JP2015105343A - Rigid foamed synthetic resin and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a rigid foam having a low density and excellent thermal insulation performance while suppressing an amount of use of a foaming agent.SOLUTION: A method of producing rigid foamed synthetic resin makes a polyol composition (A) and a polyisocyanate compound (B) react with each other in the presence of a physical foaming agent (C), a foam stabilizer (D), and a catalyst (E), wherein the polyol composition (A) has a weight average molecular weight of 100-3,000, and the physical foaming agent (C) comprises CFCF=CHCl and CFCF=CCl.

Description

  The present invention relates to a method for producing a rigid foam synthetic resin and a rigid foam synthetic resin.

  Rigid foam synthetic resin such as rigid polyurethane foam, rigid urethane modified polyisocyanurate foam or rigid polyurea foam by reacting active hydrogen compound such as polyol with polyisocyanate compound in the presence of foam stabilizer, catalyst and foaming agent (Hereinafter collectively referred to as “rigid foam”) is widely used.

Examples of the blowing agent include chlorinated fluorinated carbon compounds (chlorofluorocarbon compounds, so-called CFCs) such as CCl ₃ F, and chlorinated fluorinated hydrocarbon compounds (hydrochlorofluorocarbon compounds, so-called HCFCs) such as CCl ₂ FCH ₃ . ) Has been used in the past. However, the use of CFCs and HCFCs has been restricted from the viewpoint of environmental protection (protection of the ozone layer).

Hydrogenated fluorinated carbon compounds (hydrofluorocarbon compounds, so-called HFCs) are used as foaming agents that replace CFCs and HCFCs.
As HFCs, for example, CHF ₂ CH ₂ CF ₃ (HFC-245fa), CF ₃ CH ₂ CF ₂ CH ₃ (HFC-365mfc) and the like are used. However, these HFCs have an ozone depletion potential (ODP) of zero, but have a high global warming potential (GWP), so a blowing agent with a lower GWP is required.

Hydrofluoroolefins (HFO) have been proposed as one of candidate materials for blowing agents having a small GWP.
For example, Patent Document 1 describes hydrochlorofluoroolefin (HFO-1233zd).
Patent Documents 2 and 3 describe a method of preparing a thermoplastic or thermosetting foam using an azeotrope mixture as a foaming agent. _CF 3 CF = CHCl Examples of the azeotropic mixture with _{(HCFO-1224yd),} it has been described that the CF ₃ CH = CHCF can be used a mixture of 3 (HFO-1336mzz).
However, in Patent Documents 2 and 3, there is no specific description of the thermoplastic resin or the thermosetting resin to be foamed, and no examples for producing the foam are shown.

In claim 1 of Patent Document 4, XCF _z R _3-z (X is an unsaturated alkyl group having 2 or 3 carbon atoms and substituted with a chlorine atom and / or a fluorine atom, and R is independently Cl, F, Br, or H, and z is 1 to 3.) describes a method for producing a urethane foam using a foaming agent containing a compound represented by:
HFO-1233zd and CF ₃ CF═CCl ₂ (CFO-1214ya) are also included in the examples of the foaming agent, but no specific examples of producing urethane foam are described.

International Publication No. 2012/105657 International Publication No. 2012/106565 International Publication No. 2013/059550 US Patent Application Publication No. 2011/0269861

According to the knowledge of the present inventors, when HFO-1233zd is used as a foaming agent in the production of rigid foam, the heat insulation is not necessarily sufficient, and it is desired to further improve the heat insulation.
Further, when CFO-1214ya is used as a foaming agent, the density of the rigid foam may not be sufficiently low. In the production of rigid foam, it is desirable that low density can be achieved with a small amount of foaming agent from the viewpoint of raw material costs and the like.
This invention is made | formed in view of the said situation, and it aims at enabling it to manufacture the rigid foam which has a low density and favorable heat insulation, suppressing the usage-amount of a foaming agent.

The present invention includes the following [1] to [8].
[1] A rigid foam synthetic resin in which a polyol composition (A) and a polyisocyanate compound (B) are reacted in the presence of a physical foaming agent (C), a foam stabilizer (D), and a catalyst (E). A rigid foaming method, wherein the polyol composition (A) has a weight average molecular weight of 100 to 3,000, and the physical foaming agent (C) comprises CF ₃ CF═CHCl and CF ₃ CF═CCl ₂ A method for producing a synthetic resin.

[2] The method for producing a rigid foam synthetic resin according to [1], wherein the polyol composition (A) includes a polyol (A1) having an aromatic ring.
[3] The method for producing a rigid foam synthetic resin according to [2], wherein the polyol (A1) is a polyol (A11) having an aromatic ring and an oxyalkylene group.
[4] The rigid foam synthetic resin according to [3], wherein the polyol (A11) has an oxyethylene group, and the content of the oxyethylene group with respect to the total amount of the oxyalkylene group is 20 to 100% by mass. Method.
[5] In any one of [1] to [4], the content ratio of the physical foaming agent (C) is 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyol composition (A). The manufacturing method of the hard foam synthetic resin of description.
[6] relative to the total amount of the physical blowing agent _(C), the total content of the CF 3 CF = CHCl and _CF 3 _CF = CCl ₂ is 50 to 100% by weight, of [1] to [5] The manufacturing method of the hard foam synthetic resin as described in any one of Claims.
[7] the _{CF 3 CF = CHCl: CF 3} CF = mass ratio of CCl ₂ 99: 1 to 50: 50, the method of manufacturing a rigid foamed synthetic resin according to any one of claims 1 to 6 .

[8] A physical foaming agent (C) containing a polyol composition (A) having a weight average molecular weight of 100 to 3,000 and a polyisocyanate compound (B) containing CF ₃ CF═CHCl and CF ₃ CF═CCl _2. A rigid foamed synthetic resin obtained by reacting in the presence of a foam stabilizer (D) and a catalyst (E) and having a density of 5 to 300 kg / m ³ .

According to the present invention, by using a combination of _CF 3 CF = CHCl as physical blowing agent (HCFO-1224yd) and _{CF 3 CF = CCl 2 (CFO} -1214ya), while suppressing the amount of blowing agent, density Low and rigid foams with good thermal insulation can be produced.

