JP4355307B2 - Active hydrogen compound or active hydrogen component and method for producing foam - Google Patents

Description

The present invention relates to a novel polyether compounds, active hydrogen compound comprising from the polyether, the polyether or the active hydrogen compound resin forming composition used, and the form (in particular polyurethane foams using the polyether or the active hydrogen compound ), A method for producing an active hydrogen compound and a foam using a polyether having a high primary hydroxylation rate of the terminal hydroxyl group, and the like. More specifically, the present invention relates to a polyether having a high primary ratio of terminal hydroxyl groups and use thereof.

<Rigid polyurethane foam>
Conventionally, rigid polyurethane foam has been widely used as a heat insulating material for civil engineering construction, transportation equipment, and home appliances. In recent years, in order to improve productivity, polyols having a higher primary OH conversion rate have been used in order to improve reactivity with isocyanates. Normally, AO adducts with EO added to the ends are used as polyols with a higher primary OH conversion rate, but rigid polyurethane foams using AO adducts with EO added to the ends in the usual way Although it has excellent curability, it has problems that it swells upon demolding and foam strength is small.

<Rigid polyurethane foam>
The purpose of the present invention is excellent in curability, and is that the swelling at the time of demolding small to obtain a preparation of large rigid polyurethane foam foam strength.

As a result of intensive investigations to solve the above problems, the present inventors have found that the polyether of any one of the following first to third inventions has a small number of moles of EO added as a polyol component of the resin and is hydrophobic. Thus, the present invention has been found to have sufficient reactivity while maintaining the above. Moreover, the active hydrogen compound and resin-forming composition comprising the polyether of the following fourth to eighteenth inventions, a method for producing a foam using the active hydrogen compound, and a polyether related to the polyether were used. Invented a process for producing active hydrogen compounds and foams. (In the above invention, the first to third inventions, the sixth to eighth inventions, the 11th to 15th inventions, and the 17th to 18th inventions are reference inventions.)

[Invention related to polyether]
<First Invention (Reference Invention)> In the active hydrogen compound, the average addition mole number x of ethylene oxide per active hydrogen is 20 or less, and the primary OH conversion rate y of terminal hydroxyl groups is 40% or more. X and y are mainly composed of 1,2-alkylene oxide having 3 or more carbon atoms and satisfying the relationship of the formula (1) when x is 10 to 20, and the formula (2) when x is 10 or less. A polyether polyol obtained by random and / or block addition of an alkylene oxide.

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

  <Second invention (reference invention)> 40% or more (60% or more in the case of monool) of -AO-H group, which is represented by the following general formula (4) and is a hydroxyl group-containing group located at the terminal, is described below. It is formed by adding ethylene oxide to the terminal hydroxyl group of polyoxyalkylene polyol or monool (j), which is a primary hydroxyl group-containing group represented by the general formula (5), and satisfies the following <1> to <3> requirements Monohydroxy or polyhydroxy polyether.

<1> The average added mole number x of ethylene oxide per hydroxyl group is 20 or less,
<2> The terminal primary hydroxyl group content y is 60% or more for monohydroxy polyether and 40% or more for polyhydroxy polyether.
<3> x ≦ 5.5 × z−6.5 × Ln (z) −6.46 (3)
(Z is 1.03-y / 100; Ln (z) is the natural logarithm of z.)

R ¹ -[-(ZO) p- (AO) q-H] m (4)

[In Formula (4), R ¹ is an m-valent group obtained by removing active hydrogen from water, alcohol, phenol, amine, carboxylic acid, thiol or phosphoric acid compound; Z is substituted with a halogen atom or an aryl group; An alkylene group or a cycloalkylene group having 2 to 12 carbon atoms; A is an alkylene group having 3 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group; m is a number of 1 or 2 to 100; 0 or a number of 1 or more, q is an average of 1 or more, and p + q is an average of 1 to 200.

In Formula (5), R ² is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom. ]
<Third Invention (Reference Invention)> An active hydrogen compound is composed of 1,2-alkylene oxide having 3 or more carbon atoms as a main component, and alkylene oxide containing ethylene oxide is randomly and / or block-added to form a hydrophilic / hydrophobic balance ( A polyether polyol in which the HLB) and the primary OH conversion rate (%) of the terminal hydroxyl group of the polyether polyol are represented by the formula (6).

    (HLB) ≦ 0.1 × (primary OH conversion rate) −2 (6)

[Invention concerning active hydrogen compounds ]
<Fourth Invention> A polyhydric alcohol is represented by the following general formula (8), (9), or (10) , wherein each primary OH group has 1 or more moles of 1,2-alkylene oxide having 3 or more carbon atoms. The polyether polyol formed by adding ethylene oxide to the polyether polyol added in the presence of the catalyst (α) to be added has a hydroxyl value of 200 or more, and the average addition of ethylene oxide per active hydrogen It comprises a polyether polyol (a1) having a mole number x of 2 or less, a primary OH conversion rate y of 40 % or more, and a primary OH conversion rate of terminal hydroxyl groups of the unadded ethylene oxide of 40% or more. Active hydrogen compound for rigid polyurethane foam production.

X-(-R ³ ) ₃ (8)

[In the formulas (8) to (10), each X represents a boron atom or an aluminum atom; R ^Three Represents a (substituted) phenyl group represented by the following general formula (11) and / or a tertiary alkyl group represented by the following general formula (12); ^Three If there are multiple, multiple R ^Three May be the same or different. ]

[In Formula (11), T represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different. k represents the number of 0-5. R in formula (12) ^Four , R ^Five , R ⁶ Each independently represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ]

<Fifth Invention> An active hydrogen compound (b) having 2 or more carbon atoms added to amines and having an active hydrogen value of 200 or more, and 1 mol or more per mol of primary OH group in polyhydric alcohol A polyether polyol in which a 1,3-alkylene oxide having 3 or more carbon atoms is added in the presence of a catalyst (α) represented by the following general formula (8), (9), or (10): Or a polyol obtained by further adding ethylene oxide to the polyol, having a hydroxyl value of 200 or more, an average addition mole number x of ethylene oxide per active hydrogen of 2 or less, and a primary OH conversion rate A hard material comprising a polyether polyol (a) having y of 40% or more and a primary OH conversion rate of terminal hydroxyl groups of the unadded ethylene oxide of 40% or more Li polyurethane foam production for active hydrogen components.
X-(-R ³ ) ₃ (8)

[In the formulas (8) to (10), each X represents a boron atom or an aluminum atom; R ^Three Represents a (substituted) phenyl group represented by the following general formula (11) and / or a tertiary alkyl group represented by the following general formula (12); ^Three If there are multiple, multiple R ^Three May be the same or different. ]

[In Formula (11), T represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different. k represents the number of 0-5. R in formula (12) ^Four , R ^Five , R ⁶ Each independently represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ]

<Sixth Invention (Reference Invention)> The average added mole number x of ethylene oxide per active hydrogen is 20 or less, the primary OH conversion rate y is 40% or more, and x and y are 10 to 10. Random and / or block addition of alkylene oxide mainly composed of 1,2-alkylene oxide having 3 or more carbon atoms and satisfying the relationship of formula (1) when 20 and formula (2) when x is 10 or less An active hydrogen compound for producing a semi-rigid polyurethane foam comprising the polyether polyol (c1).

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

<Seventh invention (Reference Invention)> active water iodine value 250 or more active hydrogen compound (d), hydroxyl value of 10 to 200, an average addition mole number x of ethylene oxide per active hydrogen is 20 In the following, the number of carbon atoms satisfying the relationship of the formula (1) when the primary OH conversion rate y is 40% or more, and x is 10 to 20, and the formula (2) when x is 10 or less. An active hydrogen compound for producing a semi-rigid polyurethane foam comprising a polyether polyol (c) to which an alkylene oxide mainly composed of 3 or more 1,2-alkylene oxides is added.

