JPH01242649A - Lighting material of rigid vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain a lighting material which is excellent in flame retardancy and light transmittance and does not sag when it is supported by beams, by mixing a post-chlorinated polyvinyl chloride resin with a stabilizer and a specified flame retardant. CONSTITUTION:This lighting material comprises a rigid sheetlike molding of a composition formed by mixing a post-chlorinated polyvinyl chloride resin with a stabilizer and a flame retardant selected from among phosphorus- containing flame retardants and chlorinated paraffins and brominated flame retardants and antimony oxide. This lighting material can retain its sufficiently practical heat distortion temperature even when it contains, for example, a liquid flame retardant or a liquid stabilizer such as DOP. It is controlled in a decrease in a heat distortion temperature, and can contain a larger amount of a flame retardant, so that its flame retardancy can be markedly improved. It is very easy to raise its heat distortion temperature to 70 deg.C or above. When the material has such a high heat distortion temperature, it scarcely sags throughout the year even when it is in the form a rigid sheetlike molding and supported by beams of a span in the range of 670-800mm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hard vinyl chloride resin daylighting material used for building materials, partitions, etc.

[Prior art] Conventionally, plate-shaped extrusion molded bodies mainly made of methyl methacrylate resin polymer (MMA), which has the highest transparency among resins, have been used for daylighting materials that require excellent translucency. It is being This is because MMA is a thermoplastic resin that has excellent weather resistance as well as transparency. When using a plate-shaped molded body mainly made of MMA as a daylighting material for carports, sunroofs, etc., its thickness is set to 2 to 3IIffl, and the span gap of the beam material that supports the daylighting material is in the range of 670 to 800+1111. is set to . The reason why the span gap is set in the range shown in ``2'' is because if the span gap is narrower than this, too many beams will be used and the beams will obstruct lighting, while if the span gap is wider than this, it will be difficult to use during summer, etc. This is because the lighting materials sag when the temperature is high.

However, a plate-shaped molded body mainly composed of MMA having the above-mentioned thickness has a drawback that it has poor impact resistance and is easily cracked during transportation and especially during cold bending during construction. Furthermore, MMA is flammable and is not certified as a fire-retardant material according to the fire-retardant material tests stipulated by the Building Standards Act. Therefore, when used as a lighting material, although it is satisfactory in terms of transparency and weather resistance, it does not meet the recent trend towards flame retardant construction materials.

Tests on fireproof materials are conducted to ensure that building materials are non-combustible, with the main factors being flammability, which measures afterflame time during combustion, and smoke generation, which measures exhaust temperature (smoke temperature) and smoke emission coefficient during combustion. fire-retardant materials that fall into the categories of wood, semi-noncombustible material, flame retardant material, and semi-flame retardant material, and materials that do not pass the above tests (
Hereinafter referred to as flammable materials. ), and according to this test, building materials that belong to the category excluding combustible materials comply with the flame retardant orientation.

On the other hand, the above-mentioned lighting material is made of vinyl chloride resin polymer (PVC).
) A corrugated extrusion molded product (corrugated sheet), which mainly consists of corrugated sheets, is sometimes used. PVC itself exhibits flame retardant properties, and a hard plate-shaped molded body mainly made of PVC with a thickness of 1.4 mm or less is judged to be a semi-flame retardant material in the fire prevention material test described in -. Therefore, the 2-corrugated plate with a thickness of 1.4 mm or less meets the above-mentioned flame retardant requirements, and also satisfies the rigidity required for daylighting materials such as car boats and sunroofs due to its shape retention due to its wave shape. be done. However, car boats, sunroofs, etc. that use such corrugated sheets lack a sleek appearance compared to those that use the above-mentioned MMA-based molded bodies, and therefore, despite being semi-flammable materials, the above-mentioned MMΔ It has not reached the point where it has been replaced by the main lighting material.

Therefore, it is considered that a flat hard plate having a thickness of 1.4 mm or less, which is a semi-flame retardant material, is molded from a composition mainly composed of PVC, and such a hard flat plate-shaped molded body is used as a lighting material.

