WO2015092988A1 - 硬質ウレタンフォーム原液組成物、及び断熱施工方法 - Google Patents
硬質ウレタンフォーム原液組成物、及び断熱施工方法 Download PDFInfo
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- WO2015092988A1 WO2015092988A1 PCT/JP2014/005988 JP2014005988W WO2015092988A1 WO 2015092988 A1 WO2015092988 A1 WO 2015092988A1 JP 2014005988 W JP2014005988 W JP 2014005988W WO 2015092988 A1 WO2015092988 A1 WO 2015092988A1
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- stock solution
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
- F16L59/021—Shape or form of insulating materials, with or without coverings integral with the insulating materials comprising a single piece or sleeve, e.g. split sleeve, two half sleeves
- F16L59/022—Shape or form of insulating materials, with or without coverings integral with the insulating materials comprising a single piece or sleeve, e.g. split sleeve, two half sleeves with a single slit
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/10—Bandages or covers for the protection of the insulation, e.g. against the influence of the environment or against mechanical damage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
Definitions
- the present invention relates to a hard urethane foam stock solution composition that can be used as a foamable joint filler, and a heat insulation construction method that uses such a hard urethane foam stock solution composition as a foamable joint filler.
- a heat insulation structure for low-temperature fluid transportation pipes such as LPG and LNG
- the outer surface of the pipe is covered with a split-cylinder molded heat insulating material made of hard urethane foam, and the hardened polyurethane foam is formed on the joint joint of the molded heat insulating material.
- a heat insulation construction method for constructing a heat insulation structure in which a raw material composition is filled by in-situ foaming and a moisture-proof material is provided on the outer surface of the molded heat insulating material and an exterior material is provided on the outer surface of the molded heat insulating material. are known.
- the joint opening that opens downward is closed with an adhesive tape, and a flow path for pouring the rigid urethane foam stock solution composition needs to be provided separately so as to allow pouring from above the joint. was there.
- a method is also known in which an adhesive is applied to the abutting surface of the molded heat insulating material without leaving a space in the joint, and the molded heat insulating material is assembled to the construction object.
- an adhesive tape that closes the opening of the joint can be omitted.
- the surfaces to be abutted must be in contact with each other, and the surface where the worker cut out the molded insulation for dimensional adjustment at the construction site is surface accuracy. Therefore, the construction method using an adhesive cannot be applied.
- the inventors of the present invention have made extensive studies in view of the above circumstances, and as a result, the outer surface of an object to be constructed such as piping is covered with a molded heat insulating material, and the heat insulating structure in which the molded heat insulating materials are joined and integrated.
- the hard urethane foam stock solution composition is applied as a foamable joint filler to the abutting surface of the molded heat insulating material forming the joint, and the molded heat is foamed and cured by assembling the molded heat insulating material. If the entire space in the joint portion can be filled and integrated with the molded heat insulating material, the above troublesome work can be omitted, and an adhesive tape that closes the opening of the joint portion will be unnecessary. It was.
- a hard urethane foam stock solution composition for injection foaming generally used in this type of heat insulation construction method has high fluidity and drips even if it is applied to the butted surface of the molded heat insulating material forming the joint.
- the present inventors have made it possible to use as a foamable joint filler by imparting coating properties to the rigid urethane foam stock solution composition while preventing the generation of bubbles during foaming.
- the present invention has been completed by paying attention to the relationship between the amount of the inorganic filler added to the rigid urethane foam stock solution composition and the viscosity thereof.
- the present invention aims to provide a hard urethane foam stock solution composition that can be used as a foamable joint filler, and a heat insulation construction method that uses such a hard urethane foam stock solution composition as a foamable joint filler. .
- the rigid urethane foam stock solution composition according to the present invention is a two-component hard urethane foam stock solution composition in which a stock solution A containing a polyisocyanate component and a stock solution B containing a polyol component are mixed to form a hard urethane foam. Then, 15% by weight or more of the inorganic filler is added to the stock solution B with respect to the total weight of the stock solution A and the stock solution B to be mixed, and the viscosity ⁇ of the stock solution A is adjusted to 1 to 100 Pa ⁇ s.
