Colored insulation board and polyisocyanurate foam for colored insulation board

Abstract

The object of the present invention is to provide a colored heat insulating board that passes the cone calorimeter test as semi-incombustible or better, and has color decorativeness and good flame retardancy. The present invention comprises a polyisocyanurate foam (11) obtained from a polyisocyanurate composition containing a polyol, a blowing agent, a catalyst, a cell opener, and an aromatic polyisocyanate, aluminum layers (23, 33) bonded to both sides of the polyisocyanurate foam (11), and a colored coating layer (24) applied in color to the surface of at least one of the aluminum layers (23, 33), wherein the cell opener is a combination of a butadiene-based cell opener and a silicone-based cell opener, and the catalyst includes a trimerization catalyst. The polyisocyanurate foam (11) has a nurate content of 30 to 40%, a closed cell content of 0 to 30%, and a basis weight of the colored coating layer of 1.5 to 13 g / m. 2 It was decided.

Description

[Technical Field]

[0001] The present invention relates to a colored insulation board having a colored surface. [Background technology]

[0002] An insulating board used for the interior of buildings is made by laminating aluminum facings on both sides of a polyisocyanurate foam. Polyisocyanurate foam is used as a building material because it has heat insulating properties, flame retardancy, and strength.

[0003] Insulation boards made by laminating aluminum facings to both sides of polyisocyanurate foam have a metallic aluminum surface color with no color variation, so they may not be suitable for some applications. For this reason, there has been a demand for insulation boards in a variety of colors in recent years.

[0004] Conventionally, polyisocyanurate foams having a closed cell rate of 20% or less, or 69% or more have been disclosed (Table 2 of Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 3948014 [Patent Document 2] Patent No. 4541970 Summary of the Invention [Problem to be solved by the invention]

[0006] 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. [Means for solving the problem]

[0007] First aspect of the invention The present invention relates to 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 is a combination of a butadiene-based cell opener and a silicone-based cell opener, the catalyst contains 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 / m. 2 It is characterized in that:

[0008] The second aspect of the invention is the same as the first aspect of the invention. The polyisocyanurate composition has an isocyanate index of 300 to 600.

[0009] The third aspect of the invention is the first or second aspect of the invention. The method is characterized in that the amount of the cell opener is 0.2 to 0.5% by weight based on 100% by weight of the polyisocyanurate composition.

[0010] The fourth aspect of the invention is any one of the first to third aspects of the invention. wherein 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 / m 3 It is characterized in that:

[0011] The fifth aspect of the invention is the fourth aspect of the invention. The method is characterized in that 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.

[0012] The sixth aspect of the invention is any one of the first to fifth aspects of the invention.The polyol component has a viscosity of 25 to 6000 mPa·s at 25° C., and each polyol constituting the polyol component has a molecular weight of 100 to 900 and a functional group number of 2 to 4. [Effects of the Invention]

[0013] According to the present invention, a colored heat insulating board is obtained as a fire-retardant material having a colored surface and capable of passing the cone calorimeter test, which is a heat generation test, as a semi-noncombustible or better grade. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a cross-sectional view showing one embodiment of a colored heat insulating board of the present invention. [Figure 2] 1 is a table showing the criteria for the cone calorimeter test. [Figure 3] 1 is a table showing the configurations, blending, physical properties, heat generation test, judgment, overall evaluation, etc. of Examples 1-4. [Figure 4] 1 is a table showing the configurations, blending ratios, physical properties, evaluations, and overall evaluations of Examples 5-10. [Figure 5] 1 is a table showing the configuration of comparative examples, the composition, physical properties, heat generation test, judgment, overall evaluation, etc. DETAILED DESCRIPTION OF THE INVENTION

[0015] The colored heat insulating board 10 according to one embodiment of the present invention shown in FIG. 1 comprises a main body 11, a surface 21, and a back surface 31. It passes the heat generation test, a cone calorimeter test, with the rating of at least semi-noncombustible, and is suitable as an interior material such as a ceiling material for a building, or as an exterior material.

