JP2001098095A - Heat-screening sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-screening sheet which comprises a vinyl chloride resin having a suitable softness and containing no plasticizer and which is excellent in heat-screening properties, weather resistance, and applicability. SOLUTION: This heat-screening sheet is prepared by laminating a heat- screening layer containing a heat ray absorption agent or a heat ray reflection agent to a sheet comprising a vinyl chloride resin prepared by the graft copolymerization of 90-50 wt.% vinyl chloride monomer onto 10-50 wt.% elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-insulating and weather-resistant sheet comprising a sheet made of a vinyl chloride resin having a suitable flexibility without using a plasticizer and a heat-shielding layer for absorbing or reflecting near-infrared rays laminated thereon. Heat shield sheet with excellent workability and workability.

[0002]

2. Description of the Related Art Hitherto, a heat shielding sheet has been used for the purpose of preventing excessive heat action due to sunlight rays, for example, being applied to window glass of automobiles and the like and roofs of buildings. Of the sun's rays, the one that mainly exerts a thermal effect is a wavelength of 700 to 2500 nm.
Is a light ray in a wavelength range called a so-called near-infrared ray. Examples of such a sheet having a heat-shielding property of absorbing or reflecting near-infrared rays by absorbing or reflecting include ammonium compounds, thiourea derivatives, and copper salts of certain organic acids as an infrared absorber. And those provided with an infrared reflective layer. As the above-mentioned sheet, a sheet obtained by adding a plasticizer to polyvinyl chloride to provide an appropriate flexibility, a flat yarn cloth made of a yarn of a polyolefin such as polyethylene and polypropylene, and the like have been known.

[0003]

Problems to be Solved by the Invention Japanese Patent Application Laid-Open No. 8-81567
Japanese Patent Application Publication No. JP-A-2002-115873 discloses a heat shield sheet in which a sheet in which 100 parts by weight of polyvinyl chloride is mixed with 26 parts by weight of dioctyl phthalate is mixed with an aminium compound as an infrared absorbent. However, since the plasticizer is mixed in the base sheet, the plasticizer elutes or volatilizes on the sheet surface, and it is difficult to maintain stable physical properties over a long period of time. .

Japanese Patent Application Laid-Open No. 9-158037 discloses a heat shield sheet in which a stainless steel vapor-deposited layer is adhered to the surface of a sheet substrate woven with a plain weave structure made of polyethylene. However, since the base sheet is made of polyethylene, it is difficult to provide an adhesive layer on the sheet surface, and the workability is poor.

On the other hand, in recent years, from the viewpoint of enhancing the cooling effect in summer and saving energy, the number of cases where a heat-shielding paint is applied to the roof of factories or houses has increased. However, when the heat-shielding paint is applied directly to a roof or the like, it is conceivable that a large number of man-hours are required and that the quality varies depending on the skill of a craftsman. Therefore, in order to maintain the simplicity of construction and the uniformity of quality, the development of a heat-shielding pressure-sensitive adhesive sheet, in which a heat-shielding paint is applied to a sheet in advance at a factory or the like and an adhesive is coated on the opposite surface, is desired. .

In view of the above-mentioned problems in the prior art, the present invention provides a sheet made of a vinyl chloride resin having an appropriate flexibility without using a plasticizer, and a heat shielding layer having a function of absorbing or reflecting near infrared rays. It is an object of the present invention to provide a laminated heat shield sheet having excellent heat shield property, weather resistance and workability.

[0007]

According to the first aspect of the present invention, there is provided a sheet comprising a vinyl chloride resin obtained by graft copolymerizing 90 to 50% by weight of a vinyl chloride monomer with 10 to 50% by weight of an elastomer. Is a heat shield sheet formed by laminating a heat shield layer containing a heat ray absorbent or a heat ray reflector.