By the way, as is well known, conventional PVC-based rigid plate-shaped molded products are molded from a composition in which stabilizers such as a main stabilizer, a plasticizer, and a lubricant are blended with PVC, and the proportions of these are determined depending on the purpose. It is selected as appropriate depending on the characteristics required for the molded product. In the case of conventional rigid plate-shaped molded bodies, a tin-based substance (mainly liquid) or a lead-based substance (solid) is used as the main stabilizer. Among these, lead-based stabilizers have the advantage of not significantly lowering the heat distortion temperature of hard flat molded bodies, but on the other hand, they are inferior in transparency compared to tin-based stabilizers and reduce the lighting performance of hard flat molded bodies. Since it has the disadvantage of causing losses,
Tin-based stabilizers that do not impair translucency are mainly used as stabilizers for flat molded bodies that require translucency similar to that of MMA-based lighting materials. On the other hand, most of the tin-based stabilizers are liquid, and when used, the heat distortion temperature of the hard plate-shaped molded product is lowered. Furthermore, the viscosity of the molding raw material becomes too high, resulting in poor molding processability, making extrusion molding impossible. Therefore, by blending dioctyl phthalate (DOP), which is a -JG type plasticizer, the increase in viscosity caused by blending the tin-based stabilizer is suppressed, and molding processability is improved.

However, in order to improve moldability to the extent that extrusion molding is possible, it is necessary to mix 3 to 5 parts of DOP, and when that amount of DOP is mixed, the heat distortion temperature drops to about 60°C. If it is supported by beams arranged with the above-mentioned span gaps, the rigidity will be insufficient during high temperature periods such as summer, and the lighting material will bend downward due to its own weight in the span gaps of the beams. It cannot withstand actual use. This situation occurs regardless of the thickness, although there are differences in degree, and of course, for flat molded products with a thickness of less than 1.4au++,
This also occurs with thicker plate-shaped molded bodies. Also, 1
．． A hard plate-shaped molded body mainly composed of PVC having a thickness of 5 mm or more is determined to be combustible in terms of afterflame time, smoke generation coefficient, etc. by the above-mentioned fire prevention material test.

Therefore, a PVC-based rigid plate-shaped molded product containing 3 to 5 parts of DOP cannot be used as a substitute for conventional MMA-based daylighting materials because thin products lack deflection resistance, and thick products lack deflection resistance. It was unsuitable for practical use as a lighting material because of the lack of oxidation and the fact that it did not meet the flame retardant trend.

(Problems to be Solved by the Invention) As described above, conventionally, when a flat molded body mainly made of MMA or a hard flat molded body mainly made of PVC with a thickness of 1.5 m or more was used as a lighting material, While this goes against the desire to make the material flame retardant, when using a conventional thin hard plate-shaped molded product mainly made of PVC, although it meets the above flame retardancy goal, there are problems such as not ensuring the necessary deflection resistance. was there.

The present invention was made in view of these problems, and even though it is a flat plate-shaped molded product, it was determined to be a semi-flame retardant material in the above fire prevention material test, and it meets the recent trend towards flame retardant construction materials. Moreover, it has excellent translucency, and furthermore, the span gap mentioned above is 67.
The purpose of the present invention is to provide a hard vinyl chloride resin daylighting material that does not easily sag throughout the year even when supported by a beam H set in the range of 0 to 800 mm.

[Means to solve the problem]

The hard vinyl chloride resin lighting material of the present invention is a post-chlorinated polyvinyl chloride resin (hereinafter referred to as HT-PVC), a stabilizer and a phosphorus flame retardant selected from chlorinated paraffin, bromine, and antimony oxide. It is characterized by being made of a hard plate-shaped molded product of a composition blended with a flame retardant.

[For production]

The hard polyvinyl chloride resin lighting material of the present invention is HT-
Because it uses PVC, even liquid flame retardants and D
Even if a liquid stabilizer such as OP is used, a heat distortion temperature that can withstand practical use can be maintained.

In addition, the excellent flame retardancy and heat resistance of HT-PVC suppresses the drop in heat distortion temperature caused by adding flame retardants, making it possible to mix more flame retardants, significantly improving flame retardancy. will be able to improve. It is extremely easy to raise the heat distortion temperature to 70°C or higher, and if it has a heat distortion temperature of this level, even if it is a hard plate-like molded product, the above-mentioned span gap can be reduced. When supported by beams, it is unlikely to sag throughout the year.

〔Example〕

FIG. 1 is a sectional view of the hard vinyl chloride resin lighting material of the present invention, in which a protective film 2 mainly made of MMA and having a thickness of 25 to 200 μm is laminated on the surface of a hard vinyl chloride resin molded body 1. The hard vinyl chloride resin molded article 1 is made by blending HT-PVC with a phosphorus-based flame retardant, a chlorinated paraffin, a bromine-based flame retardant, and an antimony oxide flame retardant, as well as a tin-based flame retardant that is usually added to molding raw materials. It is a transparent product made by extruding or press-molding a composition containing stabilizers, lubricants, reinforcing agents, etc. into a flat plate using a known extruder or press machine used for PVC molding, and it is a molded product mainly made of MMA. It has the same level of transparency as that of other materials, and the light transmittance required for daylighting materials is sufficiently ensured. Moreover, it has a heat deformation temperature at which mechanical strength such as deflection resistance is sufficiently maintained. The light transmittance includes transparent or semi-transparent, and the total light transmittance is transparent and has 80 to 90%. To make it translucent, add pigments or other known substances, or make the surface matte.
Layering colored films. The heat deformation temperature of the hard vinyl chloride resin molded article 1 is 70° C. or higher, which is a temperature at which sufficient mechanical strength such as deflection resistance can be ensured. In addition, when the material is translucent, a lead-based stabilizer may be used as the main stabilizer.