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

[Invention regarding resin-forming composition]
<Eighth Invention (Reference Invention)> 40% or more (60% or more in the case of monool) of -AO-H group, which is represented by the following general formula (4) and is a hydroxyl group-containing group located at the terminal, is described below. A polyoxyalkylene polyol which is a primary hydroxyl group-containing group represented by the general formula (5) or a monool (j) which is obtained by adding ethylene oxide to a terminal hydroxyl group and satisfies the following <1> to <3> requirements A resin-forming composition comprising a hydroxy or polyhydroxy polyether (K), a compound (L) reactive with a hydroxyl group, and, if necessary, another component (M) that reacts with (K) and / or (L).

<1> The average added mole number x of ethylene oxide per hydroxyl group is 20 or less,
<2> The terminal primary hydroxyl group content y is 60% or more for monohydroxy polyether and 40% or more for polyhydroxy polyether.
<3> x ≦ 5.5 × z−6.5 × Ln (z) −6.46 (3)
(Z is 1.03-y / 100; Ln (z) is the natural logarithm of z.)

R ¹ -[-(ZO) p- (AO) q-H] m (4)

[In Formula (4), R ¹ is an m-valent group obtained by removing active hydrogen from water, alcohol, phenol, amine, carboxylic acid, thiol or phosphoric acid compound; Z is substituted with a halogen atom or an aryl group; An alkylene group or a cycloalkylene group having 2 to 12 carbon atoms; A is an alkylene group having 3 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group; m is a number of 1 or 2 to 100; 0 or a number of 1 or more, q is an average of 1 or more, and p + q is an average of 1 to 200.

In Formula (5), R ² is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom. ]

[Invention relating to foam manufacturing method]
<9th invention> Active hydrogen compound (A), organic polyisocyanate (B), foaming agent (C), urethanization catalyst (D), and additive (E) as necessary, are foam-cured and hardened A method for producing a polyurethane foam, wherein (A) is a rigid polyurethane foam comprising the active hydrogen compound of the fourth invention.

<Tenth Invention> An active hydrogen compound (A), an organic polyisocyanate (B), a foaming agent (C), a urethanization catalyst (D) and, if necessary, an additive (E) are added and hardened by foaming and hardened. The method for producing a polyurethane foam, wherein (A) is a rigid polyurethane foam comprising the active hydrogen component of the fifth invention.

<11th invention (reference invention)> Active hydrogen compound (A), organic polyisocyanate (B), foaming agent (C), urethanization catalyst (D) and, if necessary, foam curing by adding additive (E) A method for producing a semi-rigid polyurethane foam, wherein (A) comprises the active hydrogen compound of the sixth invention.

<Twelfth Invention (Reference Invention)> Active hydrogen compound (A), organic polyisocyanate (B), foaming agent (C), urethanization catalyst (D), and additive (E) as necessary, foam curing A method for producing a semi-rigid polyurethane foam, wherein (A) comprises the active hydrogen compound of the seventh invention.

  <13th Invention (Reference Invention)> An active hydrogen compound comprising a polyol (A1) and an organic polyisocyanate (B) are combined with a foaming agent (C1), a urethanization catalyst (D) and a foam stabilizer (E1) comprising water. In the method for producing a flexible polyurethane foam by reacting in the presence of the above, the hydrophilic-hydrophobic balance (HLB) of the polyether polyol contained in (A1) and the terminal hydroxyl group of the polyether polyol contained in (A1) A method for producing a flexible polyurethane foam, wherein the primary OH conversion rate (%) is represented by the formula (6).

      (HLB) ≦ 0.1 × (primary OH conversion rate) −2 (6)

  <14th Invention (Reference Invention)> An active hydrogen compound comprising a polyol (A1) and an organic polyisocyanate (B) are mixed with a foaming agent (C1), a urethanization catalyst (D) and a foam stabilizer (E1) comprising water. In the method for producing a flexible polyurethane foam by reacting in the presence of benzene, the average added mole number x of ethylene oxide per active hydrogen is 20 or less, and the primary OH conversion rate y is 40% or more. X and y are alkylenes mainly composed of 1,2-alkylene oxides having 3 or more carbon atoms and satisfying the relationship of the formula (1) when x is 10 to 20, and the formula (2) when x is 10 or less. A method for producing a flexible polyurethane foam comprising a polyether polyol (c) to which an oxide is added.

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

  <15th Invention (Reference Invention)> An active hydrogen compound comprising a polyol (A1) and an organic polyisocyanate (B) are mixed with a foaming agent (C), a catalyst (D), a foam stabilizer (E1), and others as necessary. In the method for producing a flexible polyurethane slab foam by reacting in the presence of the additive (E2), 40% or more of the -AO-H groups in which (A1) is a hydroxyl group-containing group located at the terminal are represented by the following general formula: A method for producing a flexible polyurethane slab foam which is a polyether polyol which is a primary hydroxyl group-containing group represented by (5).

[However, A is an alkylene group having 3 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group, R ² is an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 carbon atoms. -10 aryl groups. ]

[Invention regarding foam and its use]
<Sixteenth Invention> A heat insulating material or a structural material for building materials, home appliances or transportation equipment, comprising a rigid polyurethane foam obtained by the production method of the ninth or tenth invention.

  <Seventeenth Invention (Reference Invention)> An impact absorbing material or cushioning material mounted inside an automobile interior material comprising a semi-rigid polyurethane foam obtained by the production method of the eleventh or twelfth invention.

<18th Invention (Reference Invention)> A flexible polyurethane foam obtained by the production method of the 13th or 14th invention, having a core density of 20 to 33 kg / m ³ and a wet heat compression set of 15% or less.

  According to the method for producing a rigid polyurethane foam of the present invention, it is possible to produce a rigid polyurethane foam which is excellent in curability, has a small swelling at the time of demolding and has a high foam strength as compared with the conventional one.

  Because of the above effects, the rigid polyurethane foam obtained by the method of the present invention is extremely useful as a heat insulating material for refrigerators, freezers and building materials.

<< Invention related to polyether (reference invention) >>
In the present invention, the primary OH conversion rate of the terminal hydroxyl group is calculated by ¹ H-NMR method after pre-treatment of the sample in advance. Details of the ¹ H-NMR method will be specifically described below.

<Sample preparation method>
About 30 mg of a measurement sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added and the mixture is allowed to stand at 25 ° C. for about 5 minutes to make the polyol a trifluoroacetic acid ester, which is used as a sample for analysis.

  Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.

<Calculation method of primary OH ratio of terminal hydroxyl group>
The signal derived from the methylene group to which the primary hydroxyl group is bonded is observed at around 4.3 ppm, and the signal derived from the methine group to which the secondary hydroxyl group is bonded is observed at around 5.2 ppm. Is calculated by the following equation (7).

Primary OH conversion rate (%) = [r / (r + 2s)] × 100 (7)
However,
r: integrated value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm s: an integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm.

The polyether polyol of the first invention (reference invention) may be used in combination of two or more, and the hydroxyl value (average) is preferably 10 or more, more preferably 13 to 1300, particularly preferably 16 to 1000. is there.

  When the hydroxyl value is within the above range, it is suitable for uses such as polyurethane foam.

  Further, the number of moles of EO added per active hydrogen of the polyol is 20 or less, the primary OH conversion rate y is 40% or more, and x and y are formulas when x is 10 to 20 ( 1) When x is 10 or less, the relationship of Formula (2) is satisfied.

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

  The added mole number x is preferably 19 or less, more preferably 0.1 to 18. The primary OH conversion rate y is preferably 60% or more, more preferably 70% or more.