- the mixed solution of the stock solution A and the stock solution B exhibits thixotropic properties, and the viscosity ⁇ of the mixed solution is ⁇ (35 ° C., 0.1 s ⁇ 1 ) ⁇ 200 Pa ⁇ s, ⁇ (5 ° C., 100 s ⁇ 1 ) ⁇ 200 Pa ⁇ s.
- the heat insulation construction method according to the present invention covers the outer surface of the construction object with a plurality of molded heat insulating materials, and as described above in constructing a heat insulating structure in which the molded heat insulating materials are joined and integrated.
- a rigid urethane foam stock solution composition the mixed solution of the stock solution A and the stock solution B is applied to the butt surface of the molded heat insulating material forming the joint, and the molded heat insulating material is assembled, The mixed liquid is foamed and cured to fill the entire space in the joint and integrate with the molded heat insulating material.
- the hard urethane foam stock solution composition according to the present invention can be used as a foamable joint filler that is imparted with coating properties without impeding the formation of bubbles during foaming and can form a good hard urethane foam. .
- the rigid urethane foam stock solution composition in the present embodiment is a two-component hard urethane foam stock solution composition in which a stock solution A containing a polyisocyanate component and a stock solution B containing a polyol component are mixed to form a hard urethane foam. .
- the polyisocyanate component contained in the stock solution A is a known polyfunctional polyisocyanate, for example, an aromatic, aliphatic, or alicyclic polyisocyanate, or a mixture thereof, or a modification thereof. And modified polyisocyanates that can be used.
- aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), or polymethylene polyphenyl isocyanate (crude MDI) are preferable. Methylene polyphenyl isocyanate (crude MDI) is particularly preferred.
- the polyol component contained in the stock solution B is a polyol having 2 to 8 hydroxyl groups in the molecule, and the average hydroxyl value of the entire polyol component is preferably 200 to 600 mgKOH / g, more preferably 300 to 500 mgKOH / g. g, the average molecular weight is preferably 200 to 3000, more preferably 200 to 2000, still more preferably 300 to 2000, and particularly preferably 300 to 1000, and any known polyol can be used in any combination. For example, by esterification of aromatic polyols such as propylene glycol, glycerin, pentaerythritol, ethylenediamine, tolylenediamine, sorbitol, sucrose, etc.
- aromatic polyols such as propylene glycol, glycerin, pentaerythritol, ethylenediamine, tolylenediamine, sorbitol, sucrose, etc.
- alkylene oxide examples thereof include aromatic polyester polyols obtained or mixtures of two or more thereof.
- propylene glycol, glycerin, pentaerythritol, sorbitol because the reaction rate with the polyisocyanate component contained in the stock solution A is not too fast, and it is easy to ensure the pot life that can be applied at the construction site.
- a polyether polyol to which alkylene oxide is added using as an initiator is preferred.
- the stock solution B can be blended with a catalyst, a foam stabilizer, a flame retardant and the like, if necessary.
- a catalyst include tertiary amines and organic metal salts, and these can be used alone or in combination of two or more.
- the foam stabilizer include a silicone-based surfactant.
- the flame retardant include trischloropropyl phosphate (TCPP).
- blowing agent examples include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1-chloro-3,3 , 3-trifluoro-propene (HFO-1233zd), 1,1,1,4,4,4-hexafluorobutene (HFO-1336mzz) and the like, or n-pentane, isopentane, cyclopentane And the like, but it is preferable to use water that reacts with polyisocyanate to generate carbon dioxide gas.
- the equivalent ratio of the isocyanate group of the polyisocyanate component contained in the stock solution A and the hydroxyl group of the polyol component contained in the stock solution B is appropriately adjusted so that (NCO / OH) is preferably 0.9 to 2.0, more preferably 1.1 to 1.5.
