JP4881139B2 - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Description

  The present invention relates to a polyol composition for rigid polyurethane foam using water as a foaming agent, and a method for producing a rigid polyurethane foam using the polyol composition.

  Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. Such a rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and a polyisocyanate component, and foaming and curing. In the past, chlorofluorocarbon compounds such as CFC-11 were used as foaming agents, but they were prohibited because CFC compounds caused destruction of the ozone layer, and switched to HCFC-141b. Although switching to an HFC compound having a coefficient of zero has been performed, the HFC compound has a problem that it has a large GWP (global warming potential) and is currently expensive.

  Although a technique using pentane such as n-pentane, iso-pentane, cyclopentane or the like as a low-cost blowing agent instead of halogenated hydrocarbon compounds such as HFC compounds is known, pentanes are highly flammable. In addition, there is a problem that a great expense is required for the equipment for preventing fire.

  There is no problem in both the work environment and the global environment, and water is known as a low-cost foaming agent. Hard polyurethane foams using water as a foaming agent are known, but the polyester polyol as a raw material is a foaming agent. Reacts with water to cause hydrolysis, resulting in reaction delay. In addition, since carbon dioxide is used as the foaming gas, the diffusion of the carbon dioxide gas is fast, and the foam after foaming is in a reduced pressure state, which causes a problem of foam shrinkage. As a technique for solving such a problem, a technique (Patent Document 1) that limits the cream time of a rigid polyurethane foam foam concentrate solution and the closed cell ratio of the obtained rigid polyurethane foam is known.

  Further, a rigid urethane foam using water and an HFC compound in combination as a foaming agent is disclosed (Patent Documents 2 and 3).

  However, the technique described in Patent Document 1 uses a polyether polyol compound having piperazine or aminoalkylpiperazine as an initiator as a raw material, and does not have sufficient combustion resistance. The use of aromatic ester-based polyols is considered to improve combustion resistance. However, when known ester polyols of ethylene glycol or diethylene glycol and terephthalic acid or orthophthalic acid are used, hydrolysis occurs due to the presence of water as a blowing agent. Since the generated acid forms a salt with the catalyst amine, the reactivity is lowered, and it becomes difficult to produce a rigid polyurethane foam by a spray method as the polyol composition is stored.

  In addition, with respect to the techniques disclosed in Patent Documents 2 and 3, as described above, the HFC compound is expensive, and the reactivity can be adjusted mildly as compared with the conventional formulation using HCFC-141b. It is difficult, and there is a problem in that workability is poor, for example, in a refrigerated warehouse where thick spraying of rigid polyurethane foam is required by the spray method, such as being unable to blow smoothly.

Japanese Patent Laid-Open No. 2001-40054 JP 2004-51693 A JP 2004-59900 A

  In view of the problems of the above-mentioned known technology, the present invention can form a rigid polyurethane foam having water as a foaming agent, small shrinkage due to aging, and excellent in combustion resistance by a corn calorie test, and storage stability. It is an object of the present invention to provide an excellent polyol composition for rigid polyurethane foam and a method for producing a rigid polyurethane foam using the polyol composition.

The polyol composition for rigid polyurethane foam of the present invention contains a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst, and is mixed with a polyisocyanate component by a urethane foaming device and reacted to form a rigid polyurethane foam. A composition comprising:
The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid,
The weight ratio of the ester polyol (A) to the resin fine particle-containing polyether polyol (B) is (A) / (B) = 90/10 to 55/45,
The mol% of the orthophthalic acid is more than 95 mol%.

  The polyol composition having the above-described structure uses water as a foaming agent, forms a rigid polyurethane foam with small shrinkage due to aging, and excellent in resistance to combustion by the corn calorie test (hereinafter referred to as “corn calorie combustion resistance”). It is a polyol composition for rigid polyurethane foam that can be used and has excellent storage stability.