The weight average molecular weight (hereinafter sometimes referred to as Mw) in the present specification is a polystyrene equivalent molecular weight obtained by measuring by gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample having a known molecular weight. It is.
In the present specification, the physical foaming agent means a compound that foams by using a gas generated by the vaporization of the foaming agent, and the chemical foaming agent uses a gas generated by a reaction between the foaming agent and a polyisocyanate compound. Meaning a compound to be foamed.

<Polyol composition (A)>
The “polyol composition” in the present invention is a mixture of all the polyols (including polymer-dispersed polyols) used for the reaction with the polyisocyanate compound. One type of polyol may be used, or two or more types may be used in combination.
Examples of the “polyol” include polyether polyol, polyester polyol, polyester ether polyol, and polycarbonate polyol.
The polyether polyol or polyester ether polyol has an oxyalkylene group.

The weight average molecular weight of the polyol composition (A) is 100 to 3,000, preferably 100 to 1,000. When the weight average molecular weight is not more than the upper limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. When the weight average molecular weight is not less than the lower limit of the above range, the brittleness of the rigid foam is suppressed.
The weight average molecular weight of the polyol composition (A) is an average value of the weight average molecular weight of the polyol contained in the polyol composition (A).

2-8 are preferable and, as for the average hydroxyl number of a polyol composition (A), 2.5-7.5 are more preferable. When the average number of hydroxyl groups is not less than the lower limit of the above range, the compressive strength of the rigid foam is improved and shrinkage can be suppressed, so that the dimensional stability is good. When the average number of hydroxyl groups is less than or equal to the upper limit of the above range, rapid thickening behavior during foaming and molding is suppressed, and fluidity and moldability are improved.
The average hydroxyl group number of the polyol composition (A) is an average value of the average hydroxyl group number of the polyol contained in the polyol composition (A).

The average hydroxyl value of the polyol composition (A) is 100 to 800 mgKOH / g, preferably 200 to 700 mgKOH / g, particularly preferably 300 to 600 mgKOH / g. When the average hydroxyl value is at least the lower limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. When the average hydroxyl value is not more than the upper limit of the above range, brittleness of the rigid foam is suppressed.
The average hydroxyl value of a polyol composition (A) is an average value of the average hydroxyl value of the polyol contained in a polyol composition (A).

  The polyol can be broadly divided into a polyol (A1) having an aromatic ring and a polyol (A2) having no aromatic ring. When the polyol composition (A) contains the polyol (A1), the heat insulating performance of the rigid foam tends to be good, which is preferable.

<Polyol (A1) having an aromatic ring>
The polyol (A1) having an aromatic ring is preferably a polyol (A11) having an aromatic ring and having an oxyalkylene group, or a polyester polyol (A12) having an aromatic ring. It is preferable that the polyol composition (A) is the polyol (A11) in that the adhesive property of the rigid foam tends to be good.

The polyester polyol (A12) having an aromatic ring is, for example, a polyester polyol obtained by polycondensation reaction of a dicarboxylic acid compound and a polyhydric alcohol, and one or both of the dicarboxylic acid compound and the polyhydric alcohol are aromatic. What is a compound which has a ring is mentioned. In particular, an aromatic polyester polyol obtained by polycondensation reaction of a dicarboxylic acid having an aromatic ring and a polyhydric alcohol not having an aromatic ring is preferable.
Examples of the dicarboxylic acid having an aromatic ring include terephthalic acid, isophthalic acid, and orthophthalic acid.
Examples of the polyhydric alcohol having no aromatic ring include ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol, dipropylene glycol (DPG), 1,4-butanediol, 1,6-hexanediol (1,6 -HD), diol compounds such as neopentyl glycol; and triol compounds such as glycerin and trimethylolpropane.
The hydroxyl value and weight average molecular weight of the polyester polyol (A12) are preferably in the same range for the same reason as the average hydroxyl value and weight average molecular weight of the polyol composition (A).

<Polyol (A11)>
The polyol (A11) is a polyol having an aromatic ring and having an oxyalkylene group.
For example, a polyol (polyether polyol) obtained by ring-opening addition of an alkylene oxide (hereinafter also referred to as “AO”) using an aromatic amine as an initiator is preferable.
The aromatic amine as an initiator is preferably an amine having an aromatic ring having 2 to 12 active hydrogen atoms. Specific examples thereof include phenylenediamine, tolylenediamine, diaminodiphenylmethane, and Mannich condensate. As tolylenediamine, o-tolylenediamine and m-tolylenediamine are preferable.
Examples of AO include ethylene oxide (hereinafter also referred to as “EO”), propylene oxide (hereinafter also referred to as “PO”), butylene oxide (hereinafter also referred to as “BO”), and the like. The AO to be subjected to ring-opening addition preferably contains at least PO or EO.
In the polyol (A11), the content of oxyethylene groups with respect to the total amount of oxyalkylene groups is preferably 20% by mass or more. When the proportion of the oxyethylene group is not less than the above lower limit, the polarity of the polyol becomes high, the solubility with the physical foaming agent in the present invention is suppressed, and the compression strength of the rigid foam tends to be high.
The upper limit of the oxyethylene group content relative to the total amount of the oxyalkylene group may be 100% by mass.
When two or more types of polyols (A11) are contained in the polyol composition (A), the content of oxyethylene groups relative to the total amount of oxyalkylene groups in the total of all polyols (A11) may be in the above range. .

2-12 are preferable, as for the number of hydroxyl groups of a polyol (A11), 2-10 are more preferable, and 2-8 are especially preferable.
When the number of hydroxyl groups of the polyol (A11) is within the above range, the average number of hydroxyl groups of the polyol composition (A) is likely to be within the above range.

The hydroxyl value of the polyol (A11) is preferably from 100 to 800 mgKOH / g, more preferably from 200 to 700 mgKOH / g.
When the hydroxyl value of the polyol (A11) is not less than the lower limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. When the average hydroxyl value is not more than the upper limit of the above range, brittleness of the rigid foam is suppressed.

