JP7760481B2 - Colored insulation board and polyisocyanurate foam for colored insulation board - Google Patents

Description

The present invention relates to a colored insulation board with a colored surface.

Insulating boards used in building interiors are made by laminating aluminum facings to both sides of polyisocyanurate foam. Polyisocyanurate foam is used as a building material because it has insulating and flame-retardant properties as well as strength.

Insulation boards made by laminating aluminum facings to both sides of polyisocyanurate foam have a metallic aluminum surface color with no color variations, so they may not be suitable for some applications. For this reason, there has been a demand in recent years for insulation boards in a variety of colors.

Conventionally, polyisocyanurate foams with a closed cell content of 20% or less or 69% or more have been disclosed (Table 2 of Patent Document 1).

Patent No. 3948014 Patent No. 4541970

However, in a conventional board using aluminum foil on both sides of a polyisocyanurate foam, if a colored coating film is applied to the surface of the aluminum foil, the board will not pass the cone calorimeter test, which is a heat generation test, and will not meet the standard of quasi-nonflammable or better, making it unsuitable for applications requiring a fire-resistant material with quasi-nonflammable or better performance.
The present invention has been made in view of the above points, and an object of the present invention is to provide a colored heat insulating board which has a colored surface and is a fire-resistant material having at least semi-noncombustible properties.

A first aspect of the present invention comprises a polyisocyanurate foam obtained from a polyisocyanurate composition containing a polyol component, a blowing agent, a catalyst, a cell opener, and an aromatic polyisocyanate; aluminum layers bonded to both sides of the polyisocyanurate foam; and a colored coating layer provided on the surface of at least one of the aluminum layers, wherein the cell opener uses a butadiene-based cell opener and a silicone-based cell opener in combination; the catalyst includes a trimerization catalyst; the polyisocyanurate foam has a nurate content of 30 to 40% and a closed cell content of 0 to 30%, and the colored coating layer has a basis weight of 1.5 to 13 g/ ^m2 .

A second aspect of the present invention is the polyisocyanurate composition according to the first aspect of the present invention , characterized in that the polyisocyanurate composition has an isocyanate index of 300 to 600.

A third aspect of the present invention is characterized in that, in the first or second aspect of the present invention , the amount of the cell opener is 0.2 to 0.5% by weight based on 100% by weight of the polyisocyanurate composition.

A fourth aspect of the present invention is characterized in that, in any one of the first to third aspects of the present invention , the foaming agent is a chemical foaming agent or a physical foaming agent, and the density of the polyisocyanurate foam is 25 to 45 kg/ ^m3 .

A fifth aspect of the present invention is characterized in that, in the fourth aspect of the present invention , the amount of water as the blowing agent is 0.1 to 0.5% by weight based on 100% by weight of the polyisocyanurate composition.

A sixth aspect of the present invention is characterized in that, in any one of the first to fifth aspects of the present invention , the viscosity of the polyol component at 25°C is 25 to 6000 mPa s, and each polyol constituting the polyol component has a molecular weight of 100 to 900 and a functional group number of 2 to 4.

The present invention provides a colored insulation board as a fire-resistant material that has a colored surface and passes the cone calorimeter test, which is a heat generation test, with a quasi-noncombustible or higher rating.

1 is a cross-sectional view showing one embodiment of a colored heat insulating board of the present invention. 1 is a table showing the criteria for the cone calorimeter test. 1 is a table showing the configurations, formulations, physical properties, heat generation tests, judgments, overall evaluations, etc. of Examples 1-4. 1 is a table showing the constitution, composition, physical properties, evaluation, overall evaluation, etc. of Examples 5-10. 1 is a table showing the configuration of comparative examples, the composition, physical properties, heat generation test, judgment, overall evaluation, etc.

The colored insulation board 10 according to one embodiment of the present invention, shown in Figure 1, consists of a main body 11, a surface 21, and a back surface 31. It passes the cone calorimeter test, which is a heat generation test, with a rating of at least semi-non-combustible, making it suitable for use as an interior material, such as a building ceiling, or as an exterior material.

The main body 11 is made of a polyisocyanurate foam obtained by reacting a polyisocyanurate composition. The polyisocyanurate foam that constitutes the main body 11 has a nurate ratio (also referred to as an isocyanurate ratio) of 30 to 40%, more preferably 32 to 40%, and a closed cell ratio of 0 to 30%, more preferably 0 to 20%.

If the nurate ratio of the polyisocyanurate foam is low, the flame retardancy will be reduced; conversely, if the nurate ratio is high, the foam will be brittle, with reduced compressive strength and bending properties, making it unsuitable as a structure. The nurate ratio was measured using infrared absorption spectroscopy. Specifically, the nurate ratio is the ratio of nurate rings to the entire partial structure calculated by dividing the absorption peak area based on nurate rings by the sum of the absorption peak areas based on nurate rings, urethane, urea [N-H], urea [C=O], urethane, and nurate [C=O], and is calculated using the nurate ratio calculation formula using the following a, b, c, and d:

a: Absorption peak position due to nurate ring: 1410 cm ⁻¹ , area position: area from 1347.03 to 1464.67 cm ⁻¹ b: Absorption peak position due to [N—H] of urethane and urea: 1510 cm ⁻¹ , area position: area from 1460.81 to 1562.06 cm ⁻¹ c: Absorption peak position due to “C═O] of urea: 1595 cm ⁻¹ , area position: area from 1566.88 to 1638.23 cm ⁻¹ d: Absorption peak position due to “C═O] of urethane and nurate: 1710 cm ⁻¹ , area position: area from 1636.3 to 1768.4 cm ⁻¹ Nurate ratio (%)=[a/(a+b+c+d)]×100

To achieve the above-mentioned nurate conversion rate, the isocyanate index is preferably 300 or higher, and more preferably 300 to 600, or 350 to 500. Details of the isocyanate index will be described later.