[0016] The main body 11 is made of a polyisocyanurate foam obtained by reacting a polyisocyanurate composition. The polyisocyanurate foam constituting 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%.

[0017] If the nurate ratio of the polyisocyanurate foam is low, the flame retardancy will be low, and conversely, if the nurate ratio is high, the foam will become brittle, with reduced compressive strength and bending properties, making it unsuitable as a structure. The nurate ratio is measured based on 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 [NH], urea [C=O], urethane, and nurate [C=O], and is calculated using the following nurate ratio calculation formula using a, b, c, and d:

[0018] a: Absorption peak position based on nurate ring: 1410 cm -1 , Area position: 1347.03~1464.67cm -1 Area of b: Absorption peak position based on [NH] of urethane and urea: 1510 cm -1 , Area position: 1460.81~1562.06cm -1 Area of c: Absorption peak position based on urea "C=O": 1595 cm -1 , Area position: 1566.88~1638.23cm -1 Area of d: Absorption peak position based on "C=O" of urethane and nurate: 1710 cm -1 , Area position: 1636.3~1768.4cm -1 Area of Nutrate rate (%) = [a / (a+b+c+d)] x 100

[0019] To achieve the above-mentioned nurate conversion rate, the isocyanate index is preferably 300 or more, more preferably 300 to 600, or 350 to 500. Details of the isocyanate index will be described later.

[0020] The closed cell ratio in the present invention is a value measured in accordance with ASTM D 2856. If the closed cell ratio of the polyisocyanurate foam is high, thermal decomposition gas of 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 gas of the foam to flow to the end of the foam due to the interconnected structure during heat generation tests. This prevents the decomposition gas 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.

[0021] The density of the polyisocyanurate foam (JIS K7222:2005) is 25 to 45 kg / m 3 If the density is too low, the strength will be insufficient, and conversely, if the density is too high, the material will be too heavy for use as a ceiling or wall material, and lightweight materials are preferred during construction, making it undesirable from the perspective of wall structural materials, etc. The thickness of the polyisocyanurate foam constituting the main body 11 is set appropriately, and is, for example, 10 to 70 mm.

[0022] 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.

[0023] 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, as well as 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 alkylene oxides such as ethylene oxide or propylene oxide to these, polyethylene glycol, polypropylene glycol, etc.), and trifunctional polyols (trimethylolpropane, glycerin, etc., or compounds obtained by addition polymerization of alkylene oxides to these).

[0024] 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 have two or more hydroxyl groups, preferably two to three.

[0025] Furthermore, examples of polyetherester polyols include those obtained by reacting polyether polyol with a polybasic acid to form a polyester, and those having both polyether and polyester segments in one molecule.

[0026] In the present invention, when a plurality of types of polyols are used, the polyol component refers to a polyol mixture in which the polyols used are blended in the blending ratios shown in each example, or when a single polyol is used, refers to that polyol, and includes polyether polyols, polyester polyols, and polyether ester polyols.

[0027] The viscosity of the polyol component in the present invention is preferably 25 to 6000 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.

[0028] Furthermore, the viscosity at 25°C of each polyester polyol constituting the polyol component in the present invention is preferably 600 to 6000 mPa·s (ASTM D4889), more preferably 900 to 5600 mPa·s.The number average molecular weight of each polyester polyol constituting the polyol component is preferably 200 to 900, and the number of functional groups is preferably 2 to 4.

[0029] 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 buildup tests.

[0030] The amount of the polyol component is preferably 1 to 20% by weight based on 100% by weight of the polyisocyanurate composition.

[0031] The blowing agent can be water, a chemical blowing agent, or a physical blowing agent such as pentane or a hydrofluoroolefin, either alone or in combination. When water is used, carbon dioxide gas is generated during the reaction between the polyol and polyisocyanate, and this carbon dioxide gas is used to create the foam. The amount of blowing agent can be adjusted as needed. When water is used in combination with other blowing agents, the amount of water is preferably 0.1 to 1.5 wt% per 100 wt% of the polyisocyanurate composition. When water is used in combination with other blowing agents, the amount of water is preferably 0 to 1.0 wt% per 100 wt% of the polyisocyanate composition. When the physical blowing agent is pentane, the amount is preferably 8 to 0 wt%. When the physical blowing agent is hydrofluoroolefin, the amount is preferably 15 to 0 wt%.