100-1,000 are preferable and, as for the weight average molecular weight of a polyol (A11), 200-1,000 are more preferable.
When the weight average molecular weight of the polyol (A11) is not more than the upper limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. When the weight average molecular weight is not less than the lower limit of the above range, the brittleness of the rigid foam is suppressed.

A polyol (A11) may be used individually by 1 type, or may use 2 or more types together.
10-100 mass% is preferable with respect to the whole quantity of a polyol composition (A), and, as for content of the polyol (A11) in a polyol composition (A), 20-100 mass% is more preferable. When the content of the polyol (A11) is not less than the lower limit of the above range, the effect of improving the adhesiveness of the rigid foam can be sufficiently obtained. Also, heat insulation, flammability, and compressive strength are likely to be good.

<Polyol (A11m)>
Among the polyols (A11), the polyol (A11m) is preferable in terms of easy adhesion and good mixing with the polyisocyanate compound (B).
The polyol (A11m) is a polyol obtained by ring-opening addition of alkylene oxide to an initiator (S1) composed of a Mannich condensation product obtained by reacting phenols, aldehydes, and alkanolamines.
The polyol (A11m) in which the initiator (S1) is a Mannich condensation product contributes to the activity of the polyol particularly when the initiator includes an amino group, and the interface includes a hydrophilic group and a hydrophobic group. The active effect contributes to the improvement of the mixing property between the polyol and the polyisocyanate compound, and the carbonization film effect due to the fact that the initiator contains an aromatic ring contributes to the improvement of the flame retardancy of the rigid foam.

The phenol in the polyol (A11m), which is a raw material of the Mannich condensation product, is at least one selected from the group consisting of phenol and a phenol derivative having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol. It is. That is, it suffices to have a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, which may be phenol or a phenol derivative. The phenols used may be one type or two or more types.
The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and one or more of the other hydrogen atoms bonded to the aromatic ring are alkyl groups having 1 to 15 carbon atoms. Substituted alkylphenols are preferred.
The substitution position of the alkyl group in the alkylphenol may be either the ortho position or the para position. In one molecule of alkylphenol, the number of hydrogen atoms substituted with an alkyl group is 1 to 4, preferably 1 to 2, and particularly preferably 1.
It is preferable that carbon number of the alkyl group in alkylphenol is 1-10.
As the alkylphenol, nonylphenol and cresol are preferable. Nonylphenol is particularly preferable in terms of improving the compatibility between the polyol (A) and the polyisocyanate compound and improving the cell appearance.

In the raw material used for the Mannich condensation reaction, as the aldehyde, one or both of formaldehyde and acetaldehyde are preferable. Of these, formaldehyde is preferable in terms of the reactivity of the Mannich condensation reaction.
Formaldehyde may be used in any form. Specifically, it can be used as a formalin aqueous solution, a methanol solution, or paraformaldehyde. When used as paraformaldehyde, paraformaldehyde may be heated to form formaldehyde, and the formaldehyde may be used in the reaction of this step. The amount used is calculated as the number of moles in terms of formaldehyde.

  In the raw material used for the Mannich condensation reaction, the alkanolamines are preferably at least one selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol. Of these, diethanolamine is preferable in that a low-viscosity polyether polyol is easily obtained.

  In the production of the polyol (A11m), the Mannich condensation product used as an initiator is a reaction product obtained by reacting the phenols, aldehydes, and alkanolamines (Mannich condensation reaction). The reaction product includes unreacted substances remaining after the reaction. The Mannich condensation reaction can be carried out by a known method.

In the raw material used for the Mannich condensation reaction, the ratio of aldehydes to 1 mol of phenols is preferably 0.5 to 3 mol, more preferably 1 to 2.5 mol. When the ratio of the aldehydes is not less than the lower limit of the above range, good dimensional stability of the rigid foam is easily obtained. When it is at most the upper limit value, it becomes easy to obtain a low viscosity polyether polyol.
In the raw material used for the Mannich condensation reaction, the ratio of alkanolamines to 1 mol of phenols is preferably 1 to 3 mol, and more preferably 1.5 to 3 mol. When the ratio of the alkanolamines is at least the lower limit of the above range, a rigid foam having good strength can be easily obtained. When the amount is not more than the upper limit value, a favorable flame-retardant rigid foam is easily obtained.
From these facts, in the raw material used for the Mannich condensation reaction, the ratio of aldehydes to 1 mol of phenols is 0.5 to 3 mol, and the ratio of alkanolamines to 1 mol of phenols is 1 to 3 mol. It is preferable. That is, the Mannich condensation product reacts with phenols, 0.5 to 3 moles of aldehydes with respect to 1 mole of the phenols, and 1 to 3 moles of alkanolamines with respect to 1 mole of the phenols. It is preferable that it is obtained.

By reacting AO with the active hydrogen atom of the Mannich condensation product which is an initiator, AO undergoes ring-opening addition to obtain a polyether polyol having a (poly) oxyalkylene group.
It is preferable to use EO and / or PO as AO. The content of EO in the total amount of AO used for the production of the polyol (A11m) is preferably 20% by mass or more. When the ratio of EO is equal to or higher than the lower limit, the compression strength of the rigid foam tends to increase.
The upper limit of the content of EO in the total amount of AO may be 100% by mass.
In the present invention, the content of EO or PO in the total amount of AO used for the production of polyol can be regarded as being equal to the ratio of oxyethylene groups or oxypropylene groups to the total amount of oxyalkylene groups in the resulting polyol. .
When PO and EO are used in combination, PO and EO may be reacted sequentially to form a block copolymer, or a mixture of PO and EO may be reacted to form a random copolymer. The random chain of the random copolymer may contain a block portion.

  The amount (addition amount) of AO to be subjected to ring-opening addition to the initiator is preferably from 2 to 30 mol, particularly preferably from 4 to 20 mol, based on 1 mol of the phenols used for the production of the initiator. When the added amount of AO is not less than the lower limit of the above range, the hydroxyl value and viscosity of the produced polyether polyol are likely to be low. It is easy to suppress shrinkage | contraction of a rigid foam as it is below the upper limit of the said range.