The closed cell ratio in the present invention is a value measured in accordance with ASTM D 2856. If the polyisocyanurate foam has a high closed cell ratio, thermal decomposition gases from the polyisocyanurate will accumulate between the foam and the aluminum foil face material during heating, pushing up the face material and causing it to bulge, which is unfavorable in heat generation tests. In the present invention, the closed cell ratio of the polyisocyanurate foam constituting the main body 11 is set within the above range. This allows the thermal decomposition gases from the foam to flow to the ends of the foam due to its interconnected structure during heat generation tests. This prevents decomposition gases from accumulating between the polyisocyanurate foam and the face material during heating, thereby suppressing expansion of the face material. This prevents the face material from swelling, preventing contact with the spark plug and leaks, and achieving quasi-nonflammable performance or better in heat generation tests.

The density of the polyisocyanurate foam (JIS K7222:2005) is preferably 25 to 45 kg/m ^3. If the density is too low, the strength will be insufficient, whereas if the density is too high, the foam will be too heavy for use as a ceiling or wall material. In addition, lightweight materials are preferred during construction, and this is undesirable from the viewpoint of wall structural materials, etc.
The thickness of the polyisocyanurate foam constituting the main body 11 is set appropriately, and may be, for example, 10 to 70 mm.

The polyisocyanurate composition contains a polyol component, a blowing agent, a catalyst, a cell opener, an aromatic polyisocyanate, and an auxiliary agent that is optionally blended.
The polyol may be any polyol known for use in polyisocyanurate foams. The polyol is not particularly limited as long as it is a compound having multiple hydroxyl groups. The polyol may be any of polyether polyols, polyester polyols, and polyether ester polyols, and one or more of these may be used. For example, it is preferable to use a combination of a bifunctional and/or trifunctional polyether polyol and an aromatic polyester polyol having two or more hydroxyl groups at the terminal or side chain, which is obtained by condensing a polybasic acid with a polybasic acid.

Examples of polyether polyols include polyether polyols obtained by adding alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO) to polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose; bifunctional polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, etc., or compounds obtained by addition polymerization of these with alkylene oxides such as ethylene oxide or propylene oxide, polyethylene glycol, polypropylene glycol, etc.); and trifunctional polyols (trimethylolpropane, glycerin, etc., or compounds obtained by addition polymerization of these with alkylene oxides, etc.).

Examples of polyester polyols include polyester polyols obtained by polycondensation of an aliphatic carboxylic acid such as malonic acid, succinic acid, or adipic acid, or an aromatic carboxylic acid such as phthalic acid, and an aliphatic glycol such as ethylene glycol, diethylene glycol, or propylene glycol.
Examples of polybasic acids constituting aromatic polyester polyols include orthophthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, and pyromellitic acid. Polyester polyols obtained by condensing phthalic acid with one or more difunctional, trifunctional, or polyfunctional alcohols or alkylene oxide adducts thereof are preferred, and polyester polyols obtained by condensing terephthalic acid with diethylene glycol are more preferred. The aromatic polyester polyols contain two or more hydroxyl groups, preferably two to three.

Furthermore, examples of polyetherester polyols include those obtained by reacting polyether polyols with polybasic acids to form polyesters, or those having both polyether and polyester segments in one molecule.

In the present invention, the polyol component refers to a polyol mixture in which multiple types of polyols are used, blending the polyols in the blending ratios specified in each example, or to that polyol in the case where a single polyol is used, and includes polyether polyols, polyester polyols, and polyether ester polyols.

The viscosity of the polyol component in the present invention is preferably 25 to 6,000 mPa·s (ASTM D4889) at 25° C. Each polyol used in the present invention preferably has a number average molecular weight of 100 to 900 and a functionality of 2 to 4.
The viscosity of the polyol component at 25°C in the present invention was calculated by multiplying the viscosity of each polyol constituting the polyol component at 25°C by the constituent ratio of each polyol and dividing the result by the sum of the respective values.

Furthermore, the viscosity at 25°C of each polyester polyol constituting the polyol component in the present invention is preferably 600 to 6,000 mPa·s (ASTM D4889), more preferably 900 to 5,600 mPa·s. It is preferable that each polyester polyol constituting the polyol component has a number average molecular weight of 200 to 900 and a functionality of 2 to 4.

By adjusting the viscosity of the polyol component at 25°C to a low viscosity within the above range, the cell membranes of the polyisocyanurate foam are easily broken down by the effect of the cell breaker, resulting in a lower closed cell ratio (higher open cell ratio).
Furthermore, since each polyol constituting the polyol component has a number average molecular weight of 100 to 900 and a functional group number of 2 to 4, the resulting foam has a low closed cell ratio and is resistant to heat shrinkage in heat generation tests.

The amount of polyol component is preferably 1 to 20% by weight based on 100% by weight of the polyisocyanurate composition.