[0032] The catalyst essentially contains a trimerization catalyst used in the production of polyisocyanurate foams. Furthermore, the trimerization catalyst can be used in combination with a urethanization catalyst (resinization catalyst, foaming catalyst).

[0033] Examples of trimerization catalysts include: 1) metal oxides such as lithium oxide, sodium oxide, and potassium oxide; 2) alkoxides such as sodium methoxy, sodium ethoxy, sodium propoxy, sodium butoxy, potassium methoxy, potassium ethoxy, potassium propoxy, and potassium butoxy; 3) organometallic salts such as potassium acetate, potassium 2-ethylhexane, 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) ethyleneimine derivatives; 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, it is more preferable to use 3) organic metal salts and 6) quaternary ammonium salts. Preferably, a combination of potassium acetate and potassium octylate can be used.

[0034] 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 catalysts such as stannous octoate; and metal catalysts (also referred to as organometallic catalysts) such as phenylmercury propionate and lead octenate.

[0035] The amount of the trimerization catalyst is preferably 0.8 to 7% by weight based on 100% by weight of the polyisocyanurate composition.

[0036] 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, and a foam with a low closed cell ratio can be obtained in a good foaming state. The weight ratio of the butadiene-based cell opener to the silicone-based cell opener is preferably 25:1 to 1:1 (butadiene-based cell opener:silicone-based cell opener). The preferred amount of the cell opener is 0.2 to 0.5% by weight based on 100% by weight of the polyisocyanurate composition.

[0037] Examples of aromatic polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xylylene diisocyanate, polymeric polyisocyanate (crude MDI), etc. Two or more aromatic polyisocyanates may be used in combination.

[0038] The amount of aromatic polyisocyanate 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 becomes flammable and prone to heat shrinkage, whereas if it is more than 600, the foam becomes brittle and the compressive strength and bending properties decrease, making it undesirable as a structure.

[0039] Furthermore, as described above, by setting the isocyanate index within the above range and adding a trimerization catalyst appropriately, a nurate conversion rate of 30 to 40% can be achieved in the present invention. The isocyanate index is defined as the value obtained by dividing the number of moles of isocyanate groups in the polyisocyanate by the total number of moles of active hydrogen groups such as hydroxyl groups in the polyol and water as a blowing agent, and multiplying the result by 100, and is calculated as [NCO equivalent of polyisocyanate / active hydrogen equivalent × 100].

[0040] Examples of auxiliary agents that are 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, 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.

[0041] The polyisocyanurate composition is mixed in a known foaming device, whereby the polyol and aromatic polyisocyanate react with each other and foam to form a polyisocyanurate foam.

[0042] The surface portion 21 constitutes one side of the colored heat insulation board 10. As shown in the enlarged cross-sectional view of part A in FIG. 1, the surface portion 21 is made up of an adhesive resin layer 22, an aluminum layer 23, and a colored coating layer 24.

[0043] The adhesive resin layer 22 is located between the main body 11 made of polyisocyanurate foam and the aluminum layer 23, and is provided for reasons such as improving the adhesive strength between the aluminum layer 23 and the main body 11 made of polyisocyanurate foam. The adhesive resin layer 22 can be formed by applying a resin coating prepared by dissolving a synthetic resin in a solvent to one side of the aluminum layer 23 to a predetermined thickness and drying the coating. The adhesive resin layer 22 has a basis weight of 1.0 to 10.0 g / m. 2 It is preferable that the adhesive resin layer 22 has a low basis weight, which makes it difficult to form a uniform resin layer. On the other hand, if the adhesive resin layer 22 has a high basis weight, the surface material will swell in a cone calorimeter test and come into contact with the spark plug, making it difficult to obtain non-flammable performance. Examples of resins for the adhesive resin layer 22 include epoxy resin, acrylic resin, and urethane resin.