2-8 are preferable and, as for the average number of hydroxyl groups of a polyol (A11m), 3-7 are more preferable. When the average number of hydroxyl groups of the polyol (A11m) is within this range, the average number of hydroxyl groups of the polyol composition (A) can be easily within the above range.
The average number of hydroxyl groups of the polyol (A11m) is the same as the average number of active hydrogens possessed by the Mannich condensation product as an initiator. When the raw materials used in the Mannich condensation reaction and the reaction ratio are within the above ranges, the average number of hydroxyl groups of the Mannich condensation product can be adjusted to a certain range, and the average number of hydroxyl groups of the polyol (A11m) can be adjusted to the above range. Can do.

The hydroxyl value of the polyol (A11m) is preferably from 100 to 800 mgKOH / g, more preferably from 200 to 700 mgKOH / g, particularly preferably from 250 to 650 mgKOH / g.
When the hydroxyl value is at least the lower limit of the above range, the strength of the obtained rigid foam is easily secured, and good dimensional stability is easily obtained. When the hydroxyl value is not more than the upper limit of the above range, the amount of AO-derived (poly) oxyalkylene chain present in the polyol (A11m) increases, and the viscosity of the polyol (A11m) tends to decrease. Moreover, the brittleness of the manufactured rigid foam is suppressed, the adhesiveness with the base material is easily obtained when it is molded, and the compressive strength is also improved.

  The weight average molecular weight of the polyol (A11m) is preferably 100 to 1,000, and more preferably 200 to 1,000. When the weight average molecular weight of the polyol (A11m) is not more than the upper limit of the above range, it is easy to ensure the strength of the resulting rigid foam, and good dimensional stability is easily obtained. Moreover, when it is at least the lower limit of the above range, the amount of AO-derived (poly) oxyalkylene chains present in the polyol (A11m) increases, and the viscosity of the polyol (A11m) tends to decrease. Furthermore, the brittleness of the manufactured rigid foam is suppressed, the adhesiveness with the base material is easily developed when it is molded, and the compressive strength is improved.

A polyol (A11m) may be used individually by 1 type, or may use 2 or more types together.
10-100 mass% is preferable with respect to the whole quantity of a polyol composition (A), and, as for content of the polyol (A11m) in a polyol composition (A), 20-100 mass% is more preferable. When the content of the polyol (A11m) is at least the lower limit within the above range, in the case containing _CF 3 CF = CHCl as blowing agent (CFO-1214ya) and _{CF 3 CF = CCl 2 (HCFO} -1224yd), in particular, Thermal insulation, flame retardancy, and compressive strength tend to be good.
Particularly, a polyol (A11m) containing 20 to 80% by mass of an EO-derived oxyethylene group with respect to the total amount of oxyalkylene groups derived from AO is 70 to 100% by mass with respect to the total amount of the polyol composition (A). By including, it is preferable at the point which the heat insulation performance of a rigid foam becomes easy and high compressive strength is easy to be obtained.

<Polyol (A2) not having an aromatic ring>
As the polyol (A2) having no aromatic ring, a polyol (A21) having no oxyalkylene group without an aromatic ring or a polyester polyol (A22) having no aromatic ring is preferable. When the polyol composition (A) contains the polyol (A21), it is preferable in that the compressive strength of the rigid foam tends to increase.
Examples of the polyester polyol (A22) having no aromatic ring include aliphatic polyester polyols obtained by polycondensation reaction of an aliphatic dicarboxylic acid compound and an aliphatic polyhydric alcohol.
The hydroxyl value and weight average molecular weight of the polyester polyol (A22) are preferably in the same range for the same reason as the average hydroxyl value and weight average molecular weight of the polyol composition (A).

<Polyol (A21)>
A polyol (A21) is a polyol which does not have an aromatic ring and has an oxyalkylene group.
As the polyol (A21), a polyol (A21s) obtained by ring-opening addition of an alkylene oxide using an aliphatic compound containing no nitrogen atom as an initiator (S2), or an alkylene containing an aliphatic amine as an initiator (S3) Examples include aliphatic amine-based polyalkylene oxide polyols obtained by ring-opening addition of oxides. The polyol (A21) is preferably a polyol (A21s). It is preferable that the polyol composition (A) contains the polyol (A21s) in that the compressive strength of the rigid foam tends to be high.
The initiator (S2) will be described later.
The aliphatic amine that is the initiator (S3) is preferably an aliphatic amine having 2 to 4 active hydrogen atoms. Specific examples include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylamines such as ethylenediamine, propylenediamine and 1,6-hexanediamine. Of these, ethylenediamine, monoethanolamine or diethanolamine is preferred.

Examples of the alkylene oxide include EO, PO, and BO. The AO to be subjected to ring-opening addition preferably contains at least PO or EO.
The total amount of oxyalkylene groups in the polyol (A21) may be an oxypropylene group.
When the polyol (A21) contains an oxyethylene group, the content of the oxyethylene group with respect to the total amount of the oxyalkylene group is preferably more than 0% by mass, preferably 60% by mass or less, and more preferably 40% by mass or less. When the ratio of the oxyethylene group is within the above range, the compression strength of the rigid foam tends to be high.
When the polyol composition (A) contains two or more types of polyols (A21), the content of oxyethylene groups relative to the total amount of oxyalkylene groups in the total of all polyols (A21) may be in the above range. .

<Polyol (A21s)>
The polyol (A21s) is a polyol obtained by ring-opening addition of alkylene oxide using an aliphatic compound containing no nitrogen atom as an initiator (S2).
A polyhydric alcohol is mentioned as an initiator (S2). In particular, polyhydric alcohols having 4 to 12 active hydrogen atoms are preferred.
A polyether polyol obtained by ring-opening addition of alkylene oxide using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator, compresses a rigid foam by using a physical foaming agent (C) as a foaming agent. A strength improvement effect is easily obtained.

It is preferable to use a sugar alcohol or a saccharide as a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator. Specific examples of the sugar alcohol include pentaerythritol, sorbitol and the like, and specific examples of the sugar include fructose, sorbitol and sucrose. Of these, pentaerythritol, sorbitol or sucrose is preferred.
Examples of the alkylene oxide used for the production of the polyol (A21s) include EO, PO, and BO. It is preferable to contain at least PO or EO.
The AO used for the production of the polyol (A21s) is preferably a single PO or a combination of EO and PO. When used in combination, EO and PO may be reacted after mixing or sequentially.
When AO used for the production of the polyol (A21s) contains EO, the content of EO in the total amount of AO is preferably 60% by mass or less, more preferably 50% by mass or less from the viewpoint of easy control of reactivity. Preferably, 40 mass% or less is especially preferable.

