), if the alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms is less than 5% by weight, the acrylic resin (5) and the post-chlorine Since the compatibility with the vinyl chloride resin (1) and the vinyl chloride resin (2) is low, the transparency of the flame-retardant resin layer decreases when an attempt is made to recycle the edge plate of the laminate. On the other hand, if it exceeds 30% by weight, the glass transition temperature of the acrylic resin (5) will decrease, the heat resistance of the coating resin layer will decrease, and the drawdown will increase when extruding the coating layer. Inhibits coating layer formation. Furthermore, if the alkyl methacrylate whose alkyl group has 1 to 4 carbon atoms is less than 0.2% by weight, the heat decomposition resistance of the acrylic resin (3) will be insufficient, and the surface will be rough when extrusion molding the coating layer. On the other hand, if it exceeds 2% by weight, acrylic resin (5) and post-chlorinated vinyl chloride resin (
The compatibility with 1) and vinyl chloride resin (2) becomes low, and when the edge plate of the laminate is recycled, the transparency of the flame-retardant resin layer decreases, making it difficult to produce a good laminate. It is difficult to obtain. Further, if the amount of acrylonitrile exceeds 2% by weight, the resin tends to decompose and become colored during heat processing, which is not preferable.

Further, the acrylic resin (5) has a reduced viscosity of 0.4 to 0.0 when measured in chloroform at 23°C.
8 deciliter/g is used. here,
If the reduced viscosity is less than 0.4 dl/g, the mechanical strength of the coating resin layer will be insufficient, while if it exceeds 0.8 dl/g, the fluidity will decrease, resulting in a thin film-like structure. This is not preferable because it makes it difficult to mold the material.

The coating resin layer (B) of the present invention contains 0.5 to 5 parts by weight of the benzotriazole ultraviolet absorber (6) based on a total of 100 parts by weight of the above-mentioned resin. As benzotriazole ultraviolet absorbers, the following (1)
At least one expression expressed by the formula is used.

[0025]

[Case 2]

[0026] Benzotriazole ultraviolet absorber (6)
may be the same as (3) above or different, and two or more types may be used in combination. Furthermore, the coating resin layer (B) of the present invention
There is no problem in adding heat stabilizers, antioxidants, impact resistance agents, etc.

The flame-retardant resin laminate of the present invention is composed of a flame-retardant resin layer (A) and a coating resin layer (B). One side of layer (A),
Alternatively, it may be provided on either side. Further, the thickness of the coating resin layer is 10 to 100 μm per side, preferably 2 μm per side.
It is 0 to 70μ. If the thickness of the coating resin layer is less than 10 μm, it is difficult to improve the weather resistance of the laminate; on the other hand, even if the thickness exceeds 100 μm, a significant improvement in weather resistance is observed. However, both of these methods are undesirable because they actually reduce the flame retardancy of the laminate.

Methods for producing the flame-retardant resin laminate of the present invention by laminating the flame-retardant resin layer (A) and the coating resin layer (B) include a coextrusion method and a lamination method. The coextrusion method is superior in that it can match the fluidity of both layers and make them uniform during lamination, resulting in good adhesion between the two layers and similar molding distortion. The coextrusion method uses two or three ordinary extruders, and the flame retardant resin layer (A) is produced using a large extruder with a diameter of 60 mm or 90 mm, while the coating resin layer (B) is produced using a large extruder with a diameter of 30 mm or 4 mm.
It is carried out by melt extrusion from a small extruder such as 0 mmφ. The thickness of the flame-retardant resin layer (A) and the coating resin layer (B) can be controlled by the extrusion rate of two or three extruders and the distance between the polishing rolls on the exit side of the extruder. I can do it. Furthermore, it is necessary to match the fluidity of the flame-retardant resin layer (A) and the coating resin layer (B), but this can be done by adjusting the temperatures of the respective extruders and dies.

In the lamination method, a film of the coating resin layer (B) with a desired thickness is prepared in advance, and when extruding the flame-retardant resin layer (A), a polishing roll on the exit side of the die is used. This can be carried out by overlapping the film of the coating resin layer (B) at a portion. In this case, the key points are to prevent air from entering during overlapping and to improve adhesion by controlling the roll temperature.

[0030]

EXAMPLES The present invention will be explained in more detail below using Examples and Comparative Examples, but the present invention is not limited by these in any way. The evaluation and test methods used here are shown below. (1) Transparency: Haze meter manufactured by Nippon Denshoku Industries Co., Ltd.
(1001DP type), haze (%) at 23℃
) was evaluated. The results are shown using the symbols below.