[0008] The present invention according to claim 2 is that the heat ray absorbent comprises an aluminum compound, a diimonium compound, a benzenedithiol ammonium compound, a thiourea derivative, a cyanine compound, an anthraquinone compound, and a polymethine compound. The heat shield sheet according to claim 1, wherein the heat shield sheet is at least one type of heat ray absorbent selected from the group consisting of:

The present invention according to claim 3 is that the heat ray reflective agent comprises zinc aluminate, aluminum, stainless steel, nickel, tin, silver, copper, bronze, titanium oxide, shirasu balloon, ceramic balloon, and glass micro balloon. The heat shield sheet according to claim 1, wherein the heat shield sheet is at least one kind of heat ray reflective agent selected from the group consisting of:

According to a fourth aspect of the present invention, the elastomer is an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, or an acrylonitrile.
Butadiene copolymer, chlorinated polyethylene, (meth) acrylate copolymer, methyl methacrylate
The heat shield sheet according to any one of claims 1 to 3, wherein the heat shield sheet is at least one kind of elastomer selected from the group consisting of a styrene-butadiene copolymer, a chlorosulfonated polyethylene, and a polyurethane.

According to a fifth aspect of the present invention, the elastomer has a homopolymer having a glass transition temperature of -140 ° C to -2 ° C.
Alkyl (meth) acrylate monomer at 0 ° C
4. A crosslinked acrylic copolymer in which 100 parts by weight of an acrylic monomer component containing 0% by weight or more and 0.01 to 30 parts by weight of a polyfunctional monomer component are copolymerized. It is a heat sheet.

According to a sixth aspect of the present invention, there is provided the heat shield sheet according to any one of the first to fifth aspects, wherein an adhesive layer is provided on at least one surface of the heat shield sheet.

The vinyl chloride monomer used in the present invention is vinyl chloride or a vinyl monomer containing vinyl chloride as a main component. The vinyl monomer containing vinyl chloride as a main component may contain other monomers copolymerizable with vinyl chloride in addition to vinyl chloride. The monomer copolymerizable with vinyl chloride is not particularly limited as long as it is a monomer copolymerizable with vinyl chloride.

Examples of the monomers copolymerizable with vinyl chloride include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; Acrylic esters such as methyl acrylate, butyl acrylate and hydroxyethyl acrylate; methacrylic esters such as methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl fluoride, fluorine Vinyl halides such as vinylidene chloride and vinylidene chloride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

The amount of the other monomer copolymerizable with vinyl chloride in the monomer containing vinyl chloride as a main component is as follows:
Although it depends on the type, reactivity and the like of the monomer, it is usually preferably 20% by weight or less based on the total amount of the monomer and the graft copolymerized vinyl chloride. If the content exceeds 20% by weight, the intrinsic properties of the vinyl chloride resin may be lost.

The average degree of polymerization of the vinyl chloride component of the vinyl chloride resin is measured according to JIS K 6721, and is preferably 400 to 2500, more preferably 50 to 2,500.
0 to 1600. When the average degree of polymerization is less than 400, the durability is poor, and when the average degree of polymerization exceeds 2500,
The melt viscosity of the resin increases and the moldability deteriorates.

The elastomer used in the present invention is a general term for a polymer material having flexibility at room temperature, and is not particularly limited. Examples of preferred elastomers include ethylene-vinyl acetate copolymer (EVA),
Ethylene- (meth) acrylate copolymer (E
A), acrylonitrile-butadiene copolymer (NB
R), chlorinated polyethylene (CPE), methyl methacrylate-styrene-butadiene copolymer (MBS), chlorosulfonated polyethylene (CSPE), polyurethane (PU), (meth) acrylate copolymer (AC ) And the like. These may be used alone or in combination of two or more.

As the above EVA, for example, a vinyl acetate content is 10 to 80% by weight and a melt flow rate (MFR) value measured according to JIS K6760 is 0.5 to 0.5%.
300 are preferred examples.

As the EA, for example, the type of acrylate is ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., the content of the acrylate is 10 to 80% by weight, and the MFR is
And those having a value of 0.1 to 100.

As the above-mentioned NBR, for example, the content of acrylonitrile is 20 to 50% by weight, and the Mooney viscosity (M
(L1 + 4: 100 ° C.) of 10 to 200.

Examples of the CPE include those having a chlorination degree of 20 to 55% by weight and an MFR value of 0.1 to 100.