  The number of hydroxyl groups in the polyol (A21s) is 4 to 12, preferably 4 to 10, and particularly preferably 4 to 8. When the number of hydroxyl groups of the polyol (A21s) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not more than the upper limit, the viscosity becomes an appropriate range and handling is easy.

The hydroxyl value of the polyol (A21s) is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (A21s) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed and the dimensional stability is improved. When the amount is not more than the upper limit of the above range, brittleness of the rigid polyurethane foam is easily suppressed.
The weight average molecular weight of the polyol (A21s) is preferably 100 to 3,000, and more preferably 200 to 1,000. When the weight average molecular weight of the polyol (A21s) is not more than the upper limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not less than the lower limit of the above range, the brittleness of the rigid foam is easily suppressed.

A polyol (A21s) may be used individually by 1 type, or may use 2 or more types together.
30-100 mass% is preferable with respect to the whole quantity of a polyol composition (A), and, as for content of the polyol (A21s) in a polyol composition (A), 50-100 mass% is more preferable. When the content of the polyol (A21s) is not less than the lower limit of the above range, the compression strength of the rigid foam is likely to be improved.

  The polyol (A) may contain both polyols (A1) and (A2). When the polyol (A) contains both the polyol (A1) and the polyol (A2), a combination of the polyol (A11) and the polyol (A21) is preferable, and the ratio of the polyol (A11) and the polyol (A21) is a weight ratio. 10:90 to 90:10 is preferable, and 30:70 to 70:30 is more preferable.

<Polymer-dispersed polyol (W)>
The polyol composition (A) may further contain a polymer-dispersed polyol (W).
The polymer-dispersed polyol (W) is a polyol in which polymer particles are stably dispersed, obtained by reacting a monomer having a polymerizable unsaturated group in the base polyol (W ′). In the present invention, a known polymer-dispersed polyol (W) can be used.
By including the polymer-dispersed polyol (W) in the polyol composition (A), the polymer particles can be present in the polyol composition (A). By the presence of polymer particles in the polyol (A), the shrinkage of the rigid foam can be suppressed and the dimensional stability can be improved. This effect is particularly useful when producing a lower density rigid urethane foam.
The content of the polymer-dispersed polyol (W) in the polyol composition (A) is preferably such that the content ratio of the polymer particles in the polyol composition (A) is 0.01% by mass or more. It is more preferable that it is the quantity used as 01-10 mass%. Usually, the content of the polymer-dispersed polyol (W) is preferably 0.1% by mass or more.

<Polyisocyanate compound (B)>
Examples of the polyisocyanate compound include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; modified polyisocyanates obtained by modifying these.
Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates or their prepolymer-modified products, isocyanurates, urea-modified products, carbodiimide-modified products, and the like. Of these, crude MDI or a modified product thereof is preferred, and a modified product of crude MDI is particularly preferred. The polyisocyanate compound may be used alone or in combination of two or more.
The amount of the polyisocyanate compound used is represented by 100 times the number of isocyanate groups with respect to the total number of active hydrogen atoms of the polyol composition (A) and other active hydrogen compounds (hereinafter, the numerical value represented by 100 times is expressed as “ Is referred to as “isocyanate index”), preferably 50 to 300.
In particular, in the case of a urethane formulation mainly using a urethanization catalyst as a catalyst, the amount of the polyisocyanate compound is preferably 50 to 170, particularly preferably 70 to 150, in terms of the isocyanate index.
In the case of an isocyanurate formulation mainly using a catalyst that promotes a trimerization reaction of an isocyanate group as a catalyst, the polyisocyanate compound is preferably used in an amount of 110 to 400, more preferably 150 to 350 in terms of the isocyanate index. ~ 300 is particularly preferred.

<Physical foaming agent (C)>
In the present invention, at least CF ₃ CF═CHCl (hereinafter sometimes referred to as 1224yd) and CF ₃ CF═CCl ₂ (hereinafter sometimes referred to as 1214ya) are used as the physical foaming agent (C).
CF ₃ CF═CHCl is a cis type in which a trifluoromethyl group and a chlorine atom are present on the same side across a double bond (hereinafter, the cis type may be referred to as a Z form), a trifluoromethyl group and a chlorine atom. Is present on the opposite side across a double bond (hereinafter, the trans form may be referred to as E-form). What contains more cis forms than trans forms is preferable in terms of high productivity efficiency.
10-100 mass parts is preferable with respect to 100 mass parts of a polyol composition (A), and, as for the usage-amount of a physical foaming agent (C), 10-60 mass parts is more preferable, and 15-50 mass parts is especially preferable. When the amount of the physical foaming agent (C) is at least the lower limit of the above range, the density becomes appropriate and the ratio of the resin component (polyol) can be reduced. The heat insulation performance tends to be good because the cell tends to be dense and fine.

Other physical foaming agents other than 1224yd and 1214ya may be used in combination as long as the effects of the present invention are not impaired.
Other physical foaming agents can be appropriately selected from known physical foaming agents, and include CF ₂ H ₂ , CF ₃ CF ₂ H, CF ₃ CH ₃ , CHF ₂ CF ₂ H, CF ₃ CH ₂ F, and CHF _2. HFCs such as CH ₃ , CF ₃ CHFCF ₃ , CF ₃ CF ₂ CHFCHFCF ₃ , CHF ₂ CH ₂ CF ₃ (365mfc), CH ₃ CF ₂ CH ₂ CF ₃ (245fa), etc .: HCs such as cyclopentane: CCl HCFCs such as ₂ FCH ₃ (141b): HFEs such as CF ₃ CF ₂ CF ₂ OCH _{3 and} CHF ₂ CF ₂ OCH ₃ are included.
50-100 mass% is preferable and, as for the ratio of the total amount of 1224yd and 1214ya among the whole quantity of a physical foaming agent (C), 80-100 mass% is more preferable. If the ratio of the total amount of 1224yd and 1214ya is 50% by mass or more, the heat insulation performance tends to be good.
The mass ratio of the amount used of 1224yd: 1214ya is preferably 99: 1 to 50:50, more preferably 90:10 to 60:40. When the ratio of 1224yd is not less than the lower limit of the above range, a low-density rigid foam is easily obtained. When the ratio of 1214ya is equal to or more than the lower limit of the above range, good heat insulating properties are easily obtained.