- an inorganic filler is added in an amount of 15% by weight or more, preferably 15 to 45% by weight, more preferably 15 to 35% by weight based on the total weight of the stock solution A and the stock solution B to be mixed.
- the inorganic filler include inorganic compounds such as calcium carbonate and colloidal silica.
- the inorganic filler used in the present embodiment has a uniform particle size so that it is easy to adjust the thixotropy of the mixed solution of the stock solution A and the stock solution B, and if necessary, an organic material such as fatty acid and rosin acid. You may perform the surface treatment using an acid.
- the viscosity ⁇ of the stock solution A is adjusted to 1 to 100 Pa ⁇ s, the viscosity of the mixed solution mixed with the stock solution B is increased, and the film thickness of the bubbles formed during foaming is increased. By doing so, bubbles are prevented from breaking during foaming, and a good rigid urethane foam is formed.
- the viscosity ⁇ of the stock solution A is preferably 1 to 50 Pa ⁇ s, more preferably 2 to 10 Pa ⁇ s.
- the viscosity ⁇ of the liquid mixture is 35 Pa at a temperature assuming a coating viscosity of 35 ° C. and a rotational speed of 0.1 s ⁇ 1 (35 ° C., 0.1 s ⁇ 1 ) is 200 Pa ⁇ s.
- the adjustment is made so that the pressure is 220 Pa ⁇ s or more, more preferably 250 Pa ⁇ s or more.
- the viscosity ⁇ (5 ° C., 100 s ⁇ 1 ) is 200 Pa ⁇ s or less under the conditions of a temperature 5 ° C. and a rotation speed 100 s ⁇ 1 assuming the viscosity when the stock solution A and the stock solution B are mixed and stirred.
- 100 Pa ⁇ s or less Preferably 100 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or less.
- the viscosity of the stock solution A is measured under a temperature condition of 25 ° C. in accordance with JIS K7117-1.
- the viscosity ⁇ of the mixed solution of the stock solution A and the stock solution B is measured in a mixing container at a predetermined ratio, mixed and stirred for 30 seconds, and after 120 seconds from the start of mixing and stirring, conforms to JIS K7117-2. And measured.
- the polyisocyanate exemplified as the polyisocyanate component may be prepolymerized as necessary. More specifically, the polyisocyanate is preferably prepolymerized with a polyol as a chain extender at a capping rate of 3 to 15%, more preferably 4 to 13%, particularly preferably 5 to 10%. Prepolymerize. In this case, the content of isocyanate groups in the prepolymer contained as the polyisocyanate component is preferably 20 to 29%, more preferably 22 to 29%, and particularly preferably 25 to 28%.
- the capping rate of polyisocyanate indicates the ratio of capping with OH groups by prepolymerization to change to urethane bonds with respect to NCO group 100, and a weight by weight with respect to 100 parts by weight of isocyanate.
- Capping rate [%] (Number of OH groups reacting with NCO groups / number of NCO groups)
- ⁇ 100 (A [part by weight] / polyol equivalent) / (100 [part by weight] / isocyanate equivalent) ⁇ 100
- an isocyanate equivalent and a polyol equivalent are calculated
- NCO group content [%] NCO group content of polyisocyanate before prepolymerization [%] ⁇ (100-NCO group capping rate [%]) / (100 [parts by weight] + a [parts by weight])
- polymethylene polyphenyl isocyanate (crude MDI) is preferably used as the polyisocyanate.
- the polyol as a chain extender, it is preferable to use a polyether polyol having at least one selected from the group consisting of propylene glycol, glycerin, pentaerythritol, and sorbitol as an initiator.
- the hard urethane foam stock solution composition as a foamable joint filler without inhibiting the formation of a good hard urethane foam.
- the closed cell ratio of the rigid urethane foam formed by mixing is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more.