PVC, which is the starting material for HT-PVC, has a polymerization degree of 500~
800 vinyl chloride straight polymer, copolymers with other resins such as ethylene, alloys, etc. And H.T.
-PVC is obtained by chlorinating these PVCs, and the chlorine content reaches 62-68%, PVC
Contains more chlorine than 56-57% of VC. Therefore, I(T-PVC has superior heat resistance and flame retardancy compared to PVC.An example of HT-PVC is Sekisui P, a product manufactured by Tokuyama Block Chemical Industry ■.
Examples include VC-HAJ and "Nikatenbu" manufactured by Nippon Carbide Industries.

When the composition of the hard vinyl chloride resin molded article 1 contains liquid phosphorus or chlorinated paraffin as a flame retardant, the heat distortion temperature tends to be lower than that of a composition that does not contain them. If the blending ratio of these flame retardants is too large, the heat distortion temperature may drop to 70° C. or lower, leading to a risk of insufficient deflection resistance. Note that the heat distortion temperature is measured using AST
The test was carried out using MD-648 and a load of 18.6 kg/c.

Therefore, the blending ratio of liquid flame retardant is such that the heat distortion temperature is 70°C.
It is necessary to keep it within the range below. However, H
T-PVC originally has a high heat distortion temperature (90 to 110
°C), so even if a flame retardant is added, it is difficult for the temperature to drop below 70 °C. Furthermore, the heat distortion temperature is not only affected by the blending ratio of the flame retardant, but also by the blending ratio of other additives such as tin-based stabilizers, DOP, and reinforcing agents.
It is also necessary to consider their blending ratio.

On the other hand, when using bromine-based flame retardants or antimony oxide as a flame retardant, since the bromine-based flame retardant is a powder and the antimony oxyoxide is a fine particle solid, the deformation temperature does not decrease much. Depends on the blending ratio. The range in which flame retardants can be blended is extrusion or calendering.
Taking into consideration the moldability of presses, flame retardancy, cost, etc., the range in which liquid flame retardants such as phosphorus-based flame retardants can be blended is HT-
It is 6 parts or less per 100 parts of PVC. If the blending ratio of the flame retardant is too small, its effectiveness cannot be expected. The range that can be expected to be effective is 0.5 per 100 parts of HT-PVC.
It is more than 100%. In addition, there are organic phosphorus-based flame retardants such as orthophosphoric acid esters and phosphonic acid esters as phosphorus-based flame retardants that can improve transparency by using antimony pentoxide in combination with phosphoric acid esters. It is often added as a plasticizer for polyurethane resins and phenolic resins, and orthophosphoric acid ester is suitable for PVC. Phosphorous flame retardants belonging to orthophosphoric acid esters include, for example, the product name "TOP," manufactured by a@Daihachihegaku Kogyo Co., Ltd.
rTOPJ, rcLPJ, rcRP,.

rTppu, rcDP”, rXDpJ, r#41J
.

rcR-38 (b, 'CR-500J, r
CR-509,+.

rCR-513j, rCR-530J,
rCR-733J.

rCR-735'', 'UF-807J, rPPX
-33, etc., and phosphoric acid ester flame retardants include the company's product name CR-104J, r
CR-705”.

There are rCR-706J, rCR-7074, etc. Next, we will list the chemical names, molecular weights, properties, etc. of representative phosphorus-based flame retardants.

TCP: Chemical name tricresyl phosphate, M, W.

36B, provides heat resistance and electrical insulation to PVC,
Excellent lubricity.

TOP nitri-2-ethylhexyl phosphate MJ1.
435. Gives PVC cold resistance and elasticity.

CLP Nidris Chloroethyl Phosphate S.

W, 285. It has a high phosphorus and chlorine content and is insoluble in water.

CRP: I-IJ-dichloropropylphos-1-M
, W, 431. It has a higher chlorine content than CLP and is more resistant to hydrolysis.

TPP: l-Riphenylphosphate M, W, 326° Excellent water resistance.