  When the average molecular weight of polyoxyethylene glycol constituting the ester polyol (by end group quantification method) is less than 150, hydrolysis resistance is lowered and the storage stability of the polyol composition becomes insufficient. The combustion resistance of the resulting rigid polyurethane foam is lowered.

  Carbonate which is a foaming gas when the weight ratio of the ester polyol (A) and the resin polyol-containing polyether polyol (B) exceeds (A) / (B) = 90/10 and the weight ratio of the ester polyol (A) is large. The shrinkage of the foam due to gas diffusion increases, and when the weight ratio of the resin fine particle-containing polyether polyol (B) exceeds 55/45 and the closed cell ratio decreases, the thermal conductivity increases. The (A) / (B) ratio is more preferably 90/10 to 60/40, and still more preferably 90/10 to 70/30.

  In the above-mentioned polyol composition for rigid polyurethane foam, the aromatic dicarboxylic acid is composed of orthophthalic acid, or orthophthalic acid and terephthalic acid, and the mol% of the orthophthalic acid is more than 95 mol%.

  The polyol composition having such a configuration has practical storage stability to the extent that it can produce a rigid polyurethane foam even after market distribution, just as it is immediately after production, and is a hard material excellent in corn calorie combustion resistance. Polyurethane foam can be produced. When the molar ratio of terephthalic acid / orthophthalic acid exceeds 95/5 and the ratio of terephthalic acid is large, shrinkage may occur in the manufactured rigid polyurethane foam.

  In the above polyol composition for rigid polyurethane foam, the resin fine particle-containing polyether polyol is preferably a Mannich polyether polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4 containing resin fine particles. .

  By using the polyol composition having such a configuration, a rigid polyurethane foam having more excellent corn calorie combustion resistance can be produced.

In the above polyol composition for rigid polyurethane foam, the foam stabilizer is (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) _3. , silicone _{^{(R 1) 2 Si (OR}} 2) 2, which is _(R 1) 3 Si cohydrolysis condensate of at least one and Si ^(OR _{2) 4} is selected from the group consisting of (OR ²⁾ The polymer (R ¹ is an alkyl group having 1 or 2 carbon atoms or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different). It is preferable that 2 types are included.

  Rigid polyurethane foam using a polyol composition having such a composition uses water as a foaming agent, has a low density, effectively prevents shrinkage, and has excellent adhesive strength with a face material or an object. It is a form.

  The reason why foam shrinkage is prevented by the above composition is not clear, but polyurethane foam is formed by using a specific composition polyol and cyclic dialkylpolysiloxane (a) and silicone polymer (b). It is presumed that very fine pores are formed, and shrinkage due to pressure drop due to diffusion of carbon dioxide in the bubbles is prevented without impairing the heat insulation.

Another aspect of the present invention relates to a rigid polyurethane foam in which a polyol composition containing a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst and a polyisocyanate component are mixed by a urethane foaming apparatus and reacted to form a rigid polyurethane foam. A manufacturing method comprising:
The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid,
The weight ratio of the ester polyol (A) to the resin fine particle-containing polyether polyol (B) is (A) / (B) = 90/10 to 55/45,
The mol% of the orthophthalic acid is more than 95 mol%.

  By the manufacturing method having the above-described configuration, it is possible to manufacture a rigid polyurethane foam having water as a foaming agent, small shrinkage due to change with time, low density, and excellent corn calorie combustion resistance. In addition, Preferably it is (A) / (B) = 90 / 10-60 / 40, More preferably, it is 90 / 10-70 / 30 (weight ratio).

  In the above-mentioned polyol composition for rigid polyurethane foam, the aromatic dicarboxylic acid is composed of orthophthalic acid, or orthophthalic acid and terephthalic acid, and the mol% of the orthophthalic acid is more than 95 mol%.

  The polyol composition having such a configuration has practical storage stability to the extent that it can produce a rigid polyurethane foam even after market distribution, just as it is immediately after production, and is a hard material excellent in corn calorie combustion resistance. Polyurethane foam can be produced. When the molar ratio of terephthalic acid / orthophthalic acid exceeds 95/5 and the ratio of terephthalic acid is large, shrinkage may occur in the manufactured rigid polyurethane foam.