- the shrinkage ratio of the rigid urethane foam formed by mixing the stock solution A and the stock solution B is preferably 10% or less, more preferably 5% or less.
- foaming of the rigid urethane foam formed by mixing the stock solution A and the stock solution B is preferably 4 to 10 times, more preferably 5 to 8 times, and the core density of the hard urethane foam after curing is preferably 80 to 200 kg / m 3 , more preferably 100 ⁇ 180 kg / m 3 .
- the pot life that can be applied is 3 minutes or more at room temperature, more preferably 5 minutes or more, and the curing time is room temperature so as not to hinder the construction work. It is preferably within 240 minutes, and more preferably within 180 minutes.
- FIG. 1 is explanatory drawing which shows an example of the heat insulation structure constructed
- the heat insulation construction method in this embodiment can be applied as a method of constructing a heat insulation structure of a transport pipe for low-temperature fluid such as LPG and LNG. More specifically, first, a molded heat insulating material 2 in which a known hard urethane foam molded body is formed into a split cylinder so as to cover the outer peripheral surface of the pipe 1 as a construction object is prepared. Subsequently, the molded heat insulating material 2 is cut into a predetermined size, and the hard urethane foam described above is formed on the butted surface of the molded heat insulating material 2 that forms a joint when the molded heat insulating material 2 is assembled to the outer peripheral surface of the pipe 1. The mixed solution of the stock solution A and the stock solution B of the stock solution composition is applied, and the molded heat insulating material 2 is assembled to cover the pipe 1 until the pot life is elapsed.
- the moisture-proof material 4 can be provided in the outer surface of the shaping
- Example 1 ⁇ Preparation of stock solution A> Polyether polyol (Asahi Glass Co., Ltd .: EL-410NE / initiator pentaerythritol, functional group number 4.0, hydroxyl group) as a chain extender with respect to 100 parts by weight of Crude MDI (Mitsubishi Resin Co., Ltd .: RX-200) No. 410) was added in such an amount that the capping rate was 10.0%, and the mixture was reacted at 25 ° C. for 4 hours to prepare a prepolymer to prepare a stock solution A. It was 25.1% when the content rate of the isocyanate group of the prepolymer was calculated
- the viscosity ⁇ of the stock solution A was measured under the temperature condition of 25 ° C. according to JIS K7117-1, and found to be 34.55 Pa ⁇ s.
- polyether polyol As polyol components, polyether polyol (Asahi Glass Co., Ltd .: EL-410NE / initiator pentaerythritol, functional group number 4.0, hydroxyl value 410) 9 parts by weight, polyether polyol (Asahi Glass Co., Ltd .: EL-3030) / Initiator glycerin, functional group number 3.0, hydroxyl value 56) 6 parts by weight, as foam stabilizer, silicone surfactant (manufactured by Goldschmitt AG: B8404) 0.2 part by weight, as flame retardant, trischloro Propyl phosphate (Daihachi Chemical Co., Ltd .: TCPP) 3 parts by weight, as a catalyst, 1-isobutyl-2-methylimidazole (Activator Chemical Co., Ltd .: Minico R-9000) 0.005 parts by weight, as a foaming agent , 0.5 parts by weight of water, and 16 parts by
- Shrinkage [%] (H m ⁇ H 0 ) / H m ⁇ 100 Further, after the next day after curing, a cubic core foam having a side of 25 mm was cut out from the foam, and the closed cell ratio was measured according to ASTM D2856. As a result, it was 97.2%.
- Examples 2 to 11 Foaming experiment and sagging measurement were performed in the same manner as in Example 1 except that the stock solution A was prepared as shown in Table 1 and mixed with the stock solution B at the weight ratio shown in Table 1. The results are shown in Table 1.