CDP: cresyl diphenyl phosphor) M, W.

340, has excellent gelling effect on PVC, cold resistance, and stain resistance, and has higher viscosity than TCP.

XDP: xylenyl diphenyl phosphate HoW,
354. Excellent gelation effect on PVC.

#41: 2-ethylhexyldiphenylphos-1
・M, W, 362. Provides light, heat, and cold resistance to PVC.

These phosphorus-based flame retardants can improve thermal stability, weather resistance, and cold resistance when used in combination with DOP.

It is also possible to combine phosphorus-based flame retardants with each other or with other types of flame retardants.In particular, antimony oxide is a fine particle, and the heat distortion temperature can be improved by the amount that can reduce the amount of liquid phosphorus-based III flame retardant. Can be done.

When using chlorinated paraffin as a flame retardant, HT-PV
It is 10 parts or less per 100 parts of C. If the blending ratio of chlorinated paraffin is too small, its effectiveness cannot be expected. The range in which efficacy can be expected is 2 parts or more per 100 parts of HT-PVC.

As the bromine-based flame retardant, tetrabromoethane, tetrabromobutane, tri(bromochloropropyl)phosphate, high bromine-containing aromatic compounds, etc. can be used.

Flame retardants for antimony oxide include antimony trioxide,
Antimony pentoxide is mainly used, but antimony trioxide is preferably used because of its excellent transparency.

The protective film 3 may be laminated only on one side of the hard vinyl chloride resin molded body 1 as shown in FIG. 1, or may be laminated on both sides as shown in FIG. The protective film 3 may be transparent, but various types such as a printed pattern, a textured pattern (matte pattern), a colored film, etc. can be adopted. Furthermore, a two-layer structure in which a transparent film 2 is laminated on a patterned film or the like may be used. Furthermore, a fluorine film 3 may be further laminated on the protective film 2 as shown in FIGS. 3(a) and 3(b). Further, although not shown, a light-transmitting antistatic or conductive layer may be provided on the outer or inner surface of the two-layer film 2.3 to prevent dust from adhering to the surface. The protective film 2 may be a PVC film rich in ultraviolet absorbers and improved in weather resistance, and such a film may be omitted if unnecessary.

17 of hard vinyl chloride resin molded product 1 is 1.5 mark or more.
2. It is preferable to set it to 1.5 to 7.0 Peng. If the material is thinner than 1.5 mm, it is determined to be a semi-flame retardant material in the above-mentioned fire prevention material test, but it lacks flexibility and is likely to sag from the gaps between the beams due to its own weight. Moreover, if the thickness is too thick, it will cause disadvantages in terms of transparency, moldability, cost, etc. The most desirable thickness range is 1.8 to 3 m, and this range is about the same as the thickness when using a plate-shaped molded body mainly made of MMA as a lighting material, and it is also superior in terms of price etc.
It can be substituted for the M A polymer molded body.

The lighting material A may be a flat plate, or may have reinforcing ribs 4 integrally formed with the hard vinyl chloride resin molded body 1 as shown in FIG.

Further, when the daylighting material A is used for a carport or a sunroof, the shape may be a dome shape or a flat IU shape. When the span gap of the beam supporting the daylighting material A is wide, the reinforcement rib 4 described above may be provided, or two flat plate-shaped hard vinyl chloride resin molded bodies may be stacked and bound together,
Flat plate-shaped hard vinyl chloride resin molded body and reinforcing ribs 4
For example, two hard vinyl chloride resin molded bodies having the same structure are stacked with reinforcing ribs 4 in between, or metals such as piano wire, wire mesh, punched metal, etc. are embedded in the hard vinyl chloride resin molded body 1, etc. A material with improved mechanical strength may also be used.

Next, samples 1 to 8 were prepared by molding the various compositions shown in Table 1 into flat plates with different thicknesses, and the transparency and heat distortion temperature of these were shown in the same table. Table 2 shows the results of the fire protection material tests.

(Hereinafter, blank space) Table 1 ◎ indicates clear transparency, ◯ indicates transparency, △: frosted glass-like transparency.

Table 2 (hereinafter referred to as blank space) Table 2 shows that the PVC-based hard vinyl chloride resin molded product (sample 1) that does not contain TCP has a thickness of 1.
If it is thinner than 4 mm, it is determined to be a semi-flammable material, but if it is thicker than that, it is determined to be combustible, whereas a hard vinyl chloride resin molded product mainly containing H T-PVC containing TCP. It can be seen that (Sample 6) is determined to be a semi-flame retardant material even if the thickness reaches 7111111111. From this,
The hard vinyl chloride resin lighting material of the present invention is suitable for the purpose of flame retardant construction materials.