  In the method for producing a rigid polyurethane foam, the resin fine particle-containing polyether polyol is preferably a Mannich polyether polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4 containing resin fine particles.

  By the above production method, a rigid polyurethane foam having more excellent corn calorie combustion resistance can be produced.

In the above-described method of producing a rigid polyurethane foam, wherein the foam stabilizer, (a) cyclic dialkyl polysiloxane Si-O bond the containing ^{4-5, (b) (R 1)} Si (OR 2) 3, ( Silicone polymer which is a cohydrolysis condensate of at least one selected from the group consisting of R ¹ ) ₂ Si (OR ² ) ₂ and (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ (R ¹ is an alkyl group having 1 or 2 carbon atoms or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different.) It is preferable to contain.

  According to the manufacturing method having the above configuration, water is used as a foaming agent, and a rigid polyurethane foam that is low in density and effectively prevented from shrinking and has excellent adhesive strength with a face material or an object is manufactured. Can do.

  As a foaming method of the rigid polyurethane foam, a foaming method known in the technical field of polyurethane can be used without limitation. For example, a continuous production method, a discontinuous production method, a spray method, an injection method, or the like can be used. In particular, the spray method is a method in which a two-component undiluted solution is mixed and sprayed onto a construction object with a spray device, and when reaching the object, it is foamed and cured, and is an effective method because construction is easy. In addition, the continuous production method is a method in which a mixed stock solution is flowed on the lower surface material on the continuous conveyor, and the upper surface material is supplied and continuously foamed, and a sandwich panel can be produced by cutting to a predetermined length. it can.

  The polyol composition of the present invention includes a polyol compound, water as a foaming agent, a foam stabilizer, and a catalyst. The polyol compound comprises an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid, and a resin polyol-containing polyether polyol. Including. The viscosity of the polyol composition of the present invention is preferably 1000 mPa · s (20 ° C.) or less, and 800 mPa · s (20 ° C.) from the viewpoint of easily producing a rigid polyurethane foam by a continuous production method, a spray method or the like. The following is more preferable.

  The ester polyol is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid, the polyoxyethylene glycol has an average molecular weight of 150 to 500, the aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid, The orthophthalic acid has a mol% exceeding 95 mol%. The polyoxyethylene glycol having an average molecular weight of 150 to 500 may contain diethylene glycol or triethylene glycol. Diethylene glycol is preferably not included. For example, when polyoxyethylene glycol having a relatively broad molecular weight distribution including triethylene glycol (molecular weight 150) is used, since crystallization does not occur, liquid property stability is good and preferable. Such an ester polyol can be produced by the same production method as an ester polyol composed of an aromatic dicarboxylic acid and ethylene glycol or diethylene glycol which are generally used conventionally. The bifunctional polyoxyethylene glycol constituting the ester polyol can also be produced by a conventional method, and a commercially available product such as PEG400 may be used.

  The resin polyol-containing polyether polyol can be produced by a known method. For example, a resin produced by a bulk polymerization method or a solution polymerization method is pulverized into fine particles, and a resin fine powder obtained by classification as necessary is added to and mixed with a polyol compound. A resin obtained by an emulsion polymerization method Examples include a method of adding an emulsion containing fine particles as it is, a method in which a monomer is dissolved or dispersed in a polyol compound, a radical polymerization initiator such as AIBN or BPO is added, heated, and polymerized to obtain a resin fine particle polyol compound. The Among these, the method of polymerizing in a polyol compound to form resin fine particles is most preferable because the particles are less likely to settle even when left for a long period of time and a stable polyol composition is obtained.