The blowing agent can be water, a chemical blowing agent, or a physical blowing agent such as pentane, a hydrocarbon, or hydrofluoroolefin, either alone or in combination. When using water, carbon dioxide gas is generated during the reaction between the polyol and polyisocyanate, and this carbon dioxide gas causes foaming. The amount of blowing agent can be adjusted as needed, but when using water, the amount of water is 0.1 to 1.5% by weight per 100% by weight of the polyisocyanurate composition. When using water in combination with other blowing agents, the amount of water is preferably 0 to 1.0% by weight per 100% by weight of the polyisocyanate composition. When the physical blowing agent is pentane, the amount is preferably 8 to 0% by weight, and when using hydrofluoroolefin, the amount is preferably 15 to 0% by weight.

The catalyst essentially contains a trimerization catalyst used in the production of polyisocyanurate foam. Furthermore, a trimerization catalyst can be used in combination with a urethane catalyst (resinization catalyst, foaming catalyst).

Examples of trimerization catalysts include: 1) metal oxides such as lithium oxide, sodium oxide, and potassium oxide; 2) alkoxides such as methoxysodium, ethoxysodium, propoxysodium, butoxysodium, methoxypotassium, ethoxypotassium, propoxypotassium, and butoxypotassium; 3) organometallic salts such as potassium acetate, 2-ethylhexanepotassium, potassium octoate, potassium caprylate, and iron oxalate; 4) tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine, and triethylenediamine; 5) derivatives of ethyleneimine; and 6) acetylacetone chelates and quaternary ammonium salts of alkali metals, aluminum, and transition metals.
These can be used alone or in combination of two or more, and among them, 3) organic metal salts and 6) quaternary ammonium salts are more preferably used. Preferably, a combination of potassium acetate and potassium octylate can be used.

Examples of urethanization catalysts include amine catalysts such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, bis-(2-dimethylaminoethyl)ether, and dimethylethanolamine; tin-based catalysts such as stannous octoate; and metal catalysts (also known as organometallic catalysts) such as phenylmercury propionate and lead octenate.

The preferred amount of trimerization catalyst is 0.8 to 7% by weight based on 100% by weight of the polyisocyanurate composition.

The cell opener breaks down cells during foaming, promoting cell interconnection and reducing the closed cell ratio. In the present invention, a butadiene-based cell opener and a silicone-based cell opener are used in combination. By using a butadiene-based cell opener and a silicone-based cell opener in combination, the bubbles are not retained during foam growth, preventing the foam from collapsing, resulting in a foam with a good foaming state and a low closed cell ratio. The weight ratio of the butadiene-based cell opener to the silicone-based cell opener is preferably 25:1 to 1:1. The preferred amount of cell opener is 0.2 to 0.5% by weight per 100% by weight of the polyisocyanurate composition.

Examples of aromatic polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xylylene diisocyanate, and polymeric polyisocyanate (crude MDI). Two or more aromatic polyisocyanates may be used in combination.

The amount of aromatic polyisocyanate used is preferably such that the isocyanate index is 300 to 600, more preferably 350 to 500. If the isocyanate index is less than 300, the foam will be flammable and prone to heat shrinkage, while if it is more than 600, the foam will become brittle, with reduced compressive strength and bending properties, making it unsuitable for use as a structure.

Furthermore, as mentioned above, by setting the isocyanate index within the above range and adding an appropriate amount of trimerization catalyst, a nurate conversion rate of 30 to 40% can be achieved in the present invention. The isocyanate index is defined as the number of moles of isocyanate groups in the polyisocyanate divided by the total number of moles of active hydrogen groups, such as hydroxyl groups in the polyol and water as a blowing agent, multiplied by 100, and is calculated as [NCO equivalent of polyisocyanate / active hydrogen equivalent × 100].

Examples of auxiliary agents that may be appropriately blended include flame retardants, colorants, etc. Examples of flame retardants include halogenated polymers such as polyvinyl chloride, chloroprene rubber, and chlorinated polyethylene, organic flame retardants such as phosphate esters, halogenated phosphate ester compounds, melamine resins, and urea resins, and inorganic flame retardants such as antimony oxide and aluminum hydroxide. The amount of flame retardant is preferably 1 to 15% by weight, and more preferably 2 to 10% by weight, based on 100% by weight of the polyisocyanurate composition.
Examples of resins for colorants include epoxy resins, acrylic resins, and urethane resins, and pigments, dyes, carbon, and the like can also be used.

When the polyisocyanurate composition is mixed in a known foaming device, the polyol and aromatic polyisocyanate react and foam to form a polyisocyanurate foam.

The surface portion 21 forms one side of the colored insulation board 10. As shown in the enlarged cross-sectional view of part A in Figure 1, the surface portion 21 consists of an adhesive resin layer 22, an aluminum layer 23, and a colored coating layer 24.

The adhesive resin layer 22 is positioned between the polyisocyanurate foam body 11 and the aluminum layer 23 and is provided for reasons such as improving the adhesive strength between the aluminum layer 23 and the polyisocyanurate foam body 11. The adhesive resin layer 22 can be formed by applying a resin coating of synthetic resin dissolved in a solvent to one side of the aluminum layer 23 to a predetermined thickness and drying it. The adhesive resin layer 22 preferably has a basis weight of 1.0 to 10.0 g/ ^m² . If the adhesive resin layer 22 has a low basis weight, the resin layer cannot be formed uniformly. On the other hand, if the adhesive resin layer 22 has a high basis weight, the surface material will swell and come into contact with the spark plug in a cone calorimeter test, resulting in poor flame retardancy. Examples of resins for the adhesive resin layer 22 include epoxy resin, acrylic resin, and urethane resin.

