JPS5865651A - Coating sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel low-density cellular product obtained from an unsaturated I-lyester resin-based foam.Flat or molded sheets for covering buildings are of three known types: The first type is galvanized thin (1-2-) steel sheet. This sheet is light and opaque, but is easily corroded and lacks insulation. The ability to provide a walkable surface is poor, ie, if a person walks on a roof made of this sheet, it will cause deformation and damage.

The second type is obtained from a mixture of cement and aspest fibers and is commonly known under the trade name "El@rnlt". This has the advantage of being low cost despite being the thickest (5-9m) you can walk on. Furthermore, it is opaque, and both zinc and sheet metal have excellent insulation properties. However, processing asbestos is dangerous because it can easily cause cancer. It becomes brittle over time due to erosion from lightning and frost and therefore cannot provide a walkable surface.

The $3 type is reinforced with fiberglass and made from nine unsaturated polyester resin. It differs from the above two types in its transparency, which makes it desirable for covering large areas such as courtyards, and its thin thickness (0.8-2 mm).
Although it is extremely light and has excellent weather resistance, it has the disadvantage of not being able to provide a walkable surface and has poor thermal insulation properties.On the other hand, sheets can be made by adding opacifying minerals or fillers to the unsaturated polyester resin. It is impossible to make the sheet opaque unless the sheet is sufficiently thick < (5 ms or more), and it is uneconomical to make the sheet thick.

The use of a low density cellular material based on unsaturated/IJ ester resin foam reinforced with Applicant wire glass fibers provides high insulation capacity, sufficient opacity, long term weather resistance and a safe walking surface. We have found that it is possible to obtain sheets, in particular corrugated or otherwise rigid sheets, which have sufficient mechanical properties that can・The sheet of the present invention having a cell structure also has an excellent nine-stiffness structure ・The density of the sheet of the present invention contains glass fiber and other fillers In this case, preferably 0.3 to 0.9 kQ/it,
More preferably 0.5 to 0.8 kg/1. It is t. Conventional corrugated glass fiber reinforcement with a density of approximately 1.4 kg/l* and a thickness of approximately 1.5 kg/l*? If you compare the ester sheet with a density of 0.64 kg/lt and 3.3
A sheet of the present invention having a thickness of 1 has the same weight. The results of comparing the thermal insulating ability of the conventional sheet and the sheet of the present invention with the same weight are as follows: Thermal conductivity of the conventional glass fiber-reinforced polyester sheet with a thickness of 1.5 mm is as follows: 0 indicated by 113keal/na2h'tm
The thermal conductivity of the sheet according to the invention with a density of , 64 kri/At and a thickness t of 3,3 cm is given by Q = 9 kcal/m2h°C.

As is clear from the comparison of the above values, the heat insulating capacity of the sheet of the present invention is about 12 times that of the conventional glass fiber reinforced polyester sheet. Both sides exposed to sunlight may be coated with a capable metal film or metal-coated plastic film; the metal used for this coating may be aluminum, preferably anodized aluminum. The same effect can also be obtained by dispersing a metallic pigment consisting of powder of a metal such as aluminum in the foamed material constituting the sheet of the invention.

The sheet of the present invention may be colored by dispersing or dissolving pigments or dyes in the resin constituting the sheet, and the corrugated hard fibers are made of an unsaturated 4-lyester resin or laminate typically used in the production of lath sheets. Unsaturated polyester resins commonly used in the production of may be used in the production of the sheets of the present invention; if self-extinguishing properties are required for the sheets, mineral fillers such as hydrated alumina may be used. In this case, alumina water may be added to an unsaturated polyester resin in an amount of 10% by weight or more, or a carbonated resin containing 10g/15p by weight or more of bromine may be used. The maximum amount of halodane used depends on the degree of self-extinguishing desired. Commercially available glass fibers, preferably cut filament mats or continuous filament mats, or chisels, sheets, etc., are used to reinforce the sheets of the invention. Strands, drawn filaments are employed, and the glass fibers may also be used in the form of woven rovings, the amount of glass fibers used being 40 weight-trench of the sieve composite.

Continuous or discontinuous processing equipment used to make laminates of unsaturated/IJ ester resins may be used to make the sheets of the present invention.