  As the resin fine particles, known resin fine particles contained in a polyol for polyurethane foam can be used. Specifically, single weights such as acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, styrene, vinyl acetate, acrylic monomers, and the like can be used. Copolymer fine particles and copolymer fine particles of two or more monomers selected from these monomers can be used. Moreover, it is preferable that the resin fine particle in the polyol compound whole quantity which comprises a polyol composition is 0.2 to 1.0 weight%.

  Mannich polyol constituting the resin polyol-containing polyether polyol is an active hydrogen compound obtained by a Mannich reaction of phenol and / or its alkyl-substituted derivative, formaldehyde and alkanolamine, or at least one of ethylene oxide and propylene oxide in this compound. An active hydrogen compound obtained by ring-opening addition polymerization.

  Commercially available products can be used as the resin polyol-containing polyether polyol, and specific examples include Asahi Glass Urethane Co., Ltd. products.

  The polyol composition of the present invention may further contain at least one polyol compound having a hydroxyl value of 200 to 500 mgKOH / g selected from aliphatic amine polyols and aromatic amine polyols. Examples of the aliphatic amine polyol include alkylene diamine polyols and alkanol amine polyols. These polyol compounds are polyfunctional polyol compounds having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using alkylene diamine or alkanol amine as an initiator. As the alkylene diamine, known compounds can be used without limitation. Specifically, use of alkylene diamine having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, and neopentyl diamine is preferable. Among these, the use of alkylenediamine having a small number of carbon atoms is more preferable, and the use of a polyol compound having ethylenediamine or propylenediamine as an initiator is particularly preferable. In the alkylene diamine-based polyol, the alkylene diamine as the initiator may be used alone or in combination of two or more. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkylene diamine as the initiator is 4, and the number of functional groups of the polyol compound using alkanolamine as the initiator is 3.

  The aromatic amine-based polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using an aromatic diamine as an initiator. As the initiator, known aromatic diamines can be used without limitation. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine and the like. Of these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferred in that the obtained rigid polyurethane foam has excellent properties such as heat insulation and strength.

  You may use a crosslinking agent as a component which comprises the polyol composition for rigid polyurethane foams of this invention. As the crosslinking agent, low molecular weight polyhydric alcohols used in the technical field of polyurethane can be used. Specifically, trimethylolpropane, glycerin, pentaerythritol, triethanolamine and the like are exemplified.

In the present invention, the (b) silicone polymer used as the foam stabilizer component is (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) ₂ , (R ¹ ) ₃ Si (OR ² ). ) And at least one selected from the group consisting of Si (OR ² ) ₄ and co-hydrolyzing and condensing using water and a catalyst to form a polysiloxane bond. R ¹ and R ² may be the same or different and are preferably a methyl group or an ethyl group. Further, (a) cyclic dialkylpolysiloxane can also be produced by a known method, and is preferably cyclic dimethylsiloxane.

  Moreover, in addition to (a) and (b) used as a foam stabilizer component in this invention, you may contain a copolymerization silicone compound. The copolymerized silicone compound is a compound used as a foam stabilizer in the technical field of polyurethane foam. In the present invention, among these known foam stabilizers, the Si content is 10 to 40% by weight, that is, the content of the copolymerized polyoxyalkylene glycol is small, and generally the activity is low. It is preferable to use a foam stabilizer. Specifically, foam stabilizers such as S-824-02 (Si = 25 wt%; Nihon Unicar) and SZ-1704 (Si = 25 wt%; Nihon Unicar) can be used. Two or more kinds of foam stabilizers (copolymerized silicone compounds) having polyoxyalkylene glycol may be used, or (a) a cyclic dialkylpolysiloxane may be contained.

  As the silicone compounds (a) and (b), commercially available products can be used. Specifically, compositions containing (a) and (b) are suitable for use. As described above, it is preferable that (a) a cyclic dialkylpolysiloxane and (b) a silicone polymer are mixed in advance and used as a foam stabilizer composition in the production of a polyol composition.

  The mixing ratio of (a) cyclic dialkylpolysiloxane and (b) silicone polymer is preferably 1/9 to 8/2, more preferably 1/4 to 4/1 in weight ratio. More preferably, it is 1/2 to 2/1.