[0044] The aluminum layer 23 is made of aluminum foil. The thickness of the aluminum layer 23 is preferably 12 to 150 μm. If the thickness of 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 heat insulation board 10 will not perform at least semi-non-combustible in a cone calorie test. Conversely, if the thickness of the aluminum layer 23 is too thick, the colored heat insulation board 10 will become heavy and costs will increase. The aluminum foil that constitutes the aluminum layer 23 can also be coated with an adhesive resin layer 22 in advance.

[0045] 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, in which a resin is dissolved in a solvent and a colorant is dispersed, to the surface of the aluminum layer 23 (the surface opposite to the surface on which the adhesive resin layer 22 is provided) in 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 basis weight of the colored coating layer 24 is 1.5 to 12.0 g / m 2 It is preferable that the coating weight of the colored coating layer 24 is low. If the coating weight is low, the coating layer cannot be formed uniformly or the coloring will be insufficient. On the other hand, if the coating weight of the colored coating layer 24 is high, the layer will swell in a cone calorimeter test and will not pass the quasi-fireproof standard. The color of the colored coating may be white, yellow, light blue, ivory, or the like, and is determined appropriately depending on the installation location of the colored insulation board 10, etc. The colored coating layer 24 can be applied by gravure coating, spray coating, roll coating, comma coating, etc.

[0046] The back surface 31 constitutes the other surface of the colored heat insulating board 10. The back surface 21 is made up of an adhesive resin layer 32 and an aluminum layer 33, as shown in the enlarged cross-sectional view of part B in FIG.

[0047] 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 has a basis weight of 1.0 to 10.0 g / m 2 Examples of the resin that constitutes the adhesive resin layer 32 include epoxy resin, acrylic resin, and urethane resin.

[0048] 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 constituting the aluminum layer 33 may be coated with an adhesive resin layer 32 in advance.

[0049] The colored heat insulating board 10 passes the cone calorimeter test as semi-non-combustible or better. The cone calorimeter test is carried out using a radiant electric heater at 50 kW / m 2 This test, specified in ISO 5660-1, involves irradiating a sample with light and measuring the calorific value to determine heat generation. The cone calorimeter test has three classes: non-combustible, semi-non-combustible, and flame-retardant, as shown in Figure 2. Here, "non-combustible" refers to a material that meets the requirements of "non-combustible materials" as defined in Article 2, Paragraph 9 of the Building Standards Act and also meets the requirements of Article 108-2 of the Enforcement Order of the Building Standards Act. "Semi-non-combustible" refers to a "semi-non-combustible 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.

[0050] The criteria for non-combustibility are: (1) the total calorific value is 8 MJ / m within 1200 seconds (20 minutes) after the start of heating; 2 (2) There are no cracks or holes that penetrate to the back surface that are harmful to fire prevention. (3) The maximum heat generation rate is 200 kW / m for 10 seconds or more. 2 The test is passed if all of the following conditions are met: (1) the spark plug voltage does not exceed 100 V, and (4) there is no spark leakage. If any one of (1) to (3) is not met, the test is failed, and if (4) is not met, it is impossible to judge. Note that "spark leakage" refers to the phenomenon in which the spark between the plugs is absorbed by the test specimen.

[0051] The criteria for quasi-noncombustible are: (1) the total calorific value is 8 MJ / m within 600 seconds (10 minutes) after the start of heating; 2 (2) There are no cracks or holes that penetrate to the back surface that are harmful to fire prevention. (3) The maximum heat generation rate is 200 kW / m for 10 seconds or more. 2(1) The test is passed if all of the following conditions are met: (1) does not exceed (3), and (4) no spark leaks. (2) The test is failed if any of the conditions (1) to (3) is not met, and it is impossible to judge if the condition (4) is not met.