Commercially available equipment for continuously producing corrugated fiberglass sheets may be used to produce the corrugated sheets of the present invention from foam materials; in the present invention, the foam manufacturing step is performed before the sheet forming step. It is necessary. Physical or chemical foaming processes may be used to produce the foam.

Foam! ! ! fj [is usually 0.25 to 0.8 kg/Lt, without considering reinforcing glass fibers and fillers.
a preferably between 0.4 and 0.7 ky/lt, and when calculating the density of the foam, take into account the increase in density due to shrinkage of the resin through the curing process and the increase in the density of the glass fibers and fillers. In the present invention, the preferred method of producing the foam is to mechanically occlude closed-cell gases into an unsaturated 4-liester resin. This method is published in Italian Patent No. 1j No. 22578 A/7.
9 and West German Publication No. 3016333. Air or preferably an inert gas, such as nitrogen or carbon dioxide, is used as the storage gas.The foam may be partially or completely expanded by physical or chemical foaming. Alternatively, it may be replaced in whole or in part by physical foaming with low boiling materials such as fluorinated hydrocarbons.

If chemical foaming is employed, chemical reactions that generate gaseous compounds, such as the decomposition of carbonates and bicarbonates,
Also, the company's isocyanate reaction is utilized.

In the case of physical or chemical foaming, unlike in the case of mechanical loading of the lath, the foam is produced directly on the sheet-making machine or is pre-produced. If the foam is prefabricated, it must be stable and not collapse for a sufficient period of time to allow sheet production.

For this purpose, it is necessary to add a foam stabilizer as described in the above-mentioned Italian application. When glass fiber IIt is mixed, two methods are adopted.

If the foam is produced by mechanical occlusion of gas, glass fibers called strands are used;
This fiber is preferably introduced through a process using a foam manufacturing device as described in the above-mentioned Italian application. If drawn filaments are used, this is pretreated on the lamination machine. Ru. If cut filament mats or continuous filament mats are employed,
Sheet thickness l■A'#:, υ0.05~0.35 ky/
It is desirable to immerse a mat having a weight of m in a pre-prepared foam or in a resin containing a physical or chemical blowing agent through a sheet lamination process.

The second step in producing foamed sheets, particularly corrugated or otherwise formed sheets, is to use conventional continuous cycle machinery, particularly equipment for producing corrugated fiberglass sheets, to laminate the glass fiber-containing foams and to process them in a manner that does not destroy the air bubbles. The curing of the glass fiber-containing foams, consisting of curing under conditions, takes place by the action of known crosslinking agents based on organic peroxides. A preferred crosslinking composition is a combination of acetylacetone and/or cyclohexanone and/or methyl ethyl ketone 1,000-oxide with a cobalt compound promoter such as cobalt octoate. The curing time usually varies between room temperature and 100°C. For example, equipment for manufacturing corrugated sheets with a length of 50 m and a processing speed of 5 m/min and a curing furnace (length 30 m) with a heating temperature of 60-80°C.
The crosslinking composition when using is as follows.

Hyde mouth non-inhibitor = 250-350 ppm cobalt octoate accelerator (6 wt% styrene solution) = 0.
18-0.25% by weight.

Example: Acetylacetone - Oxide initiator = 0.5 to 1 weight - Both the foam making process and the sheet curing process should be carried out to obtain a cellular material containing mostly closed cells. This is due to providing a sheet with good insulation and air impermeability. Therefore, the number of closed cells is at least 709 of the total cells! , preferably at least 80%
Examples of the present invention will be described below.