  The polyisocyanate compound that forms a rigid polyurethane foam by mixing and reacting with the polyol composition is easy to handle, fast in reaction, excellent in the physical properties of the resulting rigid polyurethane foam, and low in cost. For this reason, liquid MDI is used. As liquid MDI, Crude MDI (c-MDI) (Sumijoule 44V-10, Sumijoule 44V-20, etc. (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)), uretonimine-containing MDI (Millionate) MTL (manufactured by Nippon Polyurethane Industry), prepolymer-modified crude MDI and the like are used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

  In the production of the rigid polyurethane foam of the present invention, in addition to the above components, catalysts, flame retardants, colorants, antioxidants and the like well known to those skilled in the art can be used.

  Examples of the catalyst include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine (Kaorizer No. 1), N, N, N ′, N ′, N-alkylpolyalkylenepolyamines such as N ″ -pentamethyldiethylenetriamine (Kaorizer No. 3), diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine (Polycat-8), triethylenediamine, N— It is preferable to use tertiary amines such as methylmorpholine and NIAX-A1.

  It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to improving the combustion resistance in the structure of the polyurethane molecule. For example, as a trimerization catalyst such as potassium acetate and potassium octylate, and a quaternary ammonium salt catalyst, Examples thereof include a catalyst disclosed in Japanese Patent No. 104734, a commercially available Dabco-TMR, Dabco-TMR-2 (Air Products), and the like. Some of the above-mentioned tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination.

  In the present invention, addition of a flame retardant is also a preferred embodiment, and examples of suitable flame retardants include metal compounds such as halogen-containing compounds, organophosphates, antimony trioxide, and aluminum hydroxide. .

  Organophosphates are suitable additives because they also have an action as a plasticizer and thus have an effect of improving the brittleness of rigid polyurethane foam. It also has the effect of reducing the viscosity of the polyol composition. Examples of the organic phosphate esters include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, tris (β-chloroethyl) phosphate (CLP, Daihachi Chemical), Tris (β-chloropropyl) phosphate (TMCPP, Daihachi Chemical), Tributoxyethyl phosphate (TBXP, Daihachi Chemical), Tributyl phosphate, Triethyl phosphate, Cresyl phenyl phosphate, Dimethyl methylphosphonate Etc., and one or more of these can be used. The addition amount of the organic phosphates is 40 parts by weight or less, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total polyol compound. Exceeding this range may cause problems such as insufficient plasticization and flame retardant effects and reduced foam mechanical properties.

  In the method for producing a rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixing of the polyol composition and the polyisocyanate component is 1.0 to 4.0, more preferably 1.3. It is -3.5, More preferably, it is 1.3-2.0. It is also a more preferable aspect that the NCO index is 1.3 or more and the catalyst contains a trimerization catalyst.

  With such a configuration, it is possible to produce a rigid polyurethane foam in which a large amount of isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam and the combustion resistance is further improved.

The density of the rigid polyurethane foams produced by the present invention is preferably from 20 and 100 kg / ^{m 3,} more preferably from 25~50kg / ^{m 3.}