  Further, when x is 10 or less, x and y preferably satisfy the relationship of the following formula (2 ′), and more preferably satisfy the relationship of the following formula (2 ″).

y ≧ 43x ^0.47 × (1-x / 41) (2 ′)
(However, x is 10 or less)
^{y ≧ 45x 0.47 × (1-} x / 41) (2 ")
(However, x is 10 or less)

  When the relationship between x and y and x and y is within the above ranges, both hydrophobicity and reactivity are good.

The polyol of the first invention (reference invention) is an active hydrogen compound containing AO containing mainly 1,2-alkylene oxide having 3 or more carbon atoms (hereinafter abbreviated as AO) and ethylene oxide (hereinafter abbreviated as EO). Can be obtained by the method described later.

  Specific examples of the active hydrogen compound include polyhydric alcohols, amines, polyhydric phenols, and polycarboxylic acids.

  Examples of polyhydric alcohols include dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol. And alicyclic diols such as cyclohexane diol and cycloalkylene glycol such as cyclohexane dimethanol, trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylol propane and trimethylol) Alkanetriols such as ethane and hexanetriol); 4 to 8 or more polyhydric alcohols having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, alkane polyols and their intramolecular or intermolecular dehydration products, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.

  Examples of amines include alkanolamines, polyamines and monoamines.

  Examples of the alkanolamines include alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine).

  Examples of polyamines include aliphatic amines such as alkylene diamines having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine, and hexamethylene diamine), and polyalkylene polyamines having 4 to 20 carbon atoms (the alkylene group having 2 carbon atoms). To 6 dialkylenetriamine to hexaalkyleneheptamine, such as diethylenetriamine and triethylenetetramine).

  Also, aromatic polyamines having 6 to 20 carbon atoms (for example, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); alicyclic polyamines having 4 to 20 carbon atoms ( Examples thereof include isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine); heterocyclic polyamines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine) and the like.

  As monoamines, ammonia; as aliphatic amines, alkylamines having 1 to 20 carbon atoms (for example, n-butylamine and octylamine); aromatic monoamines having 6 to 20 carbon atoms (for example, aniline and toluidine) An alicyclic monoamine having 4 to 20 carbon atoms (for example, cyclohexylamine); a heterocyclic monoamine having 4 to 20 carbon atoms (for example, piperidine), and the like.

  Examples of the polyhydric phenol include monocyclic polyphenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone; condensates of phenol and formaldehyde (novolac); for example, US Pat. No. 3,265,641 And polyphenols described in the book.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid and the like), and a mixture of two or more thereof.

  Of these, polyhydric alcohols are preferred.

  The 1,2-AO having 3 or more carbon atoms other than EO to be added to the active hydrogen-containing compound (which may be used in combination of two or more) usually has 3 to 20 carbon atoms, but 3 to 8 carbon atoms. For example, propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide (hereinafter abbreviated as BO), 1,2-pentene oxide, styrene oxide (hereinafter abbreviated as SO), and two or more thereof. In combination (block and / or random addition). Preferably, it is PO.

  The content of AO having 3 to 1,2-carbon atoms in AO is preferably 50% by mass or more, and more preferably 70% by mass or more.

The polyol of the first invention (reference invention) is obtained by random and / or block addition of EO as at least a part of AO to the active hydrogen compound. As a specific example, the active hydrogen compound has a carbon number. There may be mentioned three or more 1,2-AO (abbreviated as * AO in the following <1> to <5>) and EO added in the following manner.
<1> * Block added in the order of AO- EO (Chiped)
<2> * AO- EO- * AO- EO added in block order (balanced)
<3> EO- * AO- EO block added
<4> * AO- EO- * AO added in block order (active secondary)
<5> * Random adduct with mixed addition of AO and EO
<6> Random or block additions in the order described in JP-A-57-209920
<7> Random or block additions in the order described in JP-A-53-13700 Among these, terminal EO addition products are preferred.

  These may be used in combination.

The polyol of the first invention (reference invention) preferably has an average of 2 to 8, more preferably an average of 2.5 to 8 hydroxyl groups from the viewpoint of reactivity and viscosity.

  Examples of the method for obtaining this polyol include a method in which 1,2-AO having 3 or more carbon atoms is added to the active hydrogen-containing compound in the presence of a specific catalyst (α), and EO is further added.

  (Α) is described in International Publication No. WO00 / 02952, specifically, a compound represented by the following general formula (8), (9), or (10).

X-(-R ³ ) ₃ (8)

  In the above formulas (8) to (10), X represents a boron atom or an aluminum atom, respectively. Preferred is a boron atom.

R ³ in the formulas (8) to (10) represents a (substituted) phenyl group represented by the following general formula (11) and / or a tertiary alkyl group represented by the following general formula (12), and R ^When there are a plurality of ³ , the plurality of R ³ may be the same or different from each other.

  General formula

  T in the general formula (11) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group, and may be the same or different. Of these, a hydrogen atom, a halogen atom and a cyano group are preferred, and a halogen atom and a cyano group are more preferred. Moreover, k represents the number of 0-5.

  Specific examples of the phenyl group or substituted phenyl group represented by the general formula (11) include a phenyl group, a pentafluorophenyl group, a p-methylphenyl group, a p-cyanophenyl group, and a p-nitrophenyl group. Preferred are a phenyl group, a pentafluorophenyl group, and a p-cyanophenyl group, and more preferred are a phenyl group and a pentafluorophenyl group.

R ⁴ , R ⁵ and R ^{6 in the} general formula (12) each independently represent an alkyl group having 1 to 4 carbon atoms, and may be the same or different. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

  Specific examples of the tertiary alkyl group represented by the general formula (12) include a t-butyl group and a t-pentyl group.

  Specific examples of the catalyst (α) include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, Tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, bis (pentafluorophenyl) fluoroborane, di (T-butyl) borane fluoride, (pentafluorophenyl) difluoride borane, (t-butyl) difluoride borane, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, ( Pentafluorophenyl) difluoride Minium, (t-butyl) aluminum difluoride, and the like are preferable, and triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum are more preferable. Tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum.

  The addition condition of AO may be the same as the method described in the above publication. For example, it is usually 0.0001 to 10% by mass, preferably 0.001 to 1% by mass (α ) And usually at 0 to 250 ° C., preferably 20 to 180 ° C.

  The above AO adduct contains the catalyst (α), but (α) may be decomposed and / or removed. As a decomposition method, there is a method of adding water and / or an alcohol compound and, if necessary, a basic substance such as a caustic alkali or an amine compound. In the decomposition, the temperature is preferably 10 to 180 ° C, more preferably 80 to 150 ° C. Decomposition may be performed in a sealed state, may be performed while exhausting by connecting to a vacuum source, or may be performed while continuously adding water or an alcohol compound. Water or alcohol to be added may be added in a liquid state, or may be added in a vapor or solid state. The usage-amount of water and an alcohol compound is 0.1-100 mass% normally with respect to an addition product, Preferably it is 1-20 mass%. The usage-amount of a caustic alkali or an amine compound is 0-10 mass% normally with respect to an addition product, Preferably it is 0-2 mass%.

  Examples of the removal method include an adsorption method using an adsorbent or ion exchange resin such as synthetic silicate (magnesium silicate, aluminum silicate, etc.), activated clay, activated carbon, or a countercurrent extraction method using water or an aqueous caustic solution, or There are a stationary liquid separation method, a membrane separation method using an ion exchange membrane, and a low temperature crystallization method.