Example 1 An unsaturated polyester resin was prepared by condensing a composition consisting of 2000 moles of maleic anhydride, 1000 moles of phthalic anhydride, and 3100 moles of propylene glycol at about 190° C. for 12 hours. After reaching an acid number corresponding to 30 mQ of KOH per g of saturated-lyester, the product was cooled to 110°C and then treated with a 6% by weight styrene solution of 223 JF of styrene, 250Q of hydroquinone, and cobalt octoate. 1.5 kQ was added under stirring. The resulting resin has a viscosity of 1300 centipoise at 25°C. Using the obtained resin, the Italian Patent Applicant 225
79 A/79, West German Gazette, O, S, A301633
Based on the method described in 4, a foam with a density of 0.5 kg/lt was produced continuously by mechanical occlusion of nitrogen. of acetylacetone peroxide was continuously fed to the foam. Appearance The foam obtained in Example 1 was fed to a commercially available continuous manufacturing equipment for fiberglass sheets, so that the foam had a thickness of 3.7 wr. A 1.35°C wide flat sheet was formed at a processing speed of 5W&/min. The feed rate was 827 ka1 hour. This 7 ohm was evenly distributed on the conveyor belt of the above device and weighed 375 g at 1.35 m inside.
/m2 of continuous glass filament mat was immersed into the above foam, the resulting composite was laminated and passed through a 30°C long furnace heated to 70°C. At the exit of the furnace, the sheet was fully cured and then cut. The properties of the obtained sheet are as follows.

Density = 0.58 kQ/At glass fiber amount -18 weight- Tensile strength -1'40 kg/cm 2 Tensile modulus = 17100 and σ/32 thickness
;3.7■ Transparency to sunlight=none] 11㉋A Form 1 of Example 1 *Processed based on the method of Example 2 to obtain a sheet with a thickness of 6■. For this purpose, 13X+-4/
A continuous glass filament mat with a foam of 608 kQ/m2 was supplied. Lamination, curing, and cutting cycles are the same as in Example 1.

Large Cap 11 A corrugated sheet of thickness 3.7 snow x, os 4 m'rh was produced continuously using the form of Example 1 and the method of Example 2. The foam is supplied at a rate of 646 kg 7 tons and has a width of 1.054 ffl and a weight of a 75 a/
m2 continuous glass filaments were fed simultaneously.

Contrary to Example 2, the foam layer with the glass filament mat was placed on a mold having the shape of a commercially available "Et@rnit" corrugated sheet after lamination and before entering the heating oven. , then put into a heating furnace and cut at the exit of the furnace. The properties of the sheet obtained were the same as those of the sheet of Example 2. Example 5 An unsaturated polyester resin was produced according to the method of Example 1 using the following components.

550 moles of hexachloroendomethylenenitetrahydroheptalic acid.

450 mol maleic anhydride. 850 moles of diethylene glycol.

250 moles of globylene glycol.

In polycondensation, the acid value is unsaturated / KO per gram of 17-ester
The product was then cooled to 110 °C and added to 200 kg of styrene, 160 g of toluhydroquinone, los kg of 6% by weight cobalt styrene octoate.
lit1. A 1335 kg of I-reester was added. 543 kg of the resulting resin was mixed with 534 kg of the nine resins obtained in Example 1. This hot metal article was published in Italian Patent Application No. 22578 A/79, West German Publication, 0.
No. 8.13016333, 0.5 kJ of acetylacetone peroxide was used to continuously produce a foam containing 0.5 kJ of carbon by mechanical storage of nitrogen. was continuously added to the foam just before exiting the foam machine hold.

Example 6 The foam obtained in Example 5 was fed to a continuous resin-glass fiber sheet manufacturing apparatus at a rate of 895 kg/h, and a flat sheet 3.7 m thick and 1.35 m wide was produced at 5W. @／
Obtained in minutes. The foam is evenly distributed on the conveyor belt of the above device and is
A continuous glass filament mat weighing 75 g/m'' was immersed into the foam. The resulting composite was laminated and then passed through a 30°C long furnace heated to 70°C. At the exit of the furnace, the sheet was completely cured and then cut.The properties of the nine sheets obtained are as follows: Density = o, 62 kct/l*
Glass fiber amount = 17.5 weight - tensile strength = 132 kff/z2 tensile modulus
= 18200 kf/z2 thickness
= 3.7 ■ Transparency against sunlight = None This sheet showed self-extinguishing property.Applicant's agent Benboshi Suzue Takehiko Procedure amendment written form) F! J31 and July 19th 21゜ Kazuo Wakasugi, Commissioner of the Japan Patent Office 1, Indication of the case, Japanese Patent Application No. 1982-127436, 2, Invention title cover sheet 3, Person making the amendment, Relationship with the case, Patent applicant Esther. Resin/IJ Nistel Nis P.N. 4, Agent 6, Supplementary IE Subject Procedure Amendment 57.1021 1925/2017 Commissioner of the Japan Patent Office Kazuo Wakasugi 1, Patent Application for Indication of Case @ 57-127431 No. 2, Invention title covering sheet 3, Relationship with the case of the person making the amendment Patent applicant Esther Resin, 1F9 Nistelenis Beanie 4, Agent 5, Spontaneous amendment 6, Invention increased by amendment 17. The scope of claims of the specification to be amended 8 and the description of contents of the amendment are attached as attached.