(Polyol composition)
A polyol composition was prepared with the composition described in the upper part of Table 1. The contents and characteristics of the raw materials used are as follows.
a-1) Polyol A
Ester polyol (Hitachi Kasei Polymer) prepared from orthophthalic acid, which is an aromatic carboxylic acid, and polyoxyethylene glycol (PEG) having an average molecular weight of 400 by a conventional method; hydroxyl value = 150 mgKOH / g, viscosity = 2500 mPa · sec 25 ° C)
a-2) Polyol A ′
Esters polyol prepared from aromatic carboxylic acid mixed with terephthalic acid / orthophthalic acid molar ratio in the range of 1/1 (50/50) by a conventional method and polyoxyethylene glycol (PEG) having an average molecular weight of 400. (Hitachi Chemical Polymer); hydroxyl value = 150 mgKOH / g, viscosity = 2500 mPa · sec (25 ° C.)
a-3) Polyol A ''
Ester polyol (Hitachi Chemical Polymer) made from aromatic carboxylic acid mixed with terephthalic acid / orthophthalic acid molar ratio in the range of 3/97 and polyoxyethylene glycol (PEG) having an average molecular weight of 400 in the usual way Hydroxyl value = 150 mgKOH / g, viscosity = 2450 mPa · sec (25 ° C.)
b) Polyol B
Polyol in which resin fine particles are dispersed in a Mannich polyether polyol compound (Asahi Glass); hydroxyl value = 380 mgKOH / g
c) Polyol C
An ester polyol (Hitachi Kasei Polymer) prepared from an aromatic carboxylic acid and diethylene glycol mixed with a terephthalic acid / orthophthalic acid molar ratio of 1/1 (50/50) by a conventional method; hydroxyl value = 260 mgKOH / g
d) Polyol D
Polyol in which resin fine particles are dispersed in a Mannich polyether polyol compound (Asahi Glass); hydroxyl value = 365 mgKOH / g
e) TMCPP: Phosphorus flame retardant (plasticizer) (Daihachi Chemical Industry)
f) Catalyst (i): Quaternary ammonium salt catalyst (Dabco TMR) (Air Products)
(Ii): Tertiary amine catalyst (Kaorizer No. 1) (Kao)
(Iii): Tertiary amine catalyst (Kaorizer No. 3) (Kao)
g) Foam stabilizer composition (a) 1: 1 (weight ratio) mixture (i) of cyclic dialkylpolysiloxane and (b) silicone polymer, copolymer which is a copolymer of polydimethylsiloxane and polyoxyalkylene glycol A foam stabilizer composition in which the polymerized silicone compound (ii) was a mixture of (i) :( ii) = 1: 1 (weight ratio) was used.
h) Polyisocyanate component: Sumidur 44V-20 (Suika Bayer Urethane), NCO% = 31.0%
i) Foaming agent: water

(Examples 1-5 and Comparative Examples 1-6)
In Examples 1 to 5 and Comparative Examples 1 to 6, the polyol composition was prepared by the formulation described in the upper part of Table 1. Formulations other than the polyol compound, the foam stabilizer and the catalyst were 50 parts by weight of the flame retardant TMCPP (Daihachi Chemical Industry) and 5 parts by weight of water of the foaming agent, with the total amount of the polyol compound being 100 parts by weight. The polyol composition was prepared by first stirring and mixing the components excluding water and the foam stabilizer composition, and then adding and mixing the foam stabilizer composition. In the production of rigid polyurethane foam, the polyol composition and the polyisocyanate component were mixed with a laboratory stirrer so that the NCO index (NCO / OH equivalent ratio) was 1.33. The evaluation described below was performed, and the results are shown in the lower part of Table 1.

(Example 6)
In Example 6, a rigid polyurethane foam was prepared in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 6 except that the NCO index was 1.5.

(Evaluation)
1) Storage stability of polyol composition A sample having the same shape as the sample used for measuring the foam density by preparing a free-foam foam by leaving the polyol composition in a sealed state at a temperature of 40 ° C for one month. Was left for 48 hours under high temperature and high humidity conditions (temperature 70 ° C., relative humidity 95%), and the dimensional change rate (%) of the core in the vertical direction of foaming was measured. When a polyol composition with poor storage stability is used, the dimensional change rate increases. Those with a dimensional change rate of less than 5% were evaluated as ◎, those with 5-10% as ○, 10% or less but accompanied by distorted deformations as Δ, and those not retaining the shape as X.

2) Closed cell ratio Accu Pyc1330 (Shimadzu Corporation) was used as a measuring device, and the closed cell ratio was measured. The closed cell ratio was evaluated as ◎ for 70% or more, ◯ for 40 to less than 70%, Δ for less than 15 to 40%, and × for less than 15%.