The aluminum layer 23 is made of aluminum foil. The thickness of the aluminum layer 23 is preferably 12 to 150 μm. If the aluminum layer 23 is too thin, pinholes will form in the aluminum, the heat-shielding effect of the aluminum foil will not be obtained, and the colored insulation board 10 will not perform at or above quasi-noncombustible performance in the cone calorie test. Conversely, if the aluminum layer 23 is too thick, the colored insulation board 10 will become heavy and costly. The aluminum foil that makes up the aluminum layer 23 can also be coated with an adhesive resin layer 22 in advance.

The colored coating layer 24 is made of a colored resin coating. The colored coating layer 24 can be formed by applying a resin paint, prepared by dissolving a resin in a solvent and dispersing a colorant, to the surface of the aluminum layer 23 (the surface opposite the surface on which the adhesive resin layer 22 is formed) to a predetermined thickness and then drying the paint. Examples of resins that constitute the colored coating layer 24 include epoxy resin, acrylic resin, and urethane resin. The colored coating layer 24 preferably has a basis weight of 1.5 to 12.0 g/ ^m² . If the basis weight of the colored coating layer 24 is low, the coating layer may not be uniformly formed or the coloring may be insufficient. On the other hand, if the basis weight of the colored coating layer 24 is high, the layer may swell in a cone calorimeter test and fail to meet the quasi-noncombustible or higher standard. The color of the colored insulation board 10 may be selected from white, yellow, light blue, ivory, etc., depending on the installation location and other factors. The colored coating layer 24 can be applied by gravure coating, spray coating, roll coating, comma coating, or the like.

The back surface 31 forms the other side of the colored insulation board 10. As shown in the enlarged cross-sectional view of part B in Figure 1, the back surface 21 consists of an adhesive resin layer 32 and an aluminum layer 33.

The adhesive resin layer 32 is located between the main body 11 made of polyisocyanurate foam and the aluminum layer 33, and is provided for reasons such as improving the adhesive strength between the aluminum layer 33 and the main body 11 made of polyisocyanurate foam. The adhesive resin layer 32 is formed by applying a resin paint made by dissolving a synthetic resin in a solvent to one side of the aluminum layer 33 to a predetermined thickness and drying it. The adhesive resin layer 32 preferably has a basis weight of 1.0 to 10.0 g/ ^m2 . Examples of resins that constitute the adhesive resin layer 32 include epoxy resin, acrylic resin, and urethane resin.

The aluminum layer 33 is made of aluminum foil. The thickness of the aluminum layer 33 is preferably 12 to 150 μm. The aluminum foil that constitutes the aluminum layer 33 may be coated with an adhesive resin layer 32 in advance.

The colored insulation board 10 passes the cone calorimeter test with a semi-noncombustible or higher rating. The cone calorimeter test, specified in ISO 5660-1, involves irradiating a sample with 50 kW/ ^m² of heat from a radiant electric heater and measuring the amount of heat generated to determine heat generation. As shown in Figure 2, the cone calorimeter test results in three classes: noncombustible, semi-noncombustible, and flame-retardant. Here, "noncombustible" refers to a material that meets the requirements of "noncombustible materials" as defined in Article 2, Paragraph 9 of the Building Standards Act and Article 108-2 of the Enforcement Order of the Building Standards Act. "Semi-noncombustible" refers to a "semi-noncombustible material" as defined in Article 1, Paragraph 5 of the Enforcement Order, and "flame-retardant" refers to a "flame-retardant material" as defined in Article 1, Paragraph 6 of the Enforcement Order.

The criteria for non-combustibility are as follows: (1) the total heat generation is 8 MJ/ ^m2 or less, (2) there are no cracks or holes that penetrate to the back surface and are harmful to fire prevention, (3) the maximum heat generation rate does not exceed 200 kW/ ^m2 for 10 seconds or more, and (4) there is no spark leakage. If any one of (1) to (3) is not met, it is considered a failure, and if (4) is not met, it is impossible to judge. Note that "spark leakage" refers to the phenomenon in which sparks between the plugs are taken by the test specimen.

The criteria for quasi-noncombustible are as follows: (1) the total heat generation is 8 MJ/ ^m2 or less, (2) there are no cracks or holes that penetrate to the back surface and are harmful from a fire prevention perspective, (3) the maximum heat generation rate does not exceed 200 kW/ ^m2 for 10 seconds or more, and (4) there is no spark leakage. A product is deemed to have passed the test if any one of (1) to (3) is not met, and if (4) is not met, it is deemed to have failed the test.

The flame retardancy criteria are as follows: (1) the total heat generation is 8 MJ/ ^m2 or less, (2) there are no cracks or holes that penetrate to the back surface and are harmful from a fire prevention perspective, (3) the maximum heat generation rate does not exceed 200 kW/ ^m2 for 10 seconds or more, and (4) there is no spark leakage. If any one of (1) to (3) is not met, the product is deemed to have passed the test, and if (4) is not met, the product cannot be judged.