Moreover, it is preferable to use together a physical foaming agent (C) and water which is a chemical foaming agent. 1-25 mass parts is preferable with respect to 100 mass parts of a polyol composition (A), and, as for the usage-amount of water as a foaming agent, 1-10 mass parts is more preferable, and 1-5 mass parts is especially preferable.
When the blowing agent is 1224yd, 1214ya and water, the ratio of the total amount of 1224yd and 1214ya: water (mass ratio) is preferably 30:70 to 99: 1, and more preferably 50:50 to 98: 2.

<Foam stabilizer (D)>
The foam stabilizer is used to form good bubbles.
Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. These can use a commercial item.
Although content of the foam stabilizer in a polyol system liquid can be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of a polyol composition (A).

<Catalyst (E)>
As the catalyst, a urethanization catalyst that promotes a urethanization reaction and / or a trimerization reaction promotion catalyst that promotes a trimerization reaction of an isocyanate group is used. A tertiary amine is preferred as the urethanization catalyst. As the trimerization promoting catalyst, metal salts excluding tin salts, lead salts and mercury salts, and / or quaternary ammonium salts are preferable. In the case of an isocyanurate formulation, the combined use of a urethanization catalyst and a trimerization reaction promoting catalyst is preferable, and it is more preferable to use a tertiary amine in combination with the metal salt and / or the quaternary ammonium salt.

  As the tertiary amine, for example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ — Pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N-methyl-N- And tertiary amine compounds such as (N, N-dimethylaminoethyl) ethanolamine.

  As the metal salt excluding the tin salt, lead salt and mercury salt, carboxylic acid metal salts such as potassium acetate, potassium 2-ethylhexanoate and bismuth 2-ethylhexanoate are preferable.

Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; tetramethylammonium 2-ethylhexanoate, 2-hydroxy Tetraalkylammonium organic acid salts such as propyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate; tertiary amines such as N, N, N ′, N′-tetramethylethylenediamine and carbonic acid diesters And quaternary ammonium compounds obtained by reacting 2-ethylhexanoic acid with an anion exchange reaction.
As for the usage-amount of a catalyst, it is preferable that the total amount of a catalyst is 0.1-20 mass parts with respect to 100 mass parts of a polyol composition (A).
By adjusting the amount of catalyst used, the time from the start of mixing of the components used for foaming such as the polyol composition (A) and the polyisocyanate compound (B) to the start of the reaction (cream time), or foaming is completed. The time to rise (rise time) can be adjusted.

<Optional component>
The polyol system liquid of the present invention may further contain other components other than the components described above, if necessary.
A known compounding agent can be used as the other component. Examples of the compounding agent include a filler, an anti-aging agent, a flame retardant, a plasticizer, a colorant, an antifungal agent, a foam breaker, a dispersant, and a discoloration preventing agent. Examples of the filler include calcium carbonate and barium sulfate. Examples of the anti-aging agent include antioxidants and ultraviolet absorbers.
Although content of this other component can be suitably selected according to the objective, 0.1-30 mass parts is preferable with respect to 100 mass parts of a polyol composition (A).

<Method for manufacturing rigid foam>
The method for producing a rigid foam of the present invention comprises a polyol composition (A) and a polyisocyanate compound (B) in the presence of a physical foaming agent (C), a foam stabilizer (D), and a catalyst (E). A step of reacting.
Specifically, a polyol system liquid containing a polyol composition (A), a physical foaming agent (C), a foam stabilizer (D), and a catalyst (E) and a polyisocyanate compound are mixed, and a polyol composition ( A method of producing a rigid foam by reacting and foaming A) and the polyisocyanate compound (B) is preferred.

  A known method can be used as a method of reacting the polyol composition (A) and the polyisocyanate compound (B). For example, a rigid foam raw material composed of a polyol system liquid and polyisocyanate is injected into a frame of a mold or the like to cause foaming; a so-called injection method; by supplying a rigid foam raw material between two face materials and foaming, Examples include a so-called continuous board forming method that is a method of manufacturing a laminate in which a rigid foam is sandwiched between these face materials; a so-called spray method that is a method of spraying and applying a hard foam.

The injection method can be performed, for example, by a method using a high pressure foaming device or a low pressure foaming device. When a high pressure foaming device or a low pressure foaming device is used, a polyol system liquid is injected into various molds and then foamed and cured to produce a rigid foam. The foaming agent may be blended in advance in the polyol system liquid or may be blended when foaming is performed by the foaming apparatus.
Articles that can be manufactured using the injection method include refrigeration equipment such as electric refrigerators, panels for freezing / refrigerated vehicles, and the like.

In the continuous board molding method, a rigid foam raw material is supplied between two face materials and foamed to form a rigid foam. Thereby, the laminated body by which the rigid foam was pinched | interposed between two surface materials is obtained.
The continuous board forming method is used for manufacturing a heat insulating material for architectural use.

The spray method is roughly classified into an air spray method and an airless spray method. Of these, an airless spray method is particularly preferred in which a rigid foam material comprising a polyol system liquid and a polyisocyanate compound is mixed and foamed by a mixing head.
In this specification, the spray method includes a manufacturing method in which a rigid foam raw material is stirred and foamed by a spray method and injected into a frame of a mold. Furthermore, the foam raw material is supplied by spraying inside one side of the two pairs of face materials, and the other face material is laminated in the process of foaming, so that A method of continuously producing a laminate in which a rigid foam is sandwiched between the two is also included.
Articles that can be manufactured using the spray method include heat insulating materials such as architecture, vehicles, and aircraft, and soundproofing materials.