3) Thermal conductivity A thermal conductivity measuring device AUTO-Λ HC-074 (manufactured by Eihiro Seiki Co., Ltd.) was used, and the measurement conditions were measured in accordance with JIS A 9511. As for the result, the thermal conductivity is 0.031 (W / m · K) or less ◎, 0.031 to 0.033 or less ○, 0.033 to 0.036 or less Is shown as Δ, and those exceeding 0.036 are shown as x.

4) Dimensional stability A 25 mm thick and 200 mm long and horizontal foam sample was cut out from the rigid polyurethane foam obtained in the above example, and subjected to an exposure test for one week under the following conditions. Change rate.
Cold resistance dimensional stability: -30 ° C exposure Evaluation results are ◎ for dimensional change rate less than 5%, ○ for less than 5-7%, Δ for less than 7-10%, △ 10% or more Was evaluated as x.

5) Combustion resistance by corn calorie test (corn calorie combustion resistance)
For foamed rigid polyurethane foam, a sample of (99 ± 1) mm × (99 ± 1) mm is cut out and the maximum heat generation rate when heated for 5 minutes at a radiant heat intensity of 50 kW / m ² in accordance with ISO-5660 (Heat generation rate) and total calorific value were measured. This measurement method is a test method defined as corresponding to the standard according to the corn calorimeter method at the Building Comprehensive Testing Laboratory, which is a public institution prescribed in Article 108-2 of the Building Standard Law Enforcement Ordinance. In this test, when the maximum heat generation rate does not exceed 200 kW / m ² and the total heat generation amount for 5 minutes is less than 8 MJ / m ² under the above conditions, either ○ (pass), either the maximum heat generation rate or the total heat generation amount Or when both exceeded the above range, it was evaluated as x (failed).

  From the results shown in Table 1, the examples of the present invention show that the storage stability of the polyol composition, the heat insulation of the rigid polyurethane foam produced using the polyol composition, the cold dimensional stability, the corn calorie resistance, and the independence. All the characteristics of the bubble ratio were satisfactory. On the other hand, in the comparative example, the corn calorie combustion resistance was inferior, and those containing no aromatic dicarboxylic acid did not give sufficient results in terms of dimensional stability and heat insulation.

Claims (6)

A polyol composition comprising a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst, mixed with a polyisocyanate component by a urethane foaming device, and reacted to form a rigid polyurethane foam,
The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid,
The weight ratio of the ester polyol (A) to the resin fine particle-containing polyether polyol (B) is (A) / (B) = 90/10 to 55/45,
A polyol composition for rigid polyurethane foam, characterized in that the mol% of the orthophthalic acid exceeds 95 mol%.   2. The rigid polyurethane foam according to claim 1, wherein the resin fine particle-containing polyether polyol is a Mannich polyether polyol having a hydroxyl value of 250 to 550 mg KOH / g and a functional group number of 2 to 4 containing resin fine particles. Polyol composition. The foam stabilizer includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) ₂ , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different. 2. A polyol composition for rigid polyurethane foam according to 2. A polyol compound, a foaming agent, a polyol composition containing a foam stabilizer and a catalyst, and a polyisocyanate component are mixed by a urethane foaming device and reacted to form a rigid polyurethane foam,
The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid,
The weight ratio of the ester polyol (A) to the resin fine particle-containing polyether polyol (B) is (A) / (B) = 90/10 to 55/45,
The manufacturing method of the rigid polyurethane foam characterized by the mol% of said orthophthalic acid exceeding 95 mol%.   5. The rigid polyurethane foam according to claim 4, wherein the resin polyol-containing polyether polyol is a Mannich polyether polyol having a hydroxyl value of 250 to 550 mg KOH / g and a functional group number of 2 to 4 containing resin fine particles. Production method. The foam stabilizer includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) ₂ , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different. 6. A method for producing a rigid polyurethane foam according to 5.