A polyol having a higher primary OH conversion rate can be obtained by further adding EO to the polyol obtained by adding AO, but the primary OH conversion rate of the terminal hydroxyl group of the polyol before the addition is 40%. Since it is extremely large as described above, the primary OH conversion rate of the terminal hydroxyl group can be increased with a small amount of EO used. When the EO addition mole number per active hydrogen is x and the primary OH conversion rate is y, x and y satisfies the above relationship. In addition, the catalyst used for the EO addition may use the boron or aluminum compound as it is, or may use another catalyst that is usually used instead.
Other catalysts include basic catalysts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate and triethylenediamine; acid catalysts such as boron trifluoride, tin chloride, triethylaluminum and heteropolyacid; zinc hexacyanocobal Tate; phosphazene compounds and the like. Of these, basic catalysts are preferred. Although the usage-amount of a catalyst is not specifically limited, Preferably it is 0.0001-10 mass% with respect to the polymer to produce | generate, More preferably, it is 0.001-1 mass%.

  As a conventional method for producing a polyol, the primary OH conversion rate of a terminal hydroxyl group of a polyol obtained by reacting 1,2-AO having 3 or more carbon atoms in the presence of an alkali catalyst is extremely low (for example, hydroxylation). When potassium is used, it is usually 2% or less), and most terminal hydroxyl groups are secondary or tertiary hydroxyl groups. For this reason, this polyol has insufficient reactivity with a reactive group such as an isocyanate group, and a method in which EO is further added to secure sufficient reactivity is known.

  However, unless a large amount of EO is added, the primary OH conversion rate of the terminal hydroxyl group does not increase. Therefore, x and y do not satisfy the above range, where x is the number of moles of EO added per active hydrogen, and y is the primary OH conversion rate.

  Further, when the number of EO addition moles per active hydrogen of the active hydrogen-containing compound is 20 or less, the primary OH conversion rate y is 40% or more, and x and y are 10 to 20 When the expressions (1) and x are 10 or less, the relationship of the expression (2) is satisfied.

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

  The added mole number x is preferably 19 or less, more preferably 0.1 to 18. The primary OH conversion rate y is preferably 60% or more, more preferably 70% or more.

  Further, when x is 10 or less, x and y preferably satisfy the relationship of the following formula (2 ′), and more preferably satisfy the relationship of the following formula (2 ″).

y ≧ 43x ^0.47 × (1-x / 41) (2 ′)
(However, x is 10 or less)
^{y ≧ 45x 0.47 × (1-} x / 41) (2 ")
(However, x is 10 or less)

  When the relationship between x and y and x and y is within the above ranges, both hydrophobicity and reactivity are good.

The polyoxyalkylene polyol or monool (j ) in the second invention (reference invention) is represented by the following general formula (4) and is 40% or more of the —AO—H group which is a hydroxyl group-containing group located at the terminal. (although 60% or more in the case of mono-ol) is represented by the following general formula (5).

R ¹ -[-(ZO) p- (AO) q-H] m (4)

In formula (4), R ¹ is an m-valent group obtained by removing active hydrogen from water, an alcohol compound, a phenol compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound or a phosphate compound, Is the number of 1 (monool) or 2 to 100 (polyol).

R ¹ may be a group obtained by removing the active hydrogen from the compound (k) having m active hydrogens. Examples of the compound (k) include a hydroxyl group-containing compound, an amino group-containing compound, and a carboxyl group-containing compound. A compound, a thiol group-containing compound, a phosphate compound; a compound having two or more active hydrogen-containing functional groups in the molecule; and a mixture of two or more of these.

  Examples of the hydroxyl group-containing compound include water, monohydric alcohol, 2 to 8 valent polyhydric alcohol, monohydric phenols, polyhydric phenols and the like.

Specific examples of the polyhydric alcohol and polyhydric phenol include those similar to the first invention (reference invention) described above.

  Examples of the monohydric alcohol include alcohols having 1 to 20 carbon atoms such as methanol, ethanol, butanol, and octanol. Examples of monohydric phenols include phenols having 6 to 20 carbon atoms such as phenol and cresol.

  Examples of the hydroxyl group-containing compound further include polybutadiene polyols; castor oil-based polyols; (co) polymers of hydroxyalkyl (meth) acrylates, and polyfunctional (eg, having 2 to 100 functional groups) polyols such as polyvinyl alcohols.

  Examples of the amino group-containing compound include monoamines, polyamines, alkanolamines and the like.

Specifically, in addition to those described in the first invention (reference invention) , polyamide polyamines obtained by condensation of dicarboxylic acids and excess polyamines; polyether polyamines; hydrazines (hydrazine, monoalkylhydrazine, etc.) , Dihydrazides (succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.), guanidines (butyl guanidine, 1-cyanoguanidine, etc.); dicyandiamide; and a mixture of two or more of these.

  Examples of the carboxyl group-containing compound include aliphatic monocarboxylic acids having 2 to 18 carbon atoms such as acetic acid and propionic acid; aromatic monocarboxylic acids having 6 to 18 carbon atoms such as benzoic acid; carbon numbers such as succinic acid and adipic acid. 4-18 aliphatic polycarboxylic acids; aromatic polycarboxylic acids having 8-18 carbon atoms such as phthalic acid, terephthalic acid, trimellitic acid; polycarboxylic acid polymers (functional) such as (co) polymers of acrylic acid Base number 2-100) etc. are mentioned.

  Examples of the polythiol compound of the thiol group-containing compound include 2 to 8 valent polyvalent thiols having 2 to 18 carbon atoms. Specific examples include ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 3-methylpentanedithiol, and the like.

  Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  Of these active hydrogen-containing compounds (k), a hydroxyl group-containing compound, an amino group-containing compound, and water are preferable, and water, alcohol, and amine are particularly preferable.

  In said formula (4), Z represents the C2-C12 alkylene group and cycloalkylene group which may be substituted by the halogen atom.

  Specifically, an ethylene group, a propylene group, a butylene group, a chloropropylene group, a bromopropylene group, a laurylene group, a phenylethylene group, a chlorophenylethylene group, a 1,2-cyclohexylene group, etc., and two or more of these A combination thereof is mentioned, and among these, a propylene group, a butylene group, and an ethylene group are preferable, and a propylene group and a butylene group are particularly preferable.

  In said formula (4), A represents the C3-C12 alkylene group and cycloalkylene group which may be substituted by the halogen atom.

  Specific examples include a propylene group, a butylene group, a chloropropylene group, a bromopropylene group, a laurylene group, a phenylethylene group, a chlorophenylethylene group, a 1,2-cyclohexylene group, and the like, and combinations of two or more thereof. It is done. From the viewpoint of the hydrophobicity of the resulting polyoxyalkylene polyol or monool, when an ethylene group is used, it is preferably used in combination with another alkylene group.

In this reference invention, it is a hydroxyl group-containing group located at the terminal of the groups represented by-(AO) q-H in the general formula (4) representing the polyoxyalkylene polyol or monool (j)- the AO-H groups, and primary hydroxyl group-containing group represented by the above general formula (5), there are two types of secondary hydroxyl group-containing group represented by the following general formula (5 '), the first 2 In (j) used in the invention (reference invention) , the primary hydroxyl group-containing group represented by the general formula (5) is 40% or more of all terminal hydroxyl groups in (j) (in the case of monool) Is 60% or more), preferably 65% or more, and more preferably 70% or more.

R < ² > in said general formula (5), (5 ') represents the C1-C10 alkyl group which may be substituted by the halogen atom, or a C6-C10 aryl group.

  Specifically, linear alkyl groups such as methyl group, ethyl group, and propyl group; branched alkyl groups such as isopropyl group; substituted phenyl groups such as phenyl group and p-methylphenyl group; chloromethyl group, bromomethyl group, chloroethyl Groups, substituted alkyl groups such as bromoethyl group; substituted phenyl groups such as p-chlorophenyl group and p-bromophenyl group, and combinations of two or more thereof.

  p is 0 or 1 or more, q is a number of 1 or more, and p + q is usually 1 to 200, preferably 1 to 100. p is usually a number from 0 to 199, preferably from 0 to 100, and q is usually a number from 1 to 200, preferably from 1 to 100.