- Example 12 ⁇ Preparation of stock solution A> For 100 parts by weight of Crude MDI (manufactured by Sumika Bayer Urethane Co., Ltd .: 44V-22L), as a chain extender, polyether polyol (Asahi Glass Co., Ltd .: EL-430 / initiator glycerin, functional group number 3.0, A stock solution A was prepared by adding a hydroxyl value of 400) in an amount such that the capping rate was 7.4% and reacting at 25 ° C. for 4 hours to form a prepolymer. It was 26.7% when the content rate of the isocyanate group of the prepolymer was calculated
- Polyether polyol manufactured by
- Example 13 to 16 The viscosity of the mixed solution was measured in the same manner as in Example 11, except that the stock solution B was prepared as shown in Table 4 and mixed with the stock solution A at the weight ratio shown in Table 4. The results are shown in Table 4. Further, with respect to the liquid mixture, a foaming experiment and a sag measurement were performed in the same manner as in Example 1. The results are shown in Table 4.
- Example 17 ⁇ Preparation of stock solution A> For 100 parts by weight of Crude MDI (manufactured by Sumika Bayer Urethane Co., Ltd .: 44V-22L), as a chain extender, polyether polyol (manufactured by Asahi Glass Co., Ltd .: EL-1030 / initiator glycerin, functional group number 3.0, A stock solution A was prepared by adding a hydroxyl value of 160) in an amount to give a capping ratio of 6.6% and reacting at 25 ° C. for 4 hours to form a prepolymer. It was 24.5% when the content rate of the isocyanate group of the prepolymer was calculated
- the viscosity ⁇ of the stock solution A was measured under the temperature condition of 25 ° C. according to JIS K7117-1, and found to be 4.8 Pa ⁇ s.
- Polyether polyol manufactured by
- Examples 18 to 21 Stock solution B was prepared as shown in Table 5, and the viscosity of the mixed solution was measured in the same manner as in Example 16 except that it was mixed with stock solution A at the weight ratio shown in Table 5. The results are shown in Table 5. Further, with respect to the liquid mixture, a foaming experiment and a sag measurement were performed in the same manner as in Example 1. The results are shown in Table 5.