<Hard foam synthetic resin>
According to the present invention, in the production of rigid foam, the physical foaming agent (C), CF ₃ CF═CHCl (1224yd) and CF ₃ CF═CCl ₂ (1214ya), are used in combination, whereby the amount of foaming agent used is It is possible to reduce the density of the foam while suppressing the heat resistance, and to improve the heat insulation performance by reducing the thermal conductivity. In addition, as shown in Examples described later, it is possible to obtain a rigid foam having a low thermal conductivity, excellent heat insulation, and good compressive strength.
Preferably, a polyol composition (A) having a weight average molecular weight of 100 to 3,000, a polyisocyanate compound (B), a physical foaming agent (C) containing 1224yd and 1214ya, a foam stabilizer (D), and By reacting in the presence of the catalyst (E), a rigid foam (rigid foam synthetic resin) having a density of 5 to 300 kg / m ³ can be produced.
The density of the rigid foam can be controlled by the amount of the physical foaming agent (C) used.
The thermal conductivity can be controlled by adjusting the composition of the polyol composition (A) and the physical foaming agent (C).

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The raw materials and measurement methods used in the following examples are as follows.

(Raw materials used)
[Polyol composition (A)]
Polyol A11m-1: obtained by ring-opening addition of PO alone with a reaction product obtained by reacting 2.2 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol A polyether polyol having an average number of hydroxyl groups of 3.5 and a hydroxyl value of 470 mg / KOH. The added amount of AO was 5.5 mol of PO with respect to 1 mol of nonylphenol. The ratio of EO to the total amount of AO is zero. The weight average molecular weight was 358.
Polyol A11m-2: obtained by ring-opening addition of EO alone with a reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol A polyether polyol having an average number of hydroxyl groups of 3.5 and a hydroxyl value of 590 mg / KOH. The added amount of AO was 2.6 mol of EO with respect to 1 mol of nonylphenol. The ratio of EO to the total amount of AO is 100% by mass. The weight average molecular weight was 255.
Polyol A11m-3: PO was subjected to ring-opening addition using a reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, A polyether polyol obtained by ring-opening addition of EO in the presence of a potassium oxide catalyst and having an average hydroxyl number of 3.5 and a hydroxyl value of 575 mgKOH / g. The addition amount of AO was 1 mol of PO and 1.3 mol of EO with respect to 1 mol of nonylphenol. The ratio of EO to the total amount of AO is about 49.7% by mass, and the ratio of PO is 50.3% by mass. The weight average molecular weight was 249.

  Polyol A21s-1: A poly (polysiloxane) having an average hydroxyl number of 4.7 and a hydroxyl value of 450 mgKOH / g, obtained by ring-opening addition of only PO as an alkylene oxide to a mixture of sucrose and glycerin (mass ratio 2: 1) Ether polyol. The added amount of AO was 10 mol of PO with respect to 1 mol of glycerin. The ratio of EO to the total amount of AO is zero. The weight average molecular weight was 563.

[Physical foaming agent (C)]
Blowing agent _{C-1: HCFO-1224yd (} CF 3 CF = Z member 90 _wt% of CHCl, CF 3 CF = E 10% by weight of CHCl).
Foaming agent C-2: CFO-1214ya (CF ₃ CF═CCl ₂ ).
Comparative blowing agent 1: HFC-245fa (CHF ₂ CH ₂ CF ₃ ).
Comparative blowing agent 2: HFC-365mfc (CF ₃ CH ₂ CF ₂ CH ₃ ).
Comparative blowing agent 3: HCFO-1233zd (CF ₃ CH = CHCl E form).

[Foam stabilizer (D)]
Foam stabilizer D-1: Silicone foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193).
[Catalyst (E)]
Catalyst E-1: 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine (manufactured by Air Products, product name: Polycat 41).
Catalyst E-2: Diethylene glycol solution of potassium 2-ethylhexanoate (potassium concentration 15%, product name: PACCAT 15G, manufactured by Nippon Chemical Industry Co., Ltd.).
[Flame retardants]
Flame retardant 1: Tris (β-chloropropyl) phosphate (ICL-IP JAPAN, product name: Pyrol PCF).

[Polyisocyanate compound (B)]
Polyisocyanate compound B-1: polymethylene polyphenylene polyisocyanate (crude MDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200).

(Measuring method)
<Hydroxyl value of polyol>
The hydroxyl value of the polyol was measured according to JIS K1557-1 (2007 edition).
<Weight average molecular weight of polyol>
The weight average molecular weight of the polyol is gel permeation chromatography (manufactured by Tosoh Corp., model: HLC-8320GPC, column: TSK-GEL SuperHZ 2000 × 2 + 1000 × 2 = 6 m, manufactured by Tosoh Corp., eluent: triethylamine / amine containing polyol) THF = 0.1 mol / L, THF in the case of other polyols, flow rate: 0.35 ml / min, detector: RI 256 / UV 254, column temperature: 40 ° C., sample injection amount: 20 μL, sample concentration: 0.05 g / 10 ml), and the polystyrene equivalent molecular weight was measured from a calibration curve prepared using a standard polystyrene sample having a known molecular weight.

<Evaluation method of rigid foam>
[Reactivity]
The mixing start time of the polyol system liquid and the polyisocyanate compound was 0 second, and the cream time, gel time, and rise time were measured.
Cream time (ct) (seconds): Time from the start of mixing until the mixture of the polyol system liquid and the polyisocyanate compound starts to foam.
Gel time (gt) (seconds): From the mixing start time, as the gelation progresses, a thin glass or metal rod is gently put on the foaming stock solution composition being foamed and then foamed when quickly pulled out. The time until the stock composition begins to draw the yarn.
Rise time (rt) (seconds): Time from the start of mixing until the rising of the foam expanding in the container stops.

[Compressive strength / density]
The compressive strength of the foam was measured according to JIS A 9511.
Samples obtained by cutting the transverse (x), longitudinal (y), and height (z) directions to 50 mm each from the core portion of the free foamed foam were used. The density (unit: kg / m ³ ) of the sample piece and the compressive strength (unit: kPa) in the height (z) direction and the lateral (x) direction were measured.
The density was measured by a method based on JIS A 9511.