Examples of the MBS include those having a butadiene component of 50 to 90% by weight, a methyl methacrylate component of 5 to 45% by weight, and a styrene component of 5 to 45% by weight. However, the average particle size is not particularly limited, and is generally 0.1.
It is preferably from 1 to 5 μm.

The CSPE has, for example, a chlorine content of 20 to 50% by weight and a sulfur content of 0.5 to 2.0.
Weight%, Mooney viscosity (ML1 + 4: 100 ° C) is 10
~ 200.

Examples of the PU include those having a linear polymer or a partially crosslinked structure by reacting a polyfunctional active hydrogen compound such as a polyol with an isocyanate compound in the whole reaction system. And caprolactone type, adipate type, ether type and the like.

The AC is, for example, an acrylic acid ester, which is a glass transition temperature (T
g) a polymer mainly composed of monomers such as ethyl acrylate, n-propyl acrylate, butyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate having a temperature of −20 ° C. or less;
The monomer having a multilayer structure by copolymerization or multi-stage polymerization, and the polymer having a cross-linked structure using a monomer having two or more functionalities, and the like.
Is usually in the form of particles, but the average particle size is not particularly limited, and generally, it is preferably from 0.01 to 5 μm.

Of the above AC, 100 parts by weight of an acrylic monomer component containing 50% by weight or more of an alkyl (meth) acrylate monomer having a glass transition temperature of a homopolymer of -140 ° C to -20 ° C, and a polyfunctional monomer component 0.01
A preferred example is a crosslinked acrylic copolymer obtained by copolymerizing the copolymer with a total of 30 to 30 parts by weight.

If the alkyl (meth) acrylate monomer has a glass transition temperature of less than -140 ° C., it is not suitable as a polymer generally used industrially.
If the temperature exceeds 20 ° C., it is difficult to impart sufficient flexibility to the heat shield sheet, so the above range is preferable. Particularly preferably, it is −100 to −25 ° C.

Examples of the alkyl (meth) acrylate monomer include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate,
Examples include n-octyl (meth) acrylate, isooctyl acrylate, n-nonyl (meth) acrylate, isononyl acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

If the proportion of the alkyl (meth) acrylate having a glass transition temperature of the homopolymer of -140 to -20 ° C in the acrylic copolymer is less than 50% by weight, it is sufficient for the heat shield sheet. 50% by weight or more is preferable because flexibility cannot be imparted. A more preferred range is 80% by weight or more, and the upper limit is not particularly limited and may be 100% by weight.

The polyfunctional monomer is not particularly limited as long as it can be copolymerized with the alkyl (meth) acrylic monomer. Examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Polyfunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate; diallyl phthalate, diallyl maleate, triallyl isocyanurate And polyfunctional allyl compounds; unsaturated compounds such as butadiene. These may be used alone or in combination of two or more.

The amount of the other functional monomer in the acrylic copolymer is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the acrylic monomer. When the amount of the polyfunctional monomer is less than 0.01 part by weight or more than 30 parts by weight, the crosslinked acrylic copolymer does not function as an elastomer, and it is difficult to impart sufficient flexibility to the heat shielding sheet. The range is preferable, and the more preferable range is 0.1.
To 10 parts by weight.

The acrylic copolymer is obtained by, for example, an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or the like.
Among them, the emulsion polymerization method is preferably used because the control of the resin particle size is easy.

The above-mentioned emulsion polymerization can be carried out by a conventionally known method. For example, if necessary, an emulsifying dispersant, a polymerization initiator, a pH adjuster, an antioxidant and the like may be added.

The vinyl chloride resin used in the present invention is obtained by graft copolymerizing 90 to 50% by weight of a vinyl chloride monomer with 10 to 50% by weight of the above elastomer. When the amount of the elastomer is less than 10% by weight, the flexibility of the heat shield sheet is insufficient, and the heat shield sheet is likely to be bent, cracked, or the like, and the handling property is deteriorated. If it exceeds 50% by weight, sufficient strength cannot be obtained, and there is a possibility of causing a problem in workability as a sheet, so that it is limited to the above range.