[0052] The criteria for flame retardancy are: (1) a total calorific value of 8 MJ / m within 300 seconds (5 minutes) after the start of heating; 2 (2) There are no cracks or holes that penetrate to the back surface that are harmful to fire prevention. (3) The maximum heat generation rate is 200 kW / m for 10 seconds or more. 2 (1) The test is passed if all of the following conditions are met: (1) does not exceed (3), and (4) no spark leaks. (2) The test is failed if any of the conditions (1) to (3) is not met, and it is impossible to judge if the condition (4) is not met.

[0053] 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, discharging a polyisocyanurate composition onto the adhesive resin layer 32, and laminating the aluminum layer (aluminum foil) 23, previously coated with the adhesive resin layer 22, with the adhesive resin layer 22 facing downward on the polyisocyanurate composition during foaming due to reaction, and allowing the polyisocyanurate composition to foam and harden. This allows the aluminum layers 23, 33 to be bonded and laminated via the adhesive resin layers 22, 32 to the main body 11, which is made of a polyisocyanurate foam obtained by reacting the polyisocyanurate composition. This reduces the amount of adhesive resin layers 22, 32 applied for bonding, and reduces 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 formed by coating on the surface of the aluminum layer 23 in advance, or when colored coating layers are formed on both sides, a colored coating layer is also formed on the surface of the other aluminum layer 33. [Example]

[0054] A mold (foam molding mold) consisting of a lower and upper molds and forming 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 then placed over the lower mold to close the mold. The polyisocyanurate composition was then foamed within the cavity. The molded article was then demolded and cut into 100 mm square pieces to obtain samples for heat buildup testing 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. The closed cell content, foam density, and nurate content were measured. The configurations of the respective 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.

[0055] The surface member was prepared as follows. First, an epoxy resin (transparent, product name: RC12 [hardener], JER828 [base material], manufactured by Mitsubishi Chemical Corporation, blended at a ratio of 50% of hardener to 100% of base material) diluted with methyl ethyl ketone was applied to one side of an aluminum foil (alloy number 1N30, manufactured by Toyo Aluminum Co., Ltd.) having the thickness of each example and each comparative example shown in the aluminum layer column of the surface portion of Figures 3 to 5. A diluted resin solution was then applied with a bar coater to the basis weight of each example and each comparative example shown in the adhesive resin layer column of the surface portion of Figures 3 to 5, and the result was left at room temperature for one week to prepare an adhesive resin layer. Furthermore, a diluted resin solution was applied with a bar coater to the surface opposite the adhesive resin layer of the aluminum foil, in which an epoxy resin (white, product name: Rockhold White, manufactured by Rock Paint Co., Ltd.) containing a colorant was diluted with thinner to the basis weight of each example and each comparative example shown in the colored coating layer column on the surface side of Figures 3 to 5, and the result was left at room temperature for one week to prepare a colored coating layer.

[0056] The back surface member was produced as follows: First, a diluted resin solution prepared by diluting an epoxy resin (transparent, product names: RC12 [hardener], JER828 [base material], Mitsubishi Chemical Corporation, 100 g of base material mixed at a ratio of 50 g of hardener) with methyl ethyl ketone was applied to one surface of an aluminum foil (alloy number 1N30, manufactured by Toyo Aluminum K.K.) having the thickness of each example and each comparative example shown in the column for aluminum layer on the back surface of Figures 3 to 5, using a bar coater, so as to have the basis weight of each example and each comparative example shown in the column for adhesive resin layer on the back surface of Figures 3 to 5, and the coating was left at room temperature for one week to produce an adhesive resin layer.

[0057] 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, functional group number: 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, functional group number: 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, functionality 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.

[0058] Flame retardant: Tris(dichloropropyl)phosphate, 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 Catalyst 2: Trimerization catalyst, potassium octylate Catalyst 3: Trimerization catalyst, potassium acetate Foam stabilizer: Silicone 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 breaker 2: Silicone-based foam breaker, product name: Tegostab B8523, manufactured by Evonik Japan Co., Ltd. Foaming agent 1: Water Blowing agent 2: Cyclopentane Blowing agent 3: Hydrofluoroolefin, product name: Solstice LBA, manufactured by Honeywell Japan Co., Ltd.