  The polyoxyalkylene polyol or monool (j) is obtained by subjecting the active hydrogen-containing compound (k) to ring-opening addition polymerization of the heterocyclic compound (β) in the presence of the specific catalyst (α).

  The heterocyclic compound (β) is represented by the following general formula (13).

  In formula (13), R represents a C2-C5 alkylene group which may be substituted with a halogen atom or a hydrocarbon group. Q is —O—, —S—, —NH—, —OCOO—, —SCOO—, —OCSO—, —OCOS—, —OCSS—, —SCSO—, —SCOS—, —SCSS—, —COO—, A divalent organic group selected from the group consisting of —CSO—, —COS—, —CSS—, and —CONH—.

  Specific examples of the heterocyclic compound (β) include cyclic ethers such as EO, PO, BO, SO, oxetane and tetrahydrofuran; cyclic thioethers such as ethylene sulfide; imines such as ethyleneimine; cyclic carbonates such as ethylene carbonate Cyclic thiocarbonates such as ethylene thiocarbonate; cyclic dithiocarbonates such as ethylene dithiocarbonate; cyclic lactones such as ε-caprolactone; cyclic lactams such as ε-caprolactam.

  When (β) is added to the active hydrogen-containing compound (k) in the presence of (α) to obtain the above (j), the added mole number of (β) added is the activity of (k). The amount is usually 1 mol to 200 mol, preferably 1 to 100 mol per hydrogen, and is appropriately selected depending on the molecular weight of the hydroxyl group-containing compound to be produced and its application.

The type and use method of (α), reaction conditions, catalyst removal conditions, and the like are the same as in the first invention (reference invention) described above.

  The number-average molecular weight of the polyoxyalkylene polyol or monool (j) thus obtained (hereinafter abbreviated as Mn, hereinafter the same by gel permeation chromatograph) is usually 400 to 100,000, preferably 500 to It is 20000, and is appropriately selected depending on its use, for example, required physical properties such as a polyurethane resin to be produced.

  Specific examples of the polyoxyalkylene polyol or monool (j) include water PO adduct, methanol PO adduct, glycerin PO adduct, ammonia PO adduct, water BO adduct PO adduct, Examples thereof include a PO adduct of a methanol BO adduct, a PO adduct of a glycerin BO adduct, a PO adduct of an ammonia BO adduct, and the like.

The monohydroxy or polyhydroxy polyether of the second invention (reference invention) is obtained by adding EO to the terminal hydroxyl group of the polyoxyalkylene polyol or monool (j). The added mole number (x) of EO per hydroxyl group is 20 or less, preferably 15 or less.

When EO is ring-opened and added to the terminal hydroxyl group of (j) to obtain the polyether of the second invention (reference invention) , a catalyst may be used. As the catalyst, the same catalyst (α) as in the production of (j) from (k) may be used, or another catalyst may be used. Other catalysts include those similar to those in the first invention (reference invention) described above, and the amount used is also the same.

  When ring-opening addition of EO, the above-mentioned (j), EO and catalyst may be charged together and reacted, or EO is dropped into a mixture of (j) and the catalyst and reacted. Alternatively, EO and a catalyst may be added dropwise to (j) and reacted.

  From the viewpoint of controlling the reaction temperature, a method of dropping EO to the mixture of (j) and the catalyst, or dropping EO and the catalyst to (j) is preferable.

  The reaction temperature at the time of ring-opening addition of EO to the above (j) is usually 0 ° C to 250 ° C, preferably 20 ° C to 180 ° C.

The polyether of the second invention (reference invention) produced as described above can be purified in the same manner as in the above (j).

  The number of moles of EO added per hydroxyl group of the polyether (x) is 20 or less (preferably 15 or less) (requirement <1>), and the terminal hydroxyl group primary ratio (y) is 40% or more ( However, in the case of monool, it is 60% or more) (requirement <2>), preferably 65% or more, and more preferably 85% or more. Further, (x) and (y) can satisfy the relationship (requirement <3>) of the following equation (3), and more preferably satisfy the following equation (3 ').

x <= 5.5 * z-6.5 * Ln (z) -6.46 (3)
x <= 5.5 * z-6.5 * Ln (z) -7.85 (3 ')
(Z is 1.03-y / 100; Ln (z) is the natural logarithm of z.)

  When (x) satisfies the requirement <3>, the hydrophilicity of the polyether does not increase, the water resistance of the resin obtained by the reaction is good, and the reactivity is also good.

The Mn of the polyether of the second invention (reference invention) is preferably 400 to 100,000, more preferably 500 to 20000, and its use, for example, when a polyurethane resin is produced, the required physical properties of the polyurethane resin. Is appropriately selected.

Also preferred in the monohydroxy polyethers and polyhydroxy polyethers, from utility as a raw material, Ru polyhydroxy polyethers der.

By using a polyether that satisfies any one or more of the requirements of the first to third inventions (all of which are reference inventions) as a polyol component such as a polyurethane resin, a polyester resin, an epoxy resin, or an acrylic resin, this polyol The components are hydrophobic and highly reactive with isocyanates, carboxylic acids, and epoxies. That is, resins derived from polyethers of this reference invention has high reactivity during preparation, physical properties of the resin characteristics of low humidity dependence of (tensile strength, elongation at break, flexural strength, etc.). This resin can be used in various applications such as foams, elastomers, and coating materials. Examples of foams include automotive cushioning materials, sound-absorbing and sound-insulating materials, and handles. Examples of elastomers include cast potting materials. Examples of coating materials include adhesives and paints. It is also useful as a raw material for surfactant compositions such as fiber treatment oils, cleaning agents, and antifoaming agents.

<< Invention relating to resin-forming composition (reference invention) >>
The eighth invention (reference invention) relates to a resin-forming composition containing a novel polyether compound. In detail, it is related with the resin-forming composition containing the novel polyether compound which forms ester resin, urethane resin, an acrylic resin, etc. by reaction.

In the eighth invention (reference invention) , the polyol of the second invention (reference invention) is used as the polyether (K).

(K) is also preferably the polyol of the first invention (reference invention) .

In the eighth invention (reference invention) , the compound (L) reactive with the hydroxyl group of the polyether (K) is not particularly limited as long as it is a compound that reacts with (K) to form a stable bond. Examples thereof include polyisocyanates, polycarboxylic acids and acid halides thereof, acid anhydrides thereof, esters thereof (hereinafter referred to as polycarboxylic acids or ester-forming derivatives thereof), and epoxy group-containing compounds. Specific examples include the following.

(I) Polyisocyanate
<1> aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the carbon number in the NCO group);
1,3- and / or 1,4-phenylene diisocyanate, 2,4-, 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′-, 4,4′-diphenylmethane diisocyanate (MDI), Crude MDI, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5 -Naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, polyaryl polyisocyanate (PAPI) and the like;
<2> C2-C18 aliphatic polyisocyanate;
Ethylene diisocyanate, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, dodecane methylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, trimethylhexamethylene diisocyanate (TMDI), dimer acid Diisocyanate (DDI) and the like;
<3> C4-15 alicyclic polyisocyanate;
Isophorone diisocyanate (IPDI), dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate (H-MDI), cyclohexylene diisocyanate, hydrogenated tolylene diisocyanate (HTDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxyl Rate, 2,5- and / or 2,6-norbornane diisocyanate, etc .;
<4> aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms;
m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like;
<4> Modified product of the above polyisocyanate;
Examples of modified products include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretonimine groups, isocyanurate groups, oxazolidone group-containing modified products. / Or polymer polyol) adduct body [molar ratio of NCO / OH is preferably 1.01 to 10/1, more preferably 1.1 to 5/1. For example, 1 mol of trimethylolpropane and the above-mentioned diisocyanate 3 Molar adducts, pentaerythritol and 4 moles of the above diisocyanates, etc .;
<5> NCO-terminated urethane prepolymer;
The weight average molecular weight (hereinafter abbreviated as Mw, the same applies hereinafter by gel permeation chromatograph) is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and NCO groups in one molecule. Is preferably 1.5 or more on average, more preferably 1.5 to 5, and is produced under the same conditions by a urethanization reaction of the low-molecular polyol or high-molecular polyol described above with the above polyisocyanate. NCO-terminated urethane prepolymer;
<6> diisocyanate polymer;
Isocyanurates of polyisocyanates (trimers, pentamers), burettes of diisocyanates (trimers, pentamers) and the like;
Etc. These may be used in combination of two or more. Of these, preferred are TDI, MDI, XDI and TMXDI, and particularly preferred are MDI and TDI.