The graft copolymerization of the elastomer and the vinyl chloride monomer can be carried out according to a conventionally known method. For example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be mentioned, and generally, a suspension polymerization method is used. In the suspension polymerization method, a dispersant, a polymerization initiator and the like are used.

The dispersant is not particularly restricted but includes, for example, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, polyvinyl acetate and its saponified products, gelatin, polyvinylpyrrolidone, starch, maleic anhydride-styrene copolymer and the like. No. These may be used alone or in combination of two or more.

The polymerization initiator is not particularly limited.
For example, organic peroxides such as lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, etc. And azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile. If necessary, a pH adjuster, an antioxidant, and the like may be added.

Specifically, the following method is used for the above suspension polymerization method. That is, pure water, a dispersant, a polymerization initiator, and an elastomer are charged into a polymerization vessel equipped with a temperature controller and a stirrer, air is removed from the polymerization vessel by a vacuum pump, and then a vinyl chloride monomer is introduced into the polymerization vessel. I do. After the elastomer is dispersed or dissolved in the vinyl chloride-based monomer, the temperature is raised, and polymerization is started at a desired polymerization temperature. After completion of the reaction, the remaining monomer is discharged out of the polymerization vessel to obtain a slurry. After dehydration with a dehydrator, drying is performed to obtain a vinyl chloride resin.

The vinyl chloride resin obtained by the above method may be used, if necessary, with a stabilizer, a stabilizing aid, a lubricant, a processing aid, an ultraviolet absorber, a light stabilizer, an antioxidant, a pigment, A compounding agent such as an agent is added to form a sheet.

The stabilizer is not particularly restricted but includes, for example, dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, dibutyltin maleate polymer, dioctyltin malate, dioctyltin maleate polymer, dibutyltin laurate , Organic tin-based stabilizers such as dibutyltin laurate polymer; lead white, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, etc.
Lead-based stabilizers such as dibasic lead phosphite, silica gel coprecipitated lead silicate, lead stearate, lead benzoate, dibasic lead stearate, lead naphthenate; calcium stearate, barium stearate, zinc stearate Metal soaps such as;
Calcium-zinc stabilizer; barium-zinc stabilizer;
Barium-cadmium stabilizer; hydrotalcite;
Zeolite and the like can be mentioned. These may be used alone or in combination of two or more.

The stabilizing aid is not particularly limited.
For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, phosphate esters and the like can be mentioned. These may be used alone or in combination of two or more.

The lubricant is not particularly restricted but includes, for example, montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, butyl stearate and the like. These may be used alone or in combination of two or more.

The processing aid is not particularly limited, and examples thereof include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
Acrylate homopolymer; copolymer of two or more monomers selected from the above (meth) acrylate monomers;
(Meth) acrylate, styrene, vinyltoluene,
Copolymers with vinyl monomers such as acrylonitrile and the like can be mentioned.

The ultraviolet absorber is not particularly limited, and examples thereof include salicylate-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers.

The light stabilizer is not particularly restricted but includes, for example, hindered amine light stabilizers.

The antioxidant is not particularly limited.
For example, phenolic antioxidants and the like can be mentioned.

The pigment is not particularly limited because it is selected according to the intended use, and examples thereof include organic pigments such as azo, phthalocyanine, sulene and dye lakes; oxides, molybdenum chromates, and sulfides. Pigments such as titanium oxide, titania, titanium white, zinc white, zinc oxide, zinc white, zinc sulfide, etc.
White pigments such as lithopone, lead white, antimony white and zirconium oxide; barium sulfate, barite powder, calcium carbonate, white carbon, silica, alumina white, diatomaceous earth, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, Magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, gypsum fiber, calcium silicate, kaolin, talc, clay, mica, montmorillonite, bentonite, Activated clay, sepiolite, imogolite, sericite, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balun, charcoal powder, potassium titanate, magnesium sulfate ( OS), titanate zirconium lead, aluminum borate, molybdenum sulfide, silicon carbide, zinc borate, fly ash, and the like extender pigments such as dehydrated sludge.

The order and method of mixing the above-mentioned various compounding agents with the above-mentioned vinyl chloride resin are not particularly limited, and any method can be adopted, and a method by hot blending or a method by cold blending may be used.