2. Claims (1) A sheet consisting of a low-density cellular material based on a substantially unsaturated polyester resin, characterized in that the material is opaque and reinforced with glass fibers. A covering sheet with high heat insulation, weather resistance, and high mechanical properties.

(2) The covering sheet according to claim 1, wherein the sheet is hard (and flat).

(3) A covering sheet according to claim 1, wherein said sheet is rigid and molded.

(4) The covering sheet according to any one of claims 1 to 3, wherein the sheet contains a filler.

(5) The glass fiber is a continuous filament 7F mat.

One cut filament mat! The covering sheet according to any one of claims 1 to 4, which is used in at least one form of a twisted strand or a drawn filament.

(6) The covering sheet according to any one of claims 1 to 5, wherein the sheet has a density of 0.3 to 0.9 kl/lt.

()) The covering sheet according to any one of claims 1 to 6, wherein Sea F has a density of 0.5 to 0.8 匈/lt.

(8) What about the seat? (The covering sheet according to any one of claims W1, items 1 to 7, having one or more closed cells.

(9) The covering sheet according to any one of claims 1 to 8, wherein the sheet is self-extinguishing.

(1) The coated sheet according to claim 9, wherein the sheet contains 10 or more by weight of alumina hydrate.

The αυ sheet is manufactured from an unsaturated ester resin containing more than the chemical C=bonded bromine or other halogen tS*! The covering sheet according to item 9.

1. The coated sheet according to any one of claims 1 to 11, wherein the sheet is coated with a metal film or a metal-coated plastic film.

Ql The coated sheet according to claim 12, wherein the metal film is anodized aluminum.

I. The coated sheet according to any one of claims 1 to 11, wherein the sheet contains metal pigment tubes in the form of metal powder.

a9 The coated sheet according to any one of claims 1 to 11, wherein the sheet is colored with a pigment or dye.

Axis of claim used with stimulant-1iX16. II
Toge Higashigengaita & forming method.

Law.

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Claims (1)

[Scope of Claims] (1) An opaque, high thermal insulation sheet consisting of a low-density cellular material based on a substantially unsaturated/lyester resin, the sheet being reinforced with glass fibers. Covering sheet with high durability, weather resistance and high mechanical properties. (2) The covering sheet according to claim 1, wherein the sheet is hard and flat. (3) A covering sheet according to claim 1, wherein said sheet is rigid and molded. (4) The covering sheet according to any one of claims 1 to 3, wherein the sheet contains a filler. (5) The glass fibers may be continuous filament mats, cut filament mats, (6) The sheet has o, a to o, e ka/lt. The covering sheet according to any one of claims 1 to 5, which has a density. (7) The sheet has a density of 0.5 to 0.8 kQ/lt. The covering sheet according to any one of claim 6. (8) The covering sheet according to any one of claims 1 to 7, wherein the sheet has 70 or more closed cells. (9) Sheet The coating sheet according to any one of claims 1 to 8 is self-extinguishing. The coating sheet according to claim 9, wherein the sheet contains 10 weight or more of alumina hydrate. Covering sheet. (11) The covering sheet according to claim 9, wherein the sheet is manufactured from an unsaturated polyester resin containing at least tSs of chemically bonded bromine or other halogen. (12) The sheet is made of metal. The coated sheet according to any one of claims 1 to 11, which is coated with a film or a metal-coated glass film. (13) Claims where the metal film is anodized aluminum. The coated sheet according to claim 12. (14) The coated sheet according to any one of claims 1 to 11, wherein the sheet contains a metal pigment in the form of metal powder. (15) The sheet contains a pigment or The coated sheet according to any one of claims 1 to 11, which is colored with a dye.