- a hard urethane foam stock solution composition that can be used as a foamable joint filler is provided, and by using such a hard urethane foam stock solution composition as a foamable joint filler, various construction objects are provided. Insulation can be performed.
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Abstract
Description
しかしながら、この方法では、成形断熱材を組み付けたときに、突き合わされる面同士が接する状態である必要があり、施工現場で作業者が寸法合わせのために成形断熱材を切り出した面は面精度が低いため、接着剤を用いた施工方法を適用することができない。
このようにすることで、原液Aと原液Bとの混合、撹拌に支障を来たすことなく、原液Aと原液Bとの混合液に塗工性を付与することができ、硬質ウレタンフォーム原液組成物の発泡性目地充填剤としての使用を可能にする。
キャッピング率[%]
=(NCO基と反応するOH基の数/NCO基の数)×100
=(a[重量部]/ポリオール当量)/(100[重量部]/イソシアネート当量)×100
ここで、イソシアネート当量、ポリオール当量は、次式で求められる。
イソシアネート当量
=(NCO基の式量/イソシアネートのNCO基含有率[%])×100
ポリオール当量
=(KOHの式量/ポリオール(鎖延長剤)のOH基価)×1000
また、プレポリマーのイソシアネート基の含有率は、同様の例において、次式で求められる。
NCO基含有率[%]
=プレポリマー化前のポリイソシアネートのNCO基含有率[%]×(100-NCO基のキャッピング率[%])/(100[重量部]+a[重量部])
さらに、施工作業に支障を来たすことがないように、塗布作業が可能な可使時間が、室温で3分以上であるのが好ましく、より好ましくは5分以上であり、硬化時間は、室温で240分以内であるのが好ましく、180分以内であるのがより好ましい。
なお、図1は、本実施形態に係る断熱施工方法によって構築された断熱構造の一例を示す説明図である。
より具体的には、先ず、施工対象物である配管1の外周面を被覆できるよう、公知の硬質ウレタンフォーム成形体を割り筒状に成形した成形断熱材2を用意する。次いで、かかる成形断熱材2を所定の大きさに切り出すとともに、配管1の外周面に成形断熱材2を組み付けたときに目地部を形成する成形断熱材2の突き合わせ面に、前述した硬質ウレタンフォーム原液組成物の原液Aと原液Bとの混合液を塗布して、可使時間が経過するまでに成形断熱材2を組み付けて配管1を被覆する。
なお、配管1を被覆する成形断熱材2の外表面には防湿材4を設け、さらにその外表面に外装材5を設けることもできる。
<原液Aの調製>
クルードMDI(三菱樹脂(株)製:RX-200)100重量部に対し、鎖延長剤としてポリエーテルポリオール(旭硝子(株)製:EL-410NE/開始剤ペンタエリスリトール、官能基数4.0、水酸基価410)をキャッピング率10.0%になる量だけ加えて、25℃で4時間反応させてプレポリマー化して原液Aを調製した。
プレポリマーのイソシアネート基の含有率を計算により求めたところ、25.1%であった。また、反応を終了した翌日に、JIS K7117-1に準拠して温度25℃の温度条件下で原液Aの粘度ηを測定したところ、34.55Pa・sであった。
ポリオール成分として、ポリエーテルポリオール(旭硝子(株)製:EL-410NE/開始剤ペンタエリスリトール、官能基数4.0、水酸基価410)9重量部、ポリエーテルポリオール(旭硝子(株)製:EL-3030/開始剤グリセリン、官能基数3.0、水酸基価56)6重量部、整泡剤として、シリコーン系界面活性剤(ゴールドシュミットAG社製:B8404)0.2重量部、難燃剤として、トリスクロロプロピルホスフェート(大八化学工業(株)製:TCPP)3重量部、触媒として、1-イソブチル-2-メチルイミダゾール(活剤ケミカル社製:ミニコR-9000)0.005重量部、発泡剤として、水0.5重量部、無機充填剤として、炭酸カルシウム(白石工業(株)製:白艶華CCR)16重量部を均一に混合して原液Bを調製した。
原液Aと原液Bとを重量比(A/B)0.75で混合容器に測り取り、これをヘラで30秒間混合撹拌した。混合撹拌を開始してから120秒後にJIS K7117-2に準拠して測定したところ、η(35℃,0.1s-1)=382Pa・s、η(5℃,100s-1)=135Pa・sであった。