In addition, Table 1 shows that the reduction in heat distortion temperature due to the addition of TCP, chlorinated paraffin, or antimony trioxide is
It can be seen that the heat distortion temperature is suppressed by T-PVC and remains 80°C or higher even when the blending ratio of TCP, chlorinated paraffin, and antimony trioxide increases.

Figure 5 shows a flat plate-shaped hard vinyl chloride resin molded body (invention product: Sample 6, heat distortion temperature 84'C) used as the hard vinyl chloride resin lighting material of the present invention, and a flat plate-shaped molded body mainly composed of MMA. (Comparative product 1: Heat distortion temperature 80"C) and a PVC-based hard plate-shaped molded product containing DOP as a plasticizer (Comparison product 2: Zamble 1. Heat distortion temperature 63"C
) and a PvC-based hard plate molded body containing a phosphorous flame retardant (Comparative product 3: Sample 2, heat distortion temperature 71'C)
and the existing car boat (beam span gap 670~80
0 m) is a graph substituted for a drawing showing the results of a test comparing the deflection resistance when the material is used as a daylighting material and is actually used over a period of time when the temperature is high in the summer and a time when the temperature is low in the winter. The vertical axis indicates the deflection width, and the positive side indicates that the lighting material was deflected downward (sagging).
In this case, the negative side is that the lighting material is bent upward (bulged).
It shows 17m. Moreover, the horizontal axis is the elapsed time. Possible causes of the denting or swelling of the lighting material include the lighting material softening due to heat accumulation and bending under its own weight, as well as thermal expansion and contraction. Even taking these matters into consideration, it is thought that a material that does not sag too much can be suitably used as a lighting material in the span gap. Comparative products 2 and 3 show that if the heat distortion temperature is 70°C or higher, it can be used as a lighting material for an existing carport without causing any major problems. In addition, the invented product showed the same behavior as Comparative Product 1, indicating that Comparative Product 1 can be replaced by the present invention product, and also showing that it can be used without any problem even if the temperature rises further. There is.

〔Effect of the invention〕

The hard polyvinyl chloride resin lighting material according to the present invention is HT
- Since PVC is used, even if DOP is used, the heat deformation temperature will not be lowered much, so DOP can be used and moldability is improved.

Moreover, the hard vinyl chloride resin molded article of the present invention is HT-P
Since VC is used, it is extremely easy to maintain the heat distortion temperature at 80°C1 or at least 70°C, and the span gap of the beam material is set to about 670-800III11 to support the rigid flat plate-shaped molded body. By making the conventional M
It does not sag downward even as a substitute for a flat plate-shaped molded product mainly composed of MA. In addition, since it is a hard molded product made of a composition that is mainly made of HT-PVC and added with flame retardants such as phosphorus-based flame retardants and chlorinated paraffin, compared to conventional plate-shaped molded products that are mainly made of MMA, Of course, it has excellent flame retardancy even when compared to conventional PVC-based hard plate-shaped molded products.
Not only when the thickness is thinner than 1.5m, but even when the plate-shaped molded product is made with a thickness that can maintain the mechanical strength required for daylighting materials, such as 1.5 to 7 degrees, it cannot be tested as a fireproof material. It is judged to be a quasi-flame retardant material, and is compatible with the recent trend toward flame retardant construction materials. Therefore, it can be substituted for a daylighting material made of a plate-shaped molded body mainly composed of MMA.

In addition, since the flame retardant blended into the hard vinyl chloride resin molded article of the present invention is transparent, there is an advantage that the reduction in transparency due to the blending of the flame retardant is minimized and sufficient lighting is provided. In addition, H T -PV with excellent moldability
Since it is mainly composed of carbon, it has good moldability and is resistant to cracking, which are the properties required for daylighting materials.

[Brief explanation of the drawing]

Fig. 1 is a sectional view of a hard vinyl chloride resin daylighting material according to an embodiment of the present invention, Figs. The cross-sectional view and FIG. 5 are graphs substituted for drawings showing the deflection resistance of the hard vinyl chloride resin molded article of the present invention. 1...Hard vinyl chloride resin molded body. Patent applicant Takiron Co., Ltd. Figure 1 Figure 2 Figure 3 (a) Figure 3 (b) Figure 4

Claims (1)

[Claims] 1. It is characterized by being made of a hard plate-shaped molded product of a composition in which a post-chlorinated polyvinyl chloride resin is blended with a stabilizer and a phosphorus-based flame retardant or a flame retardant selected from chlorinated paraffin, bromine-based and antimony oxide. Hard vinyl chloride resin lighting material.