[0059] 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) in 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 of the polyisocyanurate foam (main body, free foam) in each example and comparative example was measured 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.

[0060] In Examples 1 to 5, the weight of the colored coating film layer on the surface was 5 g / m 2 The thickness of the aluminum layer is 80 μm, and the weight of the adhesive resin layer is 1.6 g / m 2 The thickness of the foam (polyisocyanurate foam) was 50 mm, the thickness of the aluminum layer on the back side was 20 μm, and the weight of the adhesive resin layer was 1.6 g / m 2 This is an example in which the amount of each material in the polyisocyanurate composition was changed.

[0061] 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.

[0062] Example 1 is an example in which the amount of cell breaker 2 (silicone-based) was reduced compared to the other examples, and health bubbles were present during foaming, with a closed cell rate of 2.4%, a nurate rate of 33.0%, and a density of 28.5 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, with an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible performance or higher.

[0063] 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.

[0064] In Example 2, there was health bubble during foaming, the closed cell rate was 1.3%, the nurate rate was 34.0%, and the density was 30.5 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, and has an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible or higher performance.

[0065] 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.

[0066] Example 3 is an example in which the amount of cell breaker 2 (silicone-based) was increased compared to the other examples, and health bubbles were formed during foaming, the closed cell rate was 2.6%, the nurate rate was 35.4%, and the density was 29.3 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, with an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible performance or higher.

[0067] 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); an isocyanate index of 420; and a viscosity of the polyol component at 25°C of 771 mPa·s.

[0068] Example 4 is an example in which water as a foaming agent is not blended, and health bubbles are present during foaming, with a closed cell rate of 4.9%, a nurate rate of 32.5%, and a density of 31.2 kg / m 3 , passed the semi-non-combustible and non-combustible standards, and the overall rating was "◎". The surface was colored and the fireproof material had performance equal to or better than semi-non-combustible. Note that Example 4 did not contain water as a foaming agent, so the closed cell ratio was higher than the other Examples.

[0069] 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); an isocyanate index of 422; and a viscosity of the polyol component at 25°C of 727 mPa·s.

[0070] Example 5 is an example in which the amount of water blended was reduced compared to Examples other than Example 4 (an example in which water was not blended as a foaming agent), and it had health bubbles when foamed, a closed cell rate of 0%, a nurate rate of 33.0%, and a density of 31.9 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, with an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible performance or higher.

[0071] In Example 6, the weight of the colored coating film layer on the surface was 13 g / m 2 The other configurations of the surface portion, the configuration of the back surface portion, and the polyisocyanurate composition were the same as those in Example 2. The isocyanate index was 412.

[0072] Example 6 is an example in which the weight of the colored coating film 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%, and a density of 30.5 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, with an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible performance or higher.

[0073] 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.

[0074] 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. The foam had no health bubbles during foaming, a closed cell rate of 15%, a nurate rate of 37.5%, and a density of 32.3 kg / m 3 , passed the quasi-noncombustible test but failed the noncombustible test, and therefore received an overall rating of "Good." Example 7, due to the inclusion of Main Polyol 1, which has a high viscosity at 25°C, could not be judged as noncombustible, but the surface was colored and the fireproof material had at least quasi-noncombustible performance.

[0075] 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.

[0076] Example 8 is an example in which a high-viscosity main polyol 3, whose viscosity at 25°C is higher than that of main polyol 2 but lower than that of main polyol 1, was blended. This example produced no health bubbles during foaming, a closed cell rate of 25%, a nurate rate of 32.6%, and a density of 31.9 kg / m 3 Example 8 failed the incombustible test due to the inclusion of Main Polyol 3, which has a high viscosity at 25°C, but the surface was colored and the fireproof material had at least semi-incombustible performance.

[0077] 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.

[0078] In Example 9, there was health bubble during foaming, the closed cell rate was 1.8%, the nurate rate was 32.0%, and the density was 30.2 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, and has an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible or higher performance.