このとき、原液Aと原液Bの総重量に対する無機充填剤(炭酸カルシウム)の割合は32.13重量%であった。また、原液Aに含まれるポリイソシアネート成分のイソシアネート基と、原液Bに含まれるポリオール成分の水酸基の当量比(NCO/OH)は、1.23であった。
原液Aと原液Bとを温度20℃に調温して、重量比(A/B)0.75で原液Aと原液Bとの総重量が約50gとなるように混合容器に測り取った。これをヘラで30秒間混合撹拌した後、約20gの混合液を容積約300ccの透明カップ内に投入した。
発泡中の最大発泡高さ(Hm)と硬化後の発泡高さ(H0)を測定して、収縮率を次式で求めたところ、6.7%であった。
収縮率[%]=(Hm-H0)/Hm×100
また、硬化後の翌日以降に、発泡体から一辺25mmの立方体のコアフォームを切り出し、ASTM D2856に準拠して、独立気泡率を測定したところ、97.2%であった。
原液Aと原液Bとを重量比(A/B)0.75で混合した後、直ちにPUFボードに、厚さtが1mm、高さhが25mmの帯状に混合液を塗布した。混合開始から60秒以内に塗布面を鉛直にして、発泡完了までに混合液がダレ落ちた最大長さDmaxを測定した(図2参照)。
ダレ落ちDの長さが5mm以内を「○」、5~50mmを「△」、50mm以上を「×」として評価した。その結果を表1に示す。
原液Aを表1に示すように調製し、表1に示す重量比で原液Bと混合した以外は、実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表1に示す。
原液Aを表2及び表3に示すように調製し、表2及び表3に示す重量比で原液Bと混合した以外は、実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表2及び表3に示す。
なお、比較例16~21では、クルードMDI(三菱樹脂(株)製:RX-200)をプレポリマー化せずに(鎖延長剤なし)、原液Aとして使用した。また、比較例3,6,11,13,15では、原液Aの粘度が高く原液Bと混合することができなかった。
<原液Aの調製>
クルードMDI(住化バイエルウレタン(株)製:44V-22L)100重量部に対し、鎖延長剤としてポリエーテルポリオール(旭硝子(株)製:EL-430/開始剤グリセリン、官能基数3.0、水酸基価400)をキャッピング率7.4%になる量だけ加えて、25℃で4時間反応させてプレポリマー化して原液Aを調製した。
プレポリマーのイソシアネート基の含有率を計算により求めたところ、26.7%であった。また、反応を終了した翌日に、JIS K7117-1に準拠して温度25℃の温度条件下で原液Aの粘度ηを測定したところ、3.4Pa・sであった。
ポリオール成分として、ポリエーテルポリオール(旭硝子(株)製:EL-410NE/開始剤ペンタエリスリトール、官能基数4.0、水酸基価410)15重量部、整泡剤として、シリコーン系界面活性剤(ゴールドシュミットAG社製:B8404)0.2重量部、難燃剤として、トリスクロロプロピルホスフェート(大八化学工業(株)製:TCPP)3重量部、触媒として、1-イソブチル-2-メチルイミダゾール(活剤ケミカル社製:ミニコR-9000)0.005重量部、発泡剤として、水0.3重量部、無機充填剤として、炭酸カルシウム(白石工業(株)製:Viscoexcel-30)12重量部を均一に混合して原液Bを調製した。
原液Aと原液Bとを重量比(A/B)0.92で混合容器に測り取り、これをヘラで30秒間混合撹拌した。混合撹拌を開始してから120秒後にJIS K7117-2に準拠して測定したところ、η(35℃,0.1s-1)=480Pa・s、η(5℃,100s-1)=21Pa・sであった。
このとき、原液Aと原液Bの総重量に対する無機充填剤(炭酸カルシウム)の割合は20.52重量%であった。また、原液Aに含まれるポリイソシアネート成分のイソシアネート基と、原液Bに含まれるポリオール成分の水酸基の当量比(NCO/OH)は、1.24であった。
実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表4に示す。
原液Bを表4に示すように調製し、表4に示す重量比で原液Aと混合した以外は、実施例11と同様にして、混合液の粘度を測定した。その結果を表4に示す。
また、当該混合液について、実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表4に示す。
原液Bを表4に示すように調製し、表4に示す重量比で原液Aと混合した以外は、実施例11と同様にして、混合液の粘度を測定した。その結果を表4に示す。
また、当該混合液について、実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表4に示す。