(II) Polycarboxylic acid or its ester-forming derivative
(i) Examples of the polycarboxylic acid include saturated carboxylic acids having 4 to 30, 2 to 8 or more carbon atoms, and specifically include the following compounds.

<1> saturated carboxylic acid;
Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid; aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid;
<2> a polycarboxylic acid having a polymerizable unsaturated group;
Polycarboxylic acids having polymerizable unsaturated groups such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid;
Etc. Of these, aromatic polycarboxylic acids and polycarboxylic acids having a polymerizable unsaturated group are preferred.

  (ii) Examples of polycarboxylic acid halides include acid chlorides, bromides, fluorides, and iodides of the above polycarboxylic acids, such as maleic acid chloride, itaconic acid chloride, fumaric acid bromide, and citraconic acid chloride. Thing etc. are mentioned.

  (iii) Examples of acid anhydrides of polycarboxylic acids include maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, hexabromophthalic anhydride, hymic anhydride, het anhydride, Examples include endomethylenetetrahydrophthalic anhydride.

  (iv) Examples of polycarboxylic acid esters include lower alkyl esters having 1 to 4 carbon atoms (such as methyl ester, ethyl ester, propyl ester, and butyl ester) of the above polycarboxylic acid.

(III) Epoxy group-containing compound The epoxy group-containing compound includes a monoepoxide (III-1) and a polyepoxide (III-2) containing two or more epoxy groups in the molecule.

  (III-1) is not particularly limited as long as it is a compound having one epoxy group in the molecule, and can be appropriately selected according to the use and purpose. Examples thereof include the following (III-1-1) to (III-1-2).

(III-1-1) C2-C24 hydrocarbon oxide (ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, vinylcyclohexene oxide, C5-C24 α-olefin oxide, styrene oxide etc);
(III-1-2) C 3-19 hydrocarbon glycidyl ether (n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl Glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, etc.);
(III-1-3) Glycidyl esters of monocarboxylic acids having 3 to 30 carbon atoms (such as glycidyl (meth) acrylate), epihalohydrins such as epichlorohydrin and epibromohydrin, and hydroxyl-containing oxides such as glycidol;
Is mentioned.

(III-2) is not particularly limited as long as it is a resin having two or more epoxy groups in the molecule, and can be appropriately selected according to the application and purpose. Examples of polyepoxides include the following (
III-2-1) to (III-2-5).

(III-2-1) Glycidyl ether type
(i) diglycidyl ethers of dihydric phenols;
Diglycidyl ethers of dihydric phenols having 6 to 30 carbon atoms, for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A Diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'- Dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9 '-Bis (4-hydroxyphenyl) furorange glycidyl ether, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, etc .;
(ii) a polyglycidyl ether of a trihydric to hexavalent or higher polyhydric phenol;
Polyglycidyl ether of polyhydric phenols having 6 to 50 or more carbon atoms and Mn of 110 to 3,000, such as pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (Hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl Ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) Phenyl glycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin (Mn: 400 to 3,000), glycidyl ether of limonene phenol novolac resin (Mn: 400 to 3,000), phenol and Polyglycidyl ether of polyphenol (Mn: 400 to 3,000) obtained by the condensation reaction of glioxal, glutaraldehyde, or formaldehyde, and polyphenol of Mn: 400 to 3,000 obtained by the condensation reaction of resorcin and acetone Polyglycidyl ether, etc .;
(iii) diglycidyl ether of an aliphatic dihydric alcohol;
Diglycidyl ether of diol having 2 to 100 carbon atoms and Mn: 62 to 3,000, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Polyethylene glycol (Mn: 150-3,000) diglycidyl ether, polypropylene glycol (Mn: 180-3,000) diglycidyl ether, polytetramethylene ether glycol (Mn: 200-3,000) diglycidyl ether, neopentyl Glycol diglycidyl ether, diglycidyl ether of AO [EO or PO (1 to 20 mol)] adduct of bisphenol A, and the like;
(iv) polyglycidyl ethers of trihydric to hexahydric or higher aliphatic alcohols; trihydric to hexahydric or higher polyhydric alcohols having 3 to 50 or more carbon atoms and Mn: 76 to 3,000 Glycidyl ethers such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly (n = 2-5) glycerol polyglycidyl ether, etc .;
(III-2-2) Glycidyl ester type; glycidyl ester of aromatic polycarboxylic acid having 6 to 20 or more carbon atoms, divalent to 6 or more carbon atoms, and 6 to 20 or more carbon atoms, A glycidyl ester of a divalent to hexavalent or higher aliphatic or alicyclic polycarboxylic acid;
(i) Aromatic polycarboxylic acids such as glycidyl esters of phthalic acids include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, trimellitic acid triglycidyl ester and the like;
(ii) As the glycidyl ester of the aliphatic or alicyclic polycarboxylic acid, aromatic phenol water additive of the above-mentioned phenolic glycidyl ester, dimer acid diglycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl ester Succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (co) polymer of glycidyl (meth) acrylate (degree of polymerization 2 to 10), tricarbyl acid triglycidyl ester, etc .;
(III-2-3) Glycidylamine type: Glycidylamine and aliphatic, alicyclic or heterocyclic ring of aromatic amines having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms Formula amines such as glycidylamine
(i) As glycidylamines of aromatic amines, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′ , N′-tetraglycidyldiaminodiphenylsulfone, N, N, N ′, N′-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like;
(ii) Examples of glycidylamines of aliphatic amines include N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidylhexamethylenediamine and the like;
(iii) As glycidylamines of alicyclic amines, hydrogenated compounds of N, N, N ′, N′-tetraglycidylxylylenediamine and the like; As glycidylamines of heterocyclic amines, trisglycidylmelamine and the like;
(III-2-4) Aliphatic epoxide; aliphatic epoxide having 6 to 50 or more carbon atoms and 2 to 6 or more valences, for example, epoxidized polybutadiene having an epoxy equivalent of 130 to 1,000 (Mn: 170 to 3) , 000), epoxidized soybean oil (Mn: 170-3000), etc .;
(III-2-5) alicyclic epoxide; alicyclic epoxide having 6 to 50 or more carbon atoms, Mn: 98 to 3,000, and 2 to 4 or more epoxy groups, for example, vinylcyclohexene Oxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis ( 3,4-epoxy-6-methylcyclohexylmethyl) butylamine and the like; nuclear hydrogenated products of the epoxy compounds of the phenols;
Any epoxy resin having a glycidyl group capable of reacting with active hydrogen can be used other than (III-2-1) to (III-2-5). These polyepoxides and monoepoxides can be used in combination of two or more.

  Of these, preferred are polyepoxides, diglycidyl ethers of dihydric phenols (6 to 30 carbon atoms), polyglycidyl ethers of 3 to 6 or more polyhydric phenols (6 to 50 carbon atoms). Particularly preferred are diglycidyl ethers of dihydric phenols (6 to 30 carbon atoms).