[0079] 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); an isocyanate index of 493; and a viscosity of the polyol component at 25°C of 727 mPa·s.

[0080] Example 10 has health bubbles when foamed, a closed cell rate of 3.5%, a nurate rate of 38.9%, and a density of 31.3 kg / m 3 It has passed the semi-non-combustible and non-combustible standards, and has an overall rating of "◎". The surface is colored and it is a fire-resistant material with semi-non-combustible or higher performance.

[0081] Comparative Example 1 is an example in which the surface portion and the back portion of Example 2 were not provided, and the formulation of the polyisocyanurate composition was almost the same as Example 2, except that the amount of cell opener 2 (silicone-based) was 0 wt %.

[0082] 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 physical properties of the foam or heat generation, and the overall evaluation was "X".

[0083] Comparative Example 2 is an example in which the formulation of the polyisocyanurate composition in Example 2 was almost the same as that in Example 2, except that both cell opener 1 (butadiene-based) and cell opener 2 (silicone-based) were set to 0 wt %. The configurations of the front and back surfaces were also the same as those in Example 2.

[0084] Comparative Example 2 is an example in which both cell opener 1 (butadiene-based) and cell opener 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%, and the density was 28.1 kg / m 3In Comparative Example 2, both cell opener 1 (butadiene-based) and cell opener 2 (silicone-based) were set to 0 wt %, resulting in an extremely high closed cell rate and failing both the semi-noncombustible and noncombustible tests.

[0085] In Comparative Example 3, the weight of the colored coating film layer on the surface of Example 2 was 35 g / m 2 This example has almost the same composition as in Example 2, except that the amount of the surface layer was increased, and the surface and back surfaces were also the same as in Example 2.

[0086] In Comparative Example 3, the weight of the colored coating film layer on the surface was 35 g / m 2 This is an example of an increased amount of foam, with health bubbles during foaming, a closed cell rate of 1.3%, a nurate rate of 34.0%, and a density of 30.5 kg / m 3 The comparative example 3 failed both the semi-non-combustible and non-combustible tests, resulting in an overall rating of "X." The comparative example 3 failed both the semi-non-combustible and non-combustible tests because the basis weight of the colored coating film layer on the surface was too high.

[0087] In Comparative Example 4, the surface portion, the basis weight of the colored coating film layer, and the configuration of the back surface portion were the same as in Examples 1 to 5 and Examples 7 and 8, and the polyisocyanurate composition contained 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, 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.

[0088] Comparative Example 4 is an example in which a main polyol 1 having a high viscosity at 25°C was blended and a foam stabilizer was blended in place of a cell breaker. The foam had no health bubbles during foaming, a closed cell rate of 89.0%, a nurate rate of 35.1%, and a density of 32.7 kg / m 3 In Comparative Example 4, a foam stabilizer was blended instead of a cell breaker, resulting in an extremely high closed cell rate and making it impossible to determine whether the composition was semi-non-combustible or non-combustible.

[0089] In this way, the colored heat insulating board of the present invention has a colored surface and passes the cone calorimeter test to a quasi-noncombustible or higher standard, making it suitable for use as a building material such as an interior material that requires both color decorativeness and flame retardancy. In the examples, a colored coating layer was provided on only one side of the colored heat insulating board, but it may also be provided on both sides. [Explanation of symbols]

[0090] 10 Colored insulation board 11 Main body made of polyisocyanurate foam 21 Surface part 22 Surface adhesive resin layer 23 Aluminum layer on the surface 24 Colored coating layer on the surface 31 Back part 32 Adhesive resin layer on the back surface 33 Aluminum layer on the backside

Claims

1. 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%.

2. A polyisocyanurate foam obtained from a polyisocyanurate composition containing a polyol component, a blowing agent, a catalyst, a cell breaker, and an aromatic polyisocyanate, wherein the catalyst contains a trimerization catalyst, and the polyisocyanurate foam has a nurate ratio of 30 to 40% and a closed cell ratio 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 weight of the colored coating layer is 1.5 to 13 g / m ２ and 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.

Images