<原液Aの調製>
クルードMDI(住化バイエルウレタン(株)製:44V-22L)100重量部に対し、鎖延長剤としてポリエーテルポリオール(旭硝子(株)製:EL-1030/開始剤グリセリン、官能基数3.0、水酸基価160)をキャッピング率6.6%になる量だけ加えて、25℃で4時間反応させてプレポリマー化して原液Aを調製した。
プレポリマーのイソシアネート基の含有率を計算により求めたところ、24.5%であった。また、反応を終了した翌日に、JIS K7117-1に準拠して温度25℃の温度条件下で原液Aの粘度ηを測定したところ、4.8Pa・sであった。
ポリオール成分として、ポリエーテルポリオール(旭硝子(株)製:EL-410NE/開始剤ペンタエリスリトール、官能基数4.0、水酸基価410)15重量部、整泡剤として、シリコーン系界面活性剤(ゴールドシュミットAG社製:B8404)0.2重量部、難燃剤として、トリスクロロプロピルホスフェート(大八化学工業(株)製:TCPP)3重量部、触媒として、1-イソブチル-2-メチルイミダゾール(活剤ケミカル社製:ミニコR-9000)0.005重量部、発泡剤として、水0.5重量部、無機充填剤として、炭酸カルシウム(白石工業(株)製:Viscoexcel-30)12重量部を均一に混合して原液Bを調製した。
原液Aと原液Bとを重量比(A/B)1.11で混合容器に測り取り、これをヘラで30秒間混合撹拌した。混合撹拌を開始してから120秒後にJIS K7117-2に準拠して測定したところ、η(35℃,0.1s-1)=490Pa・s、η(5℃,100s-1)=25Pa・sであった。
このとき、原液Aと原液Bの総重量に対する無機充填剤(炭酸カルシウム)の割合は18.55重量%であった。また、原液Aに含まれるポリイソシアネート成分のイソシアネート基と、原液Bに含まれるポリオール成分の水酸基の当量比(NCO/OH)は、1.20であった。
実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表5に示す。
原液Bを表5に示すように調製し、表5に示す重量比で原液Aと混合した以外は、実施例16と同様にして、混合液の粘度を測定した。その結果を表5に示す。
また、当該混合液について、実施例1と同様にして、発泡実験とダレの測定を行った。その結果を表5に示す。
2 成形断熱材
3 ウレタンフォーム
Claims (8)
- ポリイソシアネート成分を含む原液Aと、ポリオール成分を含む原液Bとを混合して硬質ウレタンフォームを形成する二液型の硬質ウレタンフォーム原液組成物であって、
前記原液Bに、混合される前記原液Aと前記原液Bの総重量に対して15重量%以上の無機充填剤を添加するとともに、前記原液Aの粘度ηを1~100Pa・sに調製し、
前記原液Aと前記原液Bとの混合液がチクソトロピー性を示して、当該混合液の粘度ηが、η(35℃,0.1s-1)≧200Pa・s、η(5℃,100s-1)≦200Pa・sであることを特徴とする硬質ウレタンフォーム原液組成物。 - 前記ポリイソシアネート成分が、ポリオールを鎖延長剤として、ポリイソシアネートをキャッピング率3~15%でプレポリマー化したプレポリマーを含む請求項1に記載の硬質ウレタンフォーム原液組成物。
- 前記プレポリマーのイソシアネート基の含有率が20~29%である請求項2に記載の硬質ウレタンフォーム原液組成物。
- 前記ポリイソシアネートが、ポリメチレンポリフェニルイソシアネート(クルードMDI)である請求項2又は3に記載の硬質ウレタンフォーム原液組成物。
- 前記鎖延長剤としてのポリオールが、プロピレングリコール、グリセリン、ペンタエリスリトール、及びソルビトールからなる群から選ばれる少なくとも一種を開始剤とするポリエーテルポリオールである請求項2~4のいずれか一項に記載の硬質ウレタンフォーム原液組成物。
- 前記原液Aと前記原液Bとを混合して形成された硬質ウレタンフォームの独立気泡率が50%以上である請求項1~5のいずれか一項に記載の硬質ウレタンフォーム原液組成物。
- 前記原液Aと前記原液Bとを混合して形成された硬質ウレタンフォームの収縮率が10%以下である請求項1~6のいずれか一項に記載の硬質ウレタンフォーム原液組成物。
- 施工対象物の外表面を複数の成形断熱材で被覆し、前記成形断熱材同士が接合されて一体化された断熱構造を構築するにあたり、
請求項1~7のいずれか一項に記載の硬質ウレタンフォーム原液組成物を用いて、前記原液Aと前記原液Bとの混合液を、目地部を形成する前記成形断熱材の突き合わせ面に塗布して、前記成形断熱材を組み付けて、当該混合液が発泡、硬化して前記目地部内の空間全体を充填して前記成形断熱材と一体化することを特徴とする断熱施工方法。
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