As a method for forming the above-mentioned vinyl chloride resin composition into a sheet, it is general to produce it by a calendering method. The vinyl chloride resin and the various compounding agents are mixed by heating with a ribbon type blender, a Henschel type mixer, etc., kneaded with a blend master with a Banbury mixer, etc., tempered with a roll, and then charged into a calender roll. The sheet is rolled and sheeted at a temperature, cooled and wound up to form a sheet.

Further, as an extrusion method, a method of extrusion molding at 150 to 200 ° C. using a T die, a coat hanger die, or the like may be employed. As the thickness of the above sheet,
50 to 300 μm is preferred. If it is less than 50 μm, sufficient strength as a sheet cannot be obtained, and if it exceeds 300 μm, it becomes too hard and poor in flexibility, and the workability when attaching the sheet to a wall or the like is deteriorated.

The heat shield layer used in the present invention is laminated on the vinyl chloride resin sheet. As a constituent material thereof, for example, a conventionally known heat shield paint can be used.
As a constitution of the heat shielding paint, a heat ray absorbing agent or a heat ray reflecting agent is an essential component, and a resin for forming a coating film, a solvent, and other additives are used as necessary.

Examples of the heat ray absorbent include aluminum compounds, diimonium compounds, benzenedithiol-type ammonium compounds, thiourea derivatives, cyanine compounds, anthraquinone compounds, and polymethine compounds. These may be used alone or in combination of two or more.

As the heat ray reflective agent, zinc aluminate, aluminum, stainless steel, nickel, tin, silver,
Examples include copper, bronze, titanium oxide, shirasu balloon, ceramic balloon, and micro balloon. These may be used alone or in combination of two or more.

Examples of the resin for forming a coating film include alkyd type, acrylic type, unsaturated polyester type, epoxy type,
Examples include polyurethane, silicone, vinyl chloride, fluorine, polyethersulfone, polyamide, polyimide, polyolefin, and polyethylene terephthalate. These may be used alone or in combination of two or more.

The solvent is not particularly limited as long as it can disperse the heat ray absorbing agent or the heat ray reflecting agent and can dissolve the resin for forming a coating film. One or more solvents selected from organic solvents and water can be used. Can be used. For example, alcohols such as methanol, ethanol, isopropanol, butanol and hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, 4-hydroxy-4-methyl-
Examples thereof include ketones such as 2-pentanone, hydrocarbons such as toluene, xylene, hexane, and cyclohexane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; and sulfoxides such as dimethylsulfoxide.

The thermal barrier paint further comprises a leveling agent,
Surfactants (cationic, anionic, nonionic),
A silane coupling agent, a pH adjuster (organic acid or inorganic acid), an antifoaming agent, a coloring agent, an antioxidant, and the like may be appropriately added.

As a method of laminating the above-mentioned thermal barrier paint on a vinyl chloride resin sheet, a conventionally known method can be used, for example, a roll coater, a reverse roll coater, a knife coater, a comma coater, a blade coater, a bar coater, a gravure coater. , A curtain coater, an applicator, a die coater, an edge coater and the like.

The thickness of the heat shield layer is preferably 50 to 500 μm. When the thickness is less than 50 μm, the heat shielding effect is not sufficiently exhibited, and when the thickness exceeds 500 μm, the improvement of the heat shielding effect with respect to the thickness is not obtained, and the heat shielding layer is cracked.

The heat shield sheet of the present invention is preferably provided with an adhesive layer on at least one side in order to enhance workability on site. Further, if necessary, a peelable protective layer is provided to protect the pressure-sensitive adhesive layer until the heat-shielding sheet is attached to the target attaching location.

The pressure-sensitive adhesive is not particularly limited as long as it is suitably used for a vinyl chloride resin film. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, SBR-based, polyurethane-based, chloroprene-based and butyl rubber-based adhesives. Agents. The pressure-sensitive adhesive layer is formed by applying a roll coater, a reverse roll coater, a knife coater, a comma coater, a blade coater, a bar coater, a gravure coater, a curtain coater, an applicator, a die coater, an edge coater, and the like to a required thickness. can do. The thickness of the pressure-sensitive adhesive layer is 10 to 50.
μm is preferred.