The colored insulation board 10 is manufactured by placing an aluminum layer (aluminum foil) 33, previously coated with an adhesive resin layer 32, with the adhesive resin layer 32 facing upward. A polyisocyanurate composition is then dispensed onto the adhesive resin layer 32. The aluminum layer (aluminum foil) 23, previously coated with an adhesive resin layer 22, is then laminated, with the adhesive resin layer 22 facing downward, onto the polyisocyanurate composition as it undergoes foaming reaction, allowing the polyisocyanurate composition to foam and cure. This allows the aluminum layers 23, 33 to be bonded to the main body 11, which is made of a polyisocyanurate foam obtained by reacting the polyisocyanurate composition, via the adhesive resin layers 22, 32. This reduces the amount of adhesive resin layers 22, 32 required for bonding, thereby reducing swelling due to thermal decomposition of the adhesive resin layers 22, 32 in a cone calorimeter test. A colored coating layer 24 is then applied to the surface of the aluminum layer 23. The colored coating layer 24 may be applied to the surface of the aluminum layer 23 in advance, or if colored coating layers are to be formed on both sides, a colored coating layer is also formed on the surface of the other aluminum layer 33.

A mold (foam molding mold) consisting of a lower and upper molds and having a 300 x 300 x 50 mm cavity was used. A backing member was placed on the bottom of the lower mold cavity with the adhesive resin layer facing upward. Approximately 180 g of the polyisocyanurate composition was poured into the cavity with the temperature adjusted to 90 °C. The upper mold, with the surface member set so that the adhesive resin layer faced downward, was placed over the lower mold and closed. The polyisocyanurate composition was foamed in the cavity, and the molded product was demolded and cut into 100 mm squares to obtain samples for heat generation tests for each Example and Comparative Example. The polyisocyanurate composition was also poured into a 300 x 300 x 300 mm box with an open top to produce a polyisocyanurate foam (hereinafter referred to as a free foam) without a facing material. The closed cell content, foam density, and nurate content were measured.
The configurations of the examples and comparative examples are shown in Figures 3 to 5. In Figures 3 to 5, the [wt %] in the formulation column is the weight % relative to 100% by weight of the polyisocyanurate composition.

The surface member was prepared as follows. First, a diluted resin solution prepared by diluting epoxy resin (transparent, product name: RC12 [hardener], product name: JER828 [base material], product of Mitsubishi Chemical Corporation, blended at 50 parts of hardener per 100 g of base material) with methyl ethyl ketone was applied to one side of an aluminum foil (Alloy No. 1N30, manufactured by Toyo Aluminum) having the thickness indicated in the aluminum layer column on the surface portion of Figures 3 to 5. The diluted resin solution was applied with a bar coater to the basis weight indicated in the adhesive resin layer column on the surface portion of Figures 3 to 5. The applied solution was then left at room temperature for one week to form an adhesive resin layer. Furthermore, a diluted resin solution prepared by diluting epoxy resin containing a colorant (white, product name: Rockhold White, manufactured by Rock Paint Co., Ltd.) with thinner was applied with a bar coater to the surface opposite the adhesive resin layer to the basis weight indicated in the colored coating layer column on the surface portion of Figures 3 to 5. The applied solution was then left at room temperature for one week to form a colored coating layer.

The back surface member was prepared as follows. First, a diluted resin solution prepared by diluting epoxy resin (transparent, product names: RC12 [hardener], JER828 [base material], Mitsubishi Chemical Corporation, blended at a ratio of 50 parts hardener to 100 parts base material) with methyl ethyl ketone was applied to one surface of an aluminum foil (alloy number 1N30, manufactured by Toyo Aluminum) having the thickness indicated in the aluminum layer column for the back surface portion of Figures 3 to 5 for each example and comparative example. The diluted resin solution was applied using a bar coater to the surface of one side of the aluminum foil (alloy number 1N30, manufactured by Toyo Aluminum) having the thickness indicated in the aluminum layer column for the back surface portion of Figures 3 to 5 for each example and comparative example. The applied resin solution was then left at room temperature for one week to form an adhesive resin layer.

The polyisocyanurate compositions were prepared by blending the following components in the proportions (parts by weight) shown in each of the examples and comparative examples in FIGS.
Isocyanate: Polymeric MDI, NCO%: 31.3%, Product name: MR-200, manufactured by Tosoh Corporation. Main polyol 1: Polyester polyol (OHV: 323 mg KOH/g, number average molecular weight: 350) obtained by dehydration condensation of orthophthalic acid and diethylene glycol (DEG), viscosity at 25°C: 2600 mPa·s, viscosity at 15°C: 5200 mPa·s, number of functional groups: 2
Main polyol 2: polyester polyol (OHV: 200 mg KOH/g, number average molecular weight: 561) obtained by dehydration condensation of terephthalic acid and diethylene glycol (DEG), viscosity at 25°C: 950 mPa·s, viscosity at 15°C: 1600 mPa·s, number of functional groups: 2
Main polyol 3: polyester polyol (OHV: 250 mg KOH/g, number average molecular weight: 450) obtained by dehydration condensation of terephthalic acid and diethylene glycol (DEG), viscosity at 25°C: 5500 mPa·s, viscosity at 15°C: 13450 mPa·s, number of functional groups: 2
Ether polyol: Polyether polyol, number of functional groups: 2, number average molecular weight: 106, hydroxyl value: 1057 mg KOH/g, viscosity at 25°C: 27 mPa·s, product name: diethylene glycol, manufactured by Maruzen Petrochemical Co., Ltd.