0031 Symbol Haze◎
Less than 5%○
5~10%△ 10~2
0% x 20% or more (2) Colorability: Color difference meter (TC-1500M manufactured by Nippon Denshoku Kogyo Co., Ltd.)
C type) was used to evaluate the degree of yellowness (denoted as ΔYI) based on air. The results are expressed using the symbols below.

[0032] Symbol ΔYI ◎ Less than 30○ 30-50△
50~70×7
0 or more (3) Heat resistance; ASTM D-648 (load 18.6
kg/cm2) and the heat distortion temperature (hereinafter referred to as HDT, °C). (4) Weather resistance: Du-panel optical control weather meter (DPWL-5R type) manufactured by Suga Test Instruments Co., Ltd.
The test pieces were irradiated for 1500 hours with a cycle of 4 hours of irradiation/4 hours of wetness, and then evaluated for haze and yellowness. (5) Impact resistance: Evaluated by Izod impact strength based on ASTM D256. (kg・cm/cm) (6
) Flame retardancy: Flammability in a vertical test was determined based on the UL94 standard.

[0033] Furthermore, the abbreviations used in the Examples and Comparative Examples represent the following compounds. MMA; methyl methacrylate n-BMA; n-butyl methacrylate i-BMA; isobutyl methacrylate MA; methyl acrylate AN; acrylonitrile LPO; lauroyl peroxide n-OM; n-octyl mercaptan HMBT; -5-methylphenyl)benzotriazole Unless otherwise specified, parts are by weight.

Acrylic resin production example 1 In a jacketed polymerization vessel with an internal volume of 60 liters, 34.2 liters of ion-exchanged water and 15 liters of trisodium phosphate were added.
9.6 g was charged, and the temperature was raised to 75° C. while stirring. MMA
21400g, n-BMA1140g, MA228g,
A mixture consisting of 65.0 g of LPO and 61.6 g of n-OM was charged and suspended, and polymerization was performed for 150 minutes.The internal temperature was further raised to 95° C. and polymerization was continued for 30 minutes to complete. Separate the polymer, wash and dry it to a particle size of approximately 0.3m.
A bead-like polymer of m was obtained.

In chloroform of the obtained polymer, 25
The reduced viscosity measured at °C was 0.55 deciliter/g. Production example 2 of acrylic resin The composition of the monomer mixture was 18200 g of MMA, i-B
A bead-shaped polymer was obtained in the same manner as in Example 1, except that it consisted of 2880 g of MA, 228 g of MA, 65.0 g of LPO, and 61.6 g of n-OM.

The reduced viscosity of the obtained polymer was 0.55 deciliter/g. Production example 3 of acrylic resin The composition of the monomer mixture was MMA20100g, i-B
A bead-shaped polymer was obtained in the same manner as in Example 1, except that it consisted of 2280 g of MA, 456 g of MA, 65.0 g of LPO, and 61.6 g of n-OM.

The reduced viscosity of the obtained polymer was 0.53 deciliter/g. Production example 4 of acrylic resin The composition of the monomer mixture was MMA20100g, MA2
740g, LPO68.4g and n-OM89.0g
A bead was prepared in the same manner as in Example 1 except that it was made of
A zigzag polymer was obtained.

The reduced viscosity of the obtained polymer was 0.43 deciliter/g.

[0039]

Example 1 A resin laminate of the present invention was molded by coextrusion. That is, for the flame retardant resin layer, an extruder with a barrel diameter of 65 mm and a screw L/D = 32 was used at a cylinder and die temperature of 180°C, while for the coating resin layer, a barrel diameter of 30 mm, Screw L/D=3
Using an extruder with a cylinder and die temperature of 22
The test was carried out at 0°C, and a laminate consisting of two layers was produced as a prototype. The thickness of the laminate was adjusted to a target of 3 mm by the interval between the polishing rolls, and the thickness of the flame retardant resin layer and the coating resin layer was adjusted by the discharge rate of each extruder.

The flame retardant resin layer is made of post-chlorinated vinyl chloride resin (polymerization degree before chlorination: 600, chlorine content: 65% by weight).
) 60 parts, 40 parts of the acrylic resin obtained in Production Example 1
1 part, 5 parts of chlorinated polyethylene, 0.3 parts of HMBT, 1.5 parts of butyltin maleate heat stabilizer, 0.5 part of butyltin mercapto heat stabilizer, and 1 part of glycerin monostearate in a Henschel mixer. The mixture was molded using -.