The thickness of the heat shield sheet of the present invention is 11
0 to 850 μm is preferred. If it is less than 110 μm, sufficient strength as a sheet cannot be obtained, and if it exceeds 850 μm, it becomes too hard and has poor flexibility, and the workability when attaching the heat shielding sheet to a wall or the like deteriorates. Is preferred.

[0062]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (Preparation of acrylic copolymer) 1.5 kg of pure water, emulsifier (trade name: Hytenol N-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
50 g of a 10% aqueous solution of an acrylic monomer (n-butyl acrylate, glass transition temperature: -54 ° C.) 2.4 k
g and 10 g of a polyfunctional monomer (trimethylolpropane triacrylate) to prepare an emulsion monomer.

4 kg of pure water and 24 g of a 10% aqueous solution of a polymerization initiator (ammonium persulfate) are placed in a 10 liter reactor equipped with a stirrer and a reflux condenser. Was heated to 75 ° C. After the temperature was raised, the emulsified monomer was dropped into the reactor at a constant dropping rate, and the dropping of all the emulsified monomers was completed in 3.0 hours. After that, stirring was continued for 1 hour, and then the polymerization was terminated. An acrylic copolymer latex having a solid content of 30% by weight was obtained.

(Preparation of Vinyl Chloride Resin [Graft Copolymerization]) 7.5 kg of pure water, 1.42 kg of the above acrylic copolymer latex (acryl copolymer) were placed in a 15 liter polymerization vessel equipped with a stirrer and a jacket. Solid weight 0.4
3 kg), partially saponified polyvinyl alcohol (trade name;
3% aqueous solution 30 of Kuraray Povar L-8 (Kuraray)
0 g, 1 g of t-butyl peroxydecanoate and 1 g of α-cumyl peroxydecanoate were added, and the air in the reactor was evacuated with a vacuum pump. Then, 2.8 kg of vinyl chloride monomer was added with stirring, and the reaction was continued. The vessel was heated to 64 ° C. to initiate polymerization.

The reaction was stopped when the pressure in the polymerization vessel dropped to a pressure of 5.6 kgf / cm ² . Thereafter, unreacted vinyl chloride monomer was removed, and further dehydration drying was performed to obtain a vinyl chloride resin.

(Preparation of heat shield sheet) A barium-zinc stabilizer (trade name: A) was added to 100 parts by weight of the vinyl chloride resin.
C-168, 4.0 parts by weight, Asahi Denka Co., Ltd. 4.0 parts by weight, lubricant (trade name: WAX-OP, manufactured by Hoechst) 1.0 parts by weight, titanium oxide (trade name: RTC-30, manufactured by Tyoxide Corporation)
5 parts by weight, a benzophenone-based ultraviolet absorber (trade name; U
(Vinul M40, manufactured by BASF) (0.5 parts by weight) was added and mixed using a Henschel mixer (manufactured by Kawada Industry Co., Ltd.) having a content of 100 L to prepare a mixed powder. Using the obtained powder mixture, calender molding was performed to a thickness of 200 μm.
Processed into sheets.

The obtained sheet was coated with a heat-shielding paint “T.SS-5005S” (manufactured by Nagashima Special Paint Co., Ltd.) containing a ceramic balloon as a main component at a dry coating amount of 0.3 kg / m ² (shielding). (The thickness of the heat layer was dried to 150 μm) and dried to obtain a heat shielding sheet. Both calender moldability and coatability were good.