Flame retardant: tris(dichloropropyl)phosphate, product name: TCPP, manufactured by Daihachi Chemical Co., Ltd. Catalyst 1: trimerization catalyst, 2,4,6-tris(dimethylaminomethyl)phenol, product name: Lubeac DMP-30, manufactured by Nacalai Tesque, Inc. Catalyst 2: trimerization catalyst, potassium octoate Catalyst 3: trimerization catalyst, potassium acetate Foam stabilizer: silicone-based foam stabilizer, product name: Tegostab B8443, manufactured by Evonik Japan Co., Ltd. Foam opener 1: butadiene-based foam opener, product name: Ortegol 501, manufactured by Evonik Japan Co., Ltd. Foam opener 2: silicone-based foam opener, product name: Tegostab B8523, manufactured by Evonik Japan Co., Ltd. Blowing agent 1: water Blowing agent 2: cyclopentane Blowing agent 3: hydrofluoroolefin, product name: Solstice LBA, manufactured by Honeywell Japan Co., Ltd.

The samples of each Example and Comparative Example were subjected to measurements of the presence or absence of health bubbles, the closed cell ratio, the nurate ratio, and the foam density, as well as a heat buildup test.
Health bubbles refer to gases such as carbon dioxide gas generated by the foaming reaction of the polyisocyanurate composition that escape in the form of bubbles from the surface of the expanded foam. The presence or absence of health bubbles was determined visually during free foaming.
The closed cell content was measured in accordance with ASTM D 2856 for the polyisocyanurate foam (main body) of each sample of each Example and Comparative Example.
The nurate ratio was measured by measuring a test piece 3 mm thick at a depth of 30 mm from the surface of the polyisocyanurate foam sample obtained by free foaming in each Example and Comparative Example based on the infrared absorption spectroscopy method, and calculating the nurate ratio using the formula described above.
The foam density was measured for the polyisocyanurate foam (main body, free foam) in each example and comparative example sample in accordance with JIS K7222:2005.
The heat generation test was carried out in accordance with the cone calorimeter test specified in ISO5660.
The results are shown in FIGS.

Examples 1 to 5 are examples in which the surface colored coating layer has a basis weight of 5 g/m ² , the aluminum layer has a thickness of 80 μm, the adhesive resin layer has a basis weight of 1.6 g/m ² , the foam (polyisocyanurate foam) has a thickness of 50 mm, the aluminum layer on the back surface has a thickness of 20 μm, and the adhesive resin layer has a basis weight of 1.6 g/m ² , and the amounts of each material in the polyisocyanurate composition were changed.

Example 1 is an example of a polyisocyanurate composition containing 68.0 wt% isocyanate, 8.33 wt% main polyol 2, 2.64 wt% ether polyol, 9.72 wt% flame retardant, 0.24 wt% catalyst 1, 0.80 wt% catalyst 2, 0.41 wt% catalyst 3, 0.25 wt% cell opener 1 (butadiene-based), 0.04 wt% cell opener 2 (silicone-based), 0.32 wt% blowing agent 1 (water), and 9.22 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 412 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 1 is an example in which the amount of cell breaker 2 (silicone-based) was reduced compared to the other examples, and it had health bubbles during foaming, a closed cell rate of 2.4%, a nurate rate of 33.0%, a density of 28.5 kg/m ³ , passed the semi-noncombustible and noncombustible standards, and had an overall rating of “◎”. The surface was colored, and it was a fireproof material with semi-noncombustible performance or better.

Example 2 is an example of a polyisocyanurate composition containing 68.0 wt% isocyanate, 8.32 wt% main polyol 2, 2.64 wt% ether polyol, 9.71 wt% flame retardant, 0.24 wt% catalyst 1, 0.80 wt% catalyst 2, 0.41 wt% catalyst 3, 0.25 wt% cell opener 1 (butadiene-based), 0.14 wt% cell opener 2 (silicone-based), 0.32 wt% blowing agent 1 (water), and 9.21 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 412 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 2 has health bubbles when foamed, a closed cell rate of 1.3%, a nurate rate of 34.0%, a density of 30.5 kg/m ³ , passes the semi-non-combustible and non-combustible standards, and has an overall rating of "◎". The surface is colored and the fireproof material has at least semi-non-combustible performance.

Example 3 is an example of a polyisocyanurate composition containing 67.9 wt% isocyanate, 8.32 wt% main polyol 2, 2.64 wt% ether polyol, 9.7 wt% flame retardant, 0.24 wt% catalyst 1, 0.80 wt% catalyst 2, 0.41 wt% catalyst 3, 0.25 wt% cell opener 1 (butadiene-based), 0.21 wt% cell opener 2 (silicone-based), 0.32 wt% blowing agent 1 (water), and 9.2 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 411 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 3 is an example in which the amount of cell breaker 2 (silicone-based) was increased compared to the other examples, and it had health bubbles during foaming, a closed cell rate of 2.6%, a nurate rate of 35.4%, a density of 29.3 kg/m ³ , passed the semi-noncombustible and noncombustible standards, and had an overall rating of “◎”, and was a fireproof material with a colored surface and at least semi-noncombustible performance.

Example 4 is an example of a polyisocyanurate composition containing 60.1 wt% isocyanate, 12.03 wt% main polyol 2, 2.90 wt% ether polyol, 10.94 wt% flame retardant, 0.26 wt% catalyst 1, 0.88 wt% catalyst 2, 0.45 wt% catalyst 3, 0.24 wt% cell opener 1 (butadiene-based), 0.14 wt% cell opener 2 (silicone-based), 0 wt% blowing agent 1 (water), and 12.03 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 420 and a viscosity of the polyol component at 25°C of 771 mPa·s.