[Dimensional stability]
Dimensional stability was measured by a method according to ASTM D 2126-75.
Each test of low-temperature dimensional stability and wet heat dimensional stability was performed using a test piece cut out from the core of a free foamed foam with dimensions of horizontal (x) 75 mm, vertical (y) 150 mm, and height (z) 100 mm. went.
In each test, first, the test piece was stored under the following conditions.
Low temperature dimensional stability: The specimen was stored in a thermostatic bath at -30 ° C for 24 hours.
Wet heat dimensional stability: The test piece was stored for 24 hours in a constant temperature bath at 70 ° C. in an atmosphere with a relative humidity of 95%.
After completion of the storage under each of the above conditions, the dimensional change rate was determined by the following formula in the three directions x, y, and z of the test piece. In the dimensional change rate, a negative value means shrinkage, and a large absolute value means that a dimensional change is large.
Dimensional change rate (%) = (size after storage−size before storage) / size before storage × 100

[Thermal conductivity]
The thermal conductivity (unit: W / m · K) of the rigid foam was measured according to JIS A 9511.
Samples were obtained by cutting the core of the free foaming foam into lengths of 190 mm and width of 25 mm, and using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.) as an average. Measurement was performed at a temperature of 23 ° C.

(Examples 1-3, Comparative Examples 1-9)
A polyol system solution was prepared by mixing 1.2 times the predetermined amount of each polyol, flame retardant, foam stabilizer, catalyst, and foaming agent at the blending ratio shown in Tables 1 and 2. The unit of the numerical values of the formulations shown in Tables 1 and 2 is parts by mass. That is, the amount of polyol used (100 parts by mass) was 120 g. However, the blending amount of the polyisocyanate compound also represents the isocyanate index.
The liquid temperature of the prepared polyol system liquid and the liquid temperature of the polyisocyanate compound were adjusted to 15 ° C., respectively, and a free-foaming foam (rigid foam) was produced according to the procedure shown below.

<Manufacture of free foaming foam>
Using a stirrer in which a polyisocyanate compound is added to the container containing the polyol system liquid prepared in the above procedure and a disc-shaped stirrer blade is mounted on a drilling machine manufactured by Hitachi, Ltd., rotation at 3,000 rpm The foaming stock solution composition was prepared by stirring and mixing at a speed for 5 seconds.
The foamed stock solution composition immediately after preparation was quickly put into a 200 mm long, horizontal, and height wooden box equipped with a polyethylene release bag to obtain a free foaming foam.

<Evaluation>
The physical properties (density, compressive strength, dimensional stability, thermal conductivity) of the obtained free foamed foam were measured by the procedure shown in the evaluation method for the rigid foam.
Moreover, the reactivity (cream time, gel time, rise time) was measured by the above-mentioned method in the middle of the manufacturing process. These results are shown in Tables 1 and 2.

As shown in the results of Tables 1 and 2, the _{CF 3 CF = CHCl (HCFO-} 1224yd) and _CF 3 _CF = CCl 2 Example 1~4 (CFO-1214ya) were used in combination as a physical blowing agent, density A rigid foam with low, low thermal conductivity, excellent heat insulation and good compressive strength was obtained.
On the other hand, Comparative Examples 1, 4, 7, and 10 are examples using CFO-1214ya alone as a physical foaming agent, and Comparative Examples 2, 5, 8, and 11 are HFCs with high GWP (HFC-245fa and HFC- 365 mfc), and Comparative Examples 3, 6, 9, and 12 are examples using HFO-1233zd, which is another hydrofluoroolefin.
Example 1, Example 2, Example 3, Example 4 were compared with Comparative Examples 2, 3, Comparative Examples 5, 6, Comparative Examples 8, 9, and Comparative Examples 11 and 12, respectively. ) Improved.
In Examples 1, 2, 3, and 4, the amount of foaming agent used was the same as that of Comparative Examples 1, 4, 7, and 10, but the density decreased. In Examples 2, 3, and 4, the compression strength of the rigid foam is better than that of Comparative Examples 6, 9, and 12.

  Further, when Examples 1 to 4 are compared, Examples 1, 2, and 3 using a polyol having an aromatic ring as the polyol composition (A) are Examples 4 using a polyol having no aromatic ring. The value of thermal conductivity is lower than that, and the heat insulation performance is excellent.

Claims (8)

In a method for producing a rigid foam synthetic resin in which a polyol composition (A) and a polyisocyanate compound (B) are reacted in the presence of a physical foaming agent (C), a foam stabilizer (D), and a catalyst (E). There,
The polyol composition (A) has a weight average molecular weight of 100 to 3,000,
The physical blowing agent (C) comprises _CF 3 CF = CHCl and _CF 3 _CF = CCl _2, method for producing a rigid foamed synthetic resin.   The manufacturing method of the hard foam synthetic resin of Claim 1 in which the said polyol composition (A) contains the polyol (A1) which has an aromatic ring.   The manufacturing method of the hard foam synthetic resin of Claim 2 whose said polyol (A1) is a polyol (A11) which has an aromatic ring and has an oxyalkylene group.   The method for producing a rigid foam synthetic resin according to claim 3, wherein the polyol (A11) has an oxyethylene group, and the content of the oxyethylene group with respect to the total amount of the oxyalkylene group is 20 to 100% by mass.   Hard foam synthesis as described in any one of Claims 1-4 whose content rate of the said physical foaming agent (C) is 10-100 mass parts with respect to 100 mass parts of whole quantity of a polyol composition (A). Manufacturing method of resin. Based on the total amount of the physical blowing agent _(C), the total content of the CF 3 CF = CHCl and _CF 3 _CF = CCl ₂ is 50 to 100 wt%, to any one of claims 1 to 5 The manufacturing method of the hard foam synthetic resin of description. Wherein _{CF 3 CF = CHCl: CF 3} CF = mass ratio of CCl ₂ 99: 1 to 50: 50 is a method for producing a rigid foamed synthetic resin according to any one of claims 1-6. Polyol composition having a weight average molecular weight of 100 to 3,000 and (A), polyisocyanate compound (B) and _a, CF 3 CF = CHCl and _CF 3 CF = physical blowing agent comprising CCl ₂ (C), the foam Hard foam synthetic resin obtained by reacting in the presence of the agent (D) and the catalyst (E) and having a density of 5 to 300 kg / m ³ .