(Evaluation Method) The heat-shielding sheet having a thickness of 350 μm was evaluated for heat-shielding properties and weather resistance in the following manner. The heat shield sheet was attached to a vinyl chloride plate of 110 mm long × 230 mm wide × 5 mm thick to prepare a test sample, and an accelerated weather resistance test was performed using a Sunshine Super Long Life Weather Meter (manufactured by Suga Test Instruments Co., Ltd.). , Surface condition and heat shielding performance were evaluated. The polyvinyl chloride plate is made of polyvinyl chloride “TS-100”.
0R "(polymerization degree 1000, manufactured by Tokuyama Sekisui Kogyo Co., Ltd.), 100 parts by weight of stabilizer" ONZ-142F "(manufactured by Sankyoki Gosei Co., Ltd.), 2.0 parts by weight, and filler" WAX-OP "(manufactured by Hoechst) 0.5 parts by weight, pigment "ResinoBlueR-3"
1) 0.3 parts by weight was added to prepare a compounded powder. The compounded powder was heated to 190 ° C. with an 8-inch roll, kneaded and processed into a sheet, and the sheet was press-formed at 200 ° C. to form a plate having a thickness of 5 mm.

Example 2 The procedure of Example 1 was repeated, except that the graft copolymerization was carried out so that the content of the acrylic copolymer in the vinyl chloride resin was 40% by weight. Evaluation was performed by obtaining a heat sheet.

Examples 3 to 10 In the same manner as in Example 1 except that the kind and the amount of the grafted elastomer were changed as shown in Table 1,
Evaluation was performed after obtaining a heat shield sheet.

Comparative Example 1 In Example 1, a polyvinyl chloride resin TS-800E (manufactured by Tokuyama Sekisui Kogyo Co., Ltd .;
00) A heat shield sheet was obtained in the same manner except that 43 parts by weight of a plasticizer aliphatic dicarboxylic acid polyester “Polysizer W340” (average molecular weight 1500, manufactured by Dainippon Ink and Chemicals, Inc.) was added to 100 parts by weight. The evaluation was carried out.

Comparative Example 2 The weather resistance and the heat insulation were evaluated without attaching a heat insulation sheet to a PVC plate.

[Evaluation Method] The heat-insulating sheets obtained in Examples and Comparative Examples were evaluated for weather resistance and heat-insulating properties as follows. The results are shown in Table 1 together with the composition. (Sample preparation) Polyvinyl chloride (trade name: TS-1000)
R, polymerization degree: 1000, 100 parts by weight of Tokuyama Sekisui Kogyo Co., Ltd., 2.0 parts by weight of a stabilizer (trade name: ONZ-142F, manufactured by Sankyoki Gosei Co., Ltd.), lubricant (trade name: WAX-OP, Hoechst) 0.5 parts by weight, pigment (trade name; Resin)
oBlueR-31) was added 0.3 parts by weight to prepare a compounded powder, heated to 190 ° C. with an 8-inch roll, kneaded and processed into a sheet, and the obtained sheet was press-formed at 200 ° C. to obtain a mixed powder. The heat shield sheet was attached to a plate having a length of 110 mm × a width of 230 mm × a thickness of 5 m to prepare a sample for evaluation. (Weather resistance) Using a Sunshine Super Long Life Weather Meter (manufactured by Suga Test Instruments Co., Ltd.), irradiating for 1 hour at black panel temperature of 63 ± 3 ° C., turning off for 1 hour, and sampling every 1000 hours, 4000
Went up to time. The appearance of the sample after 4000 hours was visually observed and evaluated according to the following criteria. ：: Good appearance, no damage such as blisters, dents and cracks on the sheet surface. X: Poor appearance, damage such as blisters, dents and cracks on the sheet surface are observed.

(Thermal Insulation) In the above-mentioned weather resistance test, a sample sampled every 1000 hours was used, and an infrared lamp of 125 W was irradiated from a distance of 15 cm in a room at 23 ° C. The temperature was measured and the heat insulation was evaluated.