Example 4 is an example in which water as a foaming agent is not blended, and it has health bubbles when foamed, a closed cell rate of 4.9%, a nurate rate of 32.5%, a density of 31.2 kg/m ³ , passes the quasi-noncombustible and noncombustible standards, and has an overall rating of "◎", and is a fireproof material with a colored surface and at least quasi-noncombustible performance. Note that Example 4 has a higher closed cell rate than the other examples because it does not contain water as a foaming agent.

Example 5 is an example of a polyisocyanurate composition containing 64.3 wt% isocyanate, 9.00 wt% main polyol 2, 2.85 wt% ether polyol, 10.5 wt% flame retardant, 0.26 wt% catalyst 1, 0.87 wt% catalyst 2, 0.44 wt% catalyst 3, 0.27 wt% cell opener 1 (butadiene-based), 0.15 wt% cell opener 2 (silicone-based), 0.17 wt% blowing agent 1 (water), and 11.21 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 422 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 5 is an example in which the amount of water blended is reduced compared to Examples other than Example 4 (an example in which water is not blended as a foaming agent), and has health bubbles when foamed, a closed cell rate of 0%, a nurate rate of 33.0%, a density of 31.9 kg/m ³ , passes the semi-noncombustible and noncombustible standards, and has an overall rating of "◎", and is a fireproof material with a colored surface and at least semi-noncombustible performance.

In Example 6, the basis weight of the colored coating film layer on the surface portion was increased to 13 g/ ^m2 , and the other configurations of the surface portion, the configuration of the back surface portion, and the polyisocyanurate composition were the same as those of Example 2. The isocyanate index was 412.

Example 6 is an example in which the basis weight of the colored coating layer on the surface is increased compared to the other examples, and has health bubbles when foamed, a closed cell rate of 1.3%, a nurate rate of 34.0%, a density of 30.5 kg/m ³ , passes the semi-non-combustible and non-combustible standards, and has an overall rating of "◎", making it a fireproof material with a colored surface and at least semi-non-combustible performance.

Example 7 is an example of a polyisocyanurate composition containing 69.6 wt% isocyanate, 7.32 wt% main polyol 1, 2.53 wt% ether polyol, 9.39 wt% flame retardant, 0.24 wt% catalyst 1, 0.79 wt% catalyst 2, 0.40 wt% catalyst 3, 0.22 wt% cell opener 1 (butadiene-based), 0.13 wt% cell opener 2 (silicone-based), 0.28 wt% blowing agent 1 (water), and 9.15 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 405 and a viscosity of the polyol component at 25°C of 1938 mPa·s.

Example 7 is an example in which main polyol 1, which has a high viscosity at 25°C, was blended in place of main polyol 2 in Examples 1 to 6, and the result was no health bubbles during foaming, a closed cell rate of 15%, a nurate rate of 37.5%, a density of 32.3 kg/m ³ , passed the quasi-noncombustible test, but failed the noncombustible test, resulting in an overall rating of "Good." Although Example 7 could not be judged as noncombustible due to the blending of main polyol 1, which has a high viscosity at 25°C, the surface was colored and the fireproof material had at least quasi-noncombustible performance.

Example 8 is an example of a polyisocyanurate composition containing 68.9 wt% isocyanate, 7.95 wt% main polyol 3, 2.59 wt% ether polyol, 9.28 wt% flame retardant, 0.24 wt% catalyst 1, 0.8 wt% catalyst 2, 0.41 wt% catalyst 3, 0.24 wt% cell opener 1 (butadiene-based), 0.13 wt% cell opener 2 (silicone-based), 0.3 wt% blowing agent 1 (water), and 9.14 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 410 and a viscosity of the polyol component at 25°C of 4153 mPa·s.

Example 8 is an example in which a high-viscosity main polyol 3 was blended, whose viscosity at 25°C was higher than that of main polyol 2 but lower than that of main polyol 1, and it had no health bubbles during foaming, a closed cell rate of 25%, a nurate rate of 32.6%, a density of 31.9 kg/m ³ , passed the quasi-noncombustible test, but was unable to determine whether it was noncombustible, and did not pass the noncombustible test, resulting in an overall rating of "Good." Although Example 8 failed the noncombustible test due to the blending of main polyol 3, which has a high viscosity at 25°C, the surface was colored and it was a fireproof material with at least quasi-noncombustible performance.

Example 9 is an example of a polyisocyanurate composition containing 65.3 wt% isocyanate, 9.7 wt% main polyol 2, 3.08 wt% ether polyol, 10.5 wt% flame retardant, 0.26 wt% catalyst 1, 0.88 wt% catalyst 2, 0.42 wt% catalyst 3, 0.25 wt% cell opener 1 (butadiene-based), 0.14 wt% cell opener 2 (silicone-based), 0.33 wt% blowing agent 1 (water), and 9.1 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 358 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 9 has health bubbles when foamed, a closed cell rate of 1.8%, a nurate rate of 32.0%, a density of 30.2 kg/m ³ , passes the semi-noncombustible and noncombustible standards, and has an overall rating of "◎". The surface is colored and the fireproof material has at least semi-noncombustible performance.

Example 10 is an example of a polyisocyanurate composition containing 71.6 wt% isocyanate, 7.01 wt% main polyol 2, 2.22 wt% ether polyol, 8.18 wt% flame retardant, 0.20 wt% catalyst 1, 0.67 wt% catalyst 2, 0.35 wt% catalyst 3, 0.21 wt% cell opener 1 (butadiene-based), 0.12 wt% cell opener 2 (silicone-based), 0.32 wt% blowing agent 1 (water), and 9.1 wt% blowing agent 3 (hydrofluoroolefin), with an isocyanate index of 493 and a viscosity of the polyol component at 25°C of 727 mPa·s.