The coating resin layer was formed by mixing 100 parts of the acrylic resin obtained in Production Example 1 and 2 parts of HMBT using a Henschel mixer. The resulting laminate had a thickness of 3 mm and a coating resin layer of about 20 microns on one side. Table 1 shows the structure of this laminate. Table 2 shows the results of evaluating the transparency, colorability, heat resistance, weather resistance, impact resistance, and flame retardance of this laminate.

[0042]

[Examples 2 to 5] In the same manner as in Example 1, the laminates shown in Table 1 were produced. The evaluation results are shown in Table 2.

[0043]

[Comparative Example 1] The flame retardant resin layer was made in the same manner as in Example 5 except that 100 parts of post-chlorinated vinyl chloride resin was used as the main ingredient and acrylic resin and chlorinated polyethylene were not used. (See Table 3) As shown in Table 4, the initial transparency, colorability, and impact resistance were poor.

[0044]

[Comparative Example 2] The same procedure as in Example 1 was carried out except that 30 parts of post-chlorinated vinyl chloride resin and 70 parts of acrylic resin were used as the main components of the flame-retardant resin layer. As shown in Table 4, the flame retardance was poor and the test piece was completely burnt out.

[0045]

[Comparative Example 3] As the flame retardant resin layer, vinyl chloride resin 50
Example 1 was carried out in the same manner as in Example 1, except that 50 parts of acrylic resin and 50 parts of acrylic resin were used as the main components. As shown in Table 4, the results were poor in heat resistance.

[0046]

[Comparative Example 4] Except that the thickness of the coating resin layer was 150 μm,
It was carried out in the same manner as in Example 2. As shown in Table 4, the flame retardance was poor and the test piece was completely burnt out. Also, comparative example 4
In the above, a sheet having only a flame retardant resin layer without a coating resin layer was listed as 4-2. This was extremely weather resistant.

[0047]

[Comparative Examples 5 and 6] Acrylic resin with Asahi Kasei Delpowder
80N (MMA/MA = 97.5/2.5 weight ratio, reduced viscosity 0.54 dl/g), or the same as in Example 2 except that it was replaced with that obtained in Production Example 4. did. As shown in Table 4, the initial transparency was poor.

As explained using the above comparative example, in cases where the constituent requirements of the present invention are not met, transparency,
It is not possible to obtain a laminate with improved flame retardancy, heat resistance, impact resistance, and weather resistance in a well-balanced manner.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Effects of the Invention] According to the present invention, it has a good balance of transparency, flame retardancy, heat resistance, impact resistance and weather resistance, and is suitable for exterior applications, particularly as roofing materials for carports, sunrooms, etc. It is possible to provide a resin laminate.

Claims (1)

[Claims] Claim 1: (1) Degree of polymerization before chlorination is 500-8
00, and 95 to 50 parts by weight of a post-chlorinated vinyl chloride resin with a chlorine content of 60 to 68% by weight, (2) a vinyl chloride homopolymer, or a vinyl chloride-based copolymer consisting of 80% by weight or more of vinyl chloride; A polymer with a degree of polymerization of 400 to 400.
20 parts by weight or less of vinyl chloride resin having a molecular weight of 1100, (3
) 68 to 94.8% by weight of methyl methacrylate, 5 to 30% by weight of alkyl methacrylate whose alkyl group has 2 to 18 carbon atoms, and 0.2% by weight of alkyl acrylate or acrylonitrile whose alkyl group has 1 to 4 carbon atoms.
~2% by weight of an acrylic resin with a reduced viscosity of 0.4 to 0.8 dl/g measured in chloroform at 23°C (where the sum of 1, 2 and 3 is 100 (parts by weight), (4) chlorine content is 30 to 45
One side of a flame-retardant resin layer (A) consisting of 1 to 20 parts by weight of chlorinated polyethylene, and (5) 0.1 to 0.5 parts by weight of at least one type of benzotriazole ultraviolet absorber. Or, on both sides, (6) 68 to 94.8% by weight of methyl methacrylate, the number of carbon atoms in the alkyl group is 2.
It consists of 5 to 30% by weight of alkyl methacrylate having a carbon number of 1 to 18, and 0.2 to 2% by weight of an alkyl acrylate or acrylonitrile having an alkyl group having 1 to 4 carbon atoms, and the reduced viscosity measured at 23°C in chloroform is 0.
Acrylic resin 10 with a concentration of 4 to 0.8 dl/g
0 parts by weight, and (7) 0.5 to 5 parts by weight of at least one type of benzotriazole ultraviolet absorber, the coating resin layer (B) is provided with a thickness of 10 to 100μ. Resin laminate.