[0075]

[Table 1]

The contents of the abbreviations in Table 1 are as follows. AC: Acrylic copolymer shown in Example 1 EVA1: Ethylene-vinyl acetate copolymer (trade name: Evaflex 45LX, vinyl acetate content: 45% by weight, MFR: 3, manufactured by Du Pont-Mitsui Chemicals) EVA2: Ethylene-vinyl acetate copolymer (trade name: Ultracene 634, vinyl acetate content: 26% by weight, M
EA: Ethylene-acrylate copolymer (trade name; Evaflex EEAA-709, MFR: 25, FR: 4, manufactured by Tosoh Corporation)
NBR: Acrylonitrile-butadiene copolymer (trade name; JSR PN30A, acrylonitrile content: 3)
5% by weight, Mooney viscosity (ML1 + 4: 100 ° C.): 4
2, Nippon Synthetic Rubber Co.) CPE: Chlorinated polyethylene (trade name: Eraslen 35)
1A, chlorine content: 35% by weight, MFR: 2, manufactured by Showa Denko KK MBS: Methyl methacrylate-butadiene-styrene copolymer (trade name: BTA-751, average particle size after dispersion:
CSPE: chlorsulfonated polyethylene (trade name: Hypalon 40, chlorine content: 35% by weight, sulfur content: 1.1% by weight, Mooney viscosity (ML1 + 4: 100)
° C): 30, manufactured by Tosoh Corporation PU: Polyurethane (trade name; Pandex 500E,
Caprolactone-based, manufactured by Dainippon Ink Co., Ltd.)

[0077]

The heat shield sheet of the present invention is configured as described above and exhibits excellent weather resistance and heat shield properties without containing a plasticizer. In particular, since there is no blooming of the plasticizer component, it can be suitably used for applications requiring stable performance over a long period of time.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AA04 AA12 AA13 AA15 AA17 AA22 AA37 AA58 AB13 AB18 AB19 AB24 AB34 AB35 AB36 AB37 AB38 AB39 AB42 AB64 AB65 AB66 AB73 AB74 BA03 CA00 DA04 4F100 AA21A AA21H AA04A ABH AB AB16H AB17A AB17H AB18A AB18H AB24A AB24H AB31A AB31H AC02A AC02H AD00A AD00H AG00A AG00H AH02A AH02H AH03A AH03H AH04A AH04H AK10A AK15A AK15J AK25A AK27A AK27J AK28A AK28J AK51A AK68A AK71A AK73A AL01A AL04A AL09A AL09J AR00B BA02 CA30A DE04A DE04H GB07 GB31 GB32 JJ02 JL09 JL13B 4J038 EA011 HA066 HA216 HA556 JA34 JC02 JC05 PC08

Claims (6)

[Claims] 1. A heat shield containing a heat ray absorber or a heat ray reflector in a sheet made of a vinyl chloride resin obtained by graft copolymerizing 90 to 50% by weight of a vinyl chloride monomer with 10 to 50% by weight of an elastomer. A heat shield sheet comprising a stack of layers. 2. The method according to claim 1, wherein the heat ray absorbent is at least one selected from the group consisting of aluminum compounds, diimonium compounds, benzenedithiol ammonium compounds, thiourea derivatives, cyanine compounds, anthraquinone compounds, and polymethine compounds. The heat shield sheet according to claim 1, wherein the heat shield sheet is one kind of heat ray absorbent. 3. The heat ray reflective agent is at least selected from the group consisting of zinc aluminate, aluminum, stainless steel, nickel, tin, silver, copper, bronze, titanium oxide, shirasu balloon, ceramic balloon, and glass microballoon. The heat shield sheet according to claim 1, wherein the heat shield sheet is one kind of heat ray reflective agent. 4. The elastomer according to claim 1, wherein the elastomer is an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, an acrylonitrile-butadiene copolymer, a chlorinated polyethylene, a (meth) acrylate copolymer, The heat shield according to any one of claims 1 to 3, wherein the heat shield is at least one elastomer selected from the group consisting of methyl methacrylate-styrene-butadiene copolymer, chlorosulfonated polyethylene, and polyurethane. Sheet. 5. An elastomer comprising 100 parts by weight of an acrylic monomer component containing 50% by weight or more of an alkyl (meth) acrylate monomer having a glass transition temperature of a homopolymer of -140 ° C. to -20 ° C., and a polyfunctional monomer. The heat shield sheet according to any one of claims 1 to 3, wherein the heat shield sheet is a crosslinked acrylic copolymer obtained by copolymerizing 0.01 to 30 parts by weight of a component. 6. The heat shield sheet according to claim 1, wherein an adhesive layer is provided on at least one surface.
The heat shield sheet according to any one of the above.