Example 10 has health bubbles when foamed, a closed cell rate of 3.5%, a nurate rate of 38.9%, a density of 31.3 kg/m ³ , passes the semi-non-combustible and non-combustible standards, and has an overall rating of "◎". The surface is colored and the fireproof material has at least semi-non-combustible performance.

Comparative Example 1 is an example in which the surface and back surfaces of Example 2 were not provided, and the formulation of the polyisocyanurate composition was essentially the same as Example 2, except that the amount of cell opener 2 (silicone-based) was 0% by weight.

In Comparative Example 1, foaming stopped midway and the product collapsed, so it was not possible to test for the presence or absence of health bubbles, or to test the foam's physical properties or heat generation, resulting in an overall rating of "X".

Comparative Example 2 is an example in which the formulation of the polyisocyanurate composition is nearly identical to that of Example 2, except that both cell opener 1 (butadiene-based) and cell opener 2 (silicone-based) are set to 0% by weight, and the configuration of the front and back surfaces is also identical to that of Example 2.

In Comparative Example 2, both cell breaker 1 (butadiene-based) and cell breaker 2 (silicone-based) were used at 0% by weight, and there were no health bubbles during foaming, the closed cell rate was 80.0%, the nurate rate was 36.6%, the density was 28.1 kg/m ³ , and both the quasi-noncombustible and noncombustible tests were unsuccessful, resulting in an overall rating of "X." In Comparative Example 2, both cell breaker 1 (butadiene-based) and cell breaker 2 (silicone-based) were used at 0% by weight, resulting in an extremely high closed cell rate and failing both the quasi-noncombustible and noncombustible tests.

Comparative Example 3 is an example in which the formulation is almost the same as that of Example 2, except that the basis weight of the colored coating film layer on the surface portion is increased to 35 g/ ^m2 , and the surface portion and back surface portion are also the same as those of Example 2.

Comparative Example 3 is an example in which the basis weight of the colored coating layer on the surface portion was increased to 35 g/ ^m2, and it had health bubbles when foamed, a closed cell rate of 1.3%, a nurate rate of 34.0%, a density of 30.5 kg/ ^m3 , and failed both the quasi-noncombustible and noncombustible tests, resulting in an overall rating of "X". Comparative Example 3 failed both the quasi-noncombustible and noncombustible tests because the basis weight of the colored coating layer on the surface portion was too high.

Comparative Example 4 is an example in which the surface portion, basis weight of the colored coating film layer, and back surface configuration are the same as those of Examples 1 to 5 and 7 and 8, and the polyisocyanurate composition contains 68.0 wt% isocyanate, 10.33 wt% main polyol 1, 2.81 wt% ether polyol, 11.02 wt% flame retardant, 0.17 wt% catalyst 1, 0.58 wt% catalyst 2, 0.30 wt% catalyst 3, 0.68 wt% foam stabilizer, and 6.11 wt% blowing agent 2 (cyclopentane), an isocyanate index of 432, and a viscosity of the polyol component at 25°C of 2049 mPa·s.

Comparative Example 4 is an example in which main polyol 1 having a high viscosity at 25°C was blended and a foam stabilizer was blended instead of a cell breaker, and the result was no health bubbles during foaming, a closed cell rate of 89.0%, a nurate rate of 35.1%, a density of 32.7 kg/ ^m3 , and it was impossible to determine whether it was semi-noncombustible or noncombustible, resulting in an overall rating of "X". In Comparative Example 4, because a foam stabilizer was blended instead of a cell breaker, the closed cell rate became extremely high, and it was impossible to determine whether it was semi-noncombustible or noncombustible.

As such, the colored insulation board of the present invention has a colored surface and passes the cone calorimeter test with a quasi-nonflammable or higher rating, making it suitable for use as building materials such as interior decorations that require both color decorativeness and flame retardancy. In the examples, a colored coating layer was applied to only one side of the colored insulation board, but it may also be applied to both sides.

REFERENCE SIGNS LIST 10 Colored heat insulation board 11 Main body made of polyisocyanurate foam 21 Surface portion 22 Adhesive resin layer on surface portion 23 Aluminum layer on surface portion 24 Colored coating layer on surface portion 31 Back portion 32 Adhesive resin layer on back portion 33 Aluminum layer on back portion

Claims (2)

A polyisocyanurate foam for colored heat insulation boards, obtained from a polyisocyanurate composition containing a polyol component, a blowing agent, a catalyst, a cell opener, and an aromatic polyisocyanate, characterized in that the catalyst contains a trimerization catalyst, the nurate content is 35.4 to 40%, and the closed cell content is 0 to 30%. a polyisocyanurate foam obtained from a polyisocyanurate composition comprising a polyol component, a blowing agent, a catalyst, a cell opener, and an aromatic polyisocyanate, wherein the catalyst comprises a trimerization catalyst, and the polyisocyanurate foam has a nurate content of 30 to 40% and a closed cell content of 0 to 30%;
an aluminum layer adhered to both sides of the polyisocyanurate foam;
a colored coating layer provided on at least one surface of the aluminum layer,
The color coating layer has a basis weight of 1.5 to 13 g/ ^m2 ,
A colored heat insulating board that has semi-non-flammable performance or higher in a heat generation test conducted in accordance with the cone calorimeter test specified in ISO 5660-1.