Resin-forming composition of this reference invention is a composition comprising a polyether compound (K) and the compound capable of reacting with the hydroxyl groups to form a stable bond (L), other components as required (M) may be added. (M) is not particularly limited as long as it reacts with the hydroxyl group of (K) or the functional group of (L). For example, low molecular weight polyol (N) and / or vinyl monomer (O) are preferred. It is done.

  Examples of (N) include the same as (K) above, for example, a diol having an Mn of less than 600, specifically, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, neopentyl glycol. And alkylene glycols such as cyclohexanedimethanol; polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polyester diols such as polyethylene adipate, polybutadiene adipate, and polycaprolactone.

Examples of (O) include vinyl aromatic compounds such as styrene, methyl styrene, vinyl toluene, trimethyl styrene, halogenated styrene, t-butyl styrene, styrene sulfonate, aminostyrene, p-benzyl styrene, and p-phenoxy styrene; Esters of acrylic acid or methacrylic acid with aliphatic alcohols such as methanol, ethanol, propanol, octanol, hexanol, tetrahydrofurfuryl alcohol, ethylene glycol, propylene glycol; amino such as 2-aminoethyl methacrylate and N, N-diethylaminoacrylate Group-containing acrylic acid or methacrylic acid ester; hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol monoacrylate, tripropylene Acrylates such as recall monoacrylate and trimethylolpropane diacrylate; hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, diethylene glycol monomethacrylate, polyethylene (degree of polymerization = 1-100) glycol monomethacrylate, penta Compounds having 1 to 4 or more hydroxyl groups and 1 to 4 or more polymerizable unsaturated groups in the molecule such as erythritol trimethacrylate;
Α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid or their anhydrides, esters, amides, imides; fumaric acid esters such as diethyl fumarate and dioctyl fumarate; acrylonitrile, methacrylate Ronitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinylene carbonate, vinyl-2-chloroethyl ether, alkyl vinyl ether, aliphatic vinyl ester, 2-vinyl furan, vinyl phenol, vinyl phenyl disiloxane, 2-vinyl pyridine, 4 -Vinyl monomers such as vinylpyridine, vinylpyrrole, vinylpyrrolidone, vinylsulfonic acid, vinylurethane, vinylcarbazole; 1,3-butadiene, isoprene, piperylene, methylpentadiene, chloroprene, 2-methoxy Conjugated diene compounds such as butadiene and 1-cyanobutadiene and derivatives thereof; diallyl maleate, diallyl phthalate, divinylbenzene, divinyl ether, neopentyl glycol diacrylate, diallyl cyanurate, triallyl cyanurate, diallylphenyl phosphate, 2 And polyfunctional vinyl monomers such as 3-jovinylpyridine.

This reference invention combines the above (K) and (L) to form a resin-forming composition, and further combines (M) as necessary. The combination is not limited, but the following combinations [i] to [viii] are preferable.

  [I]: a combination in which (K) is a high molecular weight polyol, (L) is a compound selected from aromatic polycarboxylic acids and derivatives thereof, and a low molecular weight polyol is added as (M) as necessary. Can do.

  [Ii]: (K) is a polyol, and (L) is a compound selected from polycarboxylic acids having a polymerizable unsaturated group and derivatives thereof, and if necessary, a vinyl monomer as (M) Can be added.

[Iii]: A combination in which (K) is a divalent to octavalent polyol and (L) is a divalent to octavalent polyisocyanate;
[Iv]: A combination in which (K) is a high molecular weight polyol and (L) is a polyisocyanate, and a low molecular weight polyol can be added as (M) if necessary. ;
[V]: a combination in which (K) is a polyol and (L) is a compound selected from a monocarboxylic acid having a polymerizable unsaturated group and a derivative thereof, and a monool is added as (M) if necessary It is preferable. ;
[Vi]: (K) is a polyol, (L) is a compound selected from polycarboxylic acids and derivatives thereof, and (M) is 1 to 4 or more hydroxyl groups and 1 to 4 in the molecule. Or a combination which is a compound having more polymerizable unsaturated groups;
[Vii]: (K) is a polyol, (L) is a polyisocyanate, (M) is 1 to 4 or more hydroxyl groups and 1 to 4 or more polymerizable unsaturations in the molecule. A combination which is a compound having a group;
[Viii]: A combination in which (K) is a di- to 8-functional polyol and (L) is an epoxy group-containing compound (III) .

  Combination [ii] is a resin-forming composition that reacts to form an unsaturated polyester. The polyol (K) is preferably a diol having a Mn of 700 to 5,000, and more preferably a polyoxyalkylene glycol having a Mn of 1,000 to 3,000. The polycarboxylic acid having a polymerizable unsaturated group (L) and derivatives thereof are preferably dicarboxylic acids having a polymerizable unsaturated group and derivatives thereof, more preferably maleic acid, itaconic acid or citraconic acid and derivatives thereof. Derivatives, particularly preferably maleic acid, itaconic acid or citraconic acid anhydride. The amount of (L) is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, based on the total mass of (K) and (L).

  In the case of the combination [ii], if necessary, a condensation catalyst, monool and aliphatic saturated polycarboxylic acid are added to obtain an unsaturated polyester polycondensate. Examples of the condensation catalyst, monool, and aliphatic saturated polycarboxylic acid are the same as in the case of the combination [i].

  The blending ratio of each component is preferably 0 to 1% by mass of the condensation catalyst, more preferably 0.01 to 0.1% by mass, and preferably 0 to 20% of monool based on the whole unsaturated polyester polycondensate. The mass%, more preferably 1 to 10 mass%, and the aliphatic saturated dicarboxylic acid is preferably 0 to 50 mass%, more preferably 1 to 20 mass%.

  An unsaturated polyester resin-forming composition can be obtained by further blending the vinyl monomer (O) and a polymerization initiation catalyst, if necessary, with the resin-forming composition of the combination [ii]. (O) is preferably styrene, vinyltoluene, α-methylstyrene, chlorostyrene, divinylbenzene, methyl methacrylate, methyl acrylate, diallyl phthalate, or triallyl cyanurate. The blending ratio of (O) is preferably 10 to 80% by mass and more preferably 20 to 70% by mass with respect to the mass of the entire resin-forming composition.

As the polymerization initiation catalyst, usual radical polymerization initiators such as organic peroxides, organic hydroperoxides, and azo compounds are used. Specifically,
(1) Organic peroxide Dialkylyl peroxide, di-t-butyl peroxide, alkyl peroxide such as t-butylcumyl peroxide; dilauroyl peroxide, dibenzoyl peroxide, dicetyl peroxide, didecanoyl peroxide Diacyl peroxides such as oxide and diisononanoyl peroxide; peracid esters such as t-butyl peroctoate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, and cyclohexanone peroxide;
(2) Organic hydroperoxide t-butyl hydroperoxide, cumyl hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, p-methane hydroperoxide, diisopropylbenzene hydroperoxide, etc .;
(3) Azo compound Diazoaminobenzene, N, N′-dichloroazodicarboxylic acid amide, azodicarboxylic acid diethyl ester, 1-cyano-1- (t-butylazo) cyclohexanone, azobis (isobutyronitrile) and the like;
Etc. Of these, organic peroxides are preferable, and t-butyl peroxybenzoate is more preferable. The blending ratio of the polymerization initiation catalyst is preferably 0.1 to 15% by mass, more preferably 0.5 to 5% by mass with respect to the mass of the entire resin-forming composition.

  In addition, aromatic or aliphatic saturated dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, pimelic acid; monobasic acid, polybasic acid of 3 or more bases Modifiers such as monohydric alcohols, trihydric or higher polyhydric alcohols; low shrinkage agents such as polystyrene, polyacrylate, polyvinyl acetate, polycarbonate; thickeners such as magnesium hydroxide, calcium oxide, barium hydroxide, zinc oxide Agent: Fiber reinforcing agent such as glass, metal, silicate, asbestos, carbon, polyester, polyamide, etc .; Inorganic filler; Pigment such as titanium oxide, carbon black, phthalocyanine; Lubricant or mold release such as aluminum stearate, calcium stearate Agents; Stabilizers such as barium soap, stannous octoate, BHT; Coupling agents, it may be added an additive such as a flame retardant. The blending ratio of each component is preferably 0 to 30% by mass, more preferably 0.5 to 10% by mass, and the low shrinkage agent is preferably 0 to 70% by mass with respect to the entire resin-forming composition. More preferably 1 to 20% by mass; the thickener is preferably 0 to 10% by mass, more preferably 0.5 to 5% by mass; the fiber reinforcing agent is preferably 0 to 60% by mass, and more preferably. 10 to 50% by mass; the inorganic filler is preferably 0 to 80% by mass, more preferably 10 to 50% by mass; the lubricant or mold release agent, stabilizer, silane coupling agent, and flame retardant are preferably in total mass It is 0-30 mass%, More preferably, it is 1-20 mass%.

  The production method of the unsaturated polyester resin-forming composition of the combination [ii] is not particularly limited. For example, the raw materials constituting the combination of [ii] are first stirred in a reaction vessel, preferably 80 to 250 ° C. More preferably, it is heated to 100 to 230 ° C. for 3 to 10 hours to obtain a polycondensate by dehydration reaction. At this time, a modifying agent may coexist. The reaction end point can be checked by the acid value and the hydroxyl value. Then, the method of mixing the said additive with this polycondensate is mentioned. As a mixing method, a first mixture in which a polycondensate and a vinyl monomer are mixed, and a second mixture is prepared by mixing a low shrinkage agent and a vinyl monomer, and one or both of them are hardeners. If necessary, the additive is mixed, and the first mixture and the second mixture are further mixed.

  The unsaturated polyester resin-forming composition thus obtained can be molded into a cured product by a method such as compression molding or injection molding through an intermediate compound such as SMC or BMC. The cured product is used for automobile parts, transport equipment such as boats, construction equipment such as bathtubs and septic tanks, chairs and other industrial goods.

  The combination [iii] is a cast urethane resin, preferably a combination of a divalent to tetravalent polyol (K) and preferably a divalent to tetravalent polyisocyanate (L). (L) is more preferably TDI, MDI, XDI, TMXDI, and particularly preferably MDI and TDI. The blending ratio of (K) and (L) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass with respect to the total mass of (K) and (L).

  In the case of the combination [iii], if necessary, a high-molecular diol other than polyether, monool, a low molecular weight polyol (urethane curing agent) having a molecular weight of 62 to 400, a urethane-forming catalyst, and a cast urethane resin-forming composition. Things are obtained. Further, if necessary, a filler, a plasticizer, an antioxidant, an ultraviolet absorber and the like can be blended.

  Examples of polymer diols other than polyether include diols of Mn: 600 to 4000, for example, one or more alkylene glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and adipic acid, Polycondensates of one or more alkylene dicarboxylic acids such as suberic acid and sebacic acid; lactone polyols such as polypropiolactone polyol, polycaprolactone polyol, and polyvalerolactone polyol obtained by ring-opening polymerization of lactone; polycarbonate Etc. Monools include those mentioned above.

  As the low molecular weight polyol (urethane curing agent) having a molecular weight of 62 to 400, 1,4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,6-hexane among the above (N) Dihydric alcohols such as diol, dipropylene glycol, 3-methyl-1,5-pentanediol; trimethylolpropane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, Examples include trivalent or higher alcohols such as diglycerin and pentaerythritol; amine-containing polyhydric alcohols such as triethanolamine, triisopropanolamine, and diisopropanolamine.

  Examples of urethanization-promoting catalysts include tin-based catalysts such as trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate; lead oleate, 2- Lead catalysts such as lead ethylhexanoate, lead naphthenate, lead octenoate; naphthenic acid metal salts such as cobalt naphthenate, phenylmercurypropionate, etc .; triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diaza Bicycloalkenes; dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, 2- (1- Dilydinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine, and other amine-based catalysts and organic acid salts (formate, etc.) ) Etc .; and combinations of two or more of these. The blending ratio of the urethanization accelerating catalyst used in the present invention is preferably 0 to 10% by mass, more preferably 0.01 to 5% by mass, based on the entire cast urethane resin-forming composition.

  Examples of the filler include clay, heavy calcium carbonate, fatty acid-treated calcium carbonate, barium sulfate, alumina, silica, carbon black, calcium oxide, titanium oxide, diatomaceous earth, glass fiber and crushed materials thereof (cut glass, Milled glass, glass flakes, etc.), Shirasu balloon, carbon fiber, potassium titanate, boron fiber, gypsum fiber, talc, mica, wollastonite, calcium silicate, chalk, glass beads, quartz and the like. The blending ratio of the filler is preferably 5 to 50% by mass and more preferably 10 to 30% by mass with respect to the entire cast urethane resin-forming composition.

  Examples of the plasticizer include ester plasticizers [dibutyl phthalate, dioctyl phthalate, dioctyl adipate, polyethylene glycol (Mn: 200) diadipate, etc.]; tar plasticizers (tar, asphalt, etc.); petroleum resin plasticizers. The blending ratio of the plasticizer is preferably 5 to 70% by mass, and more preferably 15 to 50% by mass.

  Antioxidants include hindered phenol antioxidants [Irganox 1010 (Ciba Geigy), Octadecyl-3- (3,5-di-t-butyl-4hydroxyphenyl) propionate (Irganox 1076, Ciba Geigy). Etc.], hindered amine antioxidants [Sanol LS770 (manufactured by Ciba Geigy), 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine (Sankyo sanol LS-744)] and the like. The blending ratio of the antioxidant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

  Examples of ultraviolet absorbers include triazole ultraviolet absorbers [2- (5-methyl-2-hydroxyphenyl) benzotriazole, tinuvin 320 (manufactured by Ciba Geigy), etc.], benzophenone ultraviolet absorbers [2-hydroxy-4-methoxy Benzophenone, Siasorb UV9 (manufactured by Cyanamid Co., Ltd.), etc.]. The blending ratio of the ultraviolet absorber is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

The method for producing the cast urethane resin is not particularly limited. For example, (K) and excess polyisocyanate, and if necessary, high molecular weight diol other than (K) are preferably 50 to 120 ° C., more preferably 70 to 100. After making a prepolymer of terminal isocyanate by reacting at a temperature of ° C., this prepolymer and a low molecular weight diol, if necessary, the above-mentioned monool, additional diol, high molecular weight diol other than polyether, filler, plasticizer, The method of making it react with antioxidant, a ultraviolet absorber, etc. is mentioned. The reaction with the polyisocyanate is, for example, a method in which each component is metered and stirred; and metered with a metering pump, and after intensely mixing and stirring, it is poured onto a vat and further, for example, preferably 80 to 200 ° C. Preferably, it can be produced by a method of reacting at a temperature of 120 to 160 ° C. and pulverizing. Further, for example, the above raw material is preferably supplied to an extruder set at 80 to 260 ° C., more preferably 120 to 250 ° C., polymerization is performed while kneading and conveying the raw material in the extruder, and the method is extruded from a die. Ru can be produced.

<Invention concerning rigid polyurethane foam>
Next, the fourth, fifth, ninth, tenth and sixteenth aspects of the rigid polyurethane foam will be described.

  The hydroxyl value in the present invention is the usual mg of KOH equivalent to neutralizing 1 g of a sample and means 56100 / molecular weight per hydroxyl group.

  Further, the active hydrogen value means 56100 / molecular weight per active hydrogen-containing group, and in the above-mentioned invention (b), it means the sum of the hydroxyl value and the primary and secondary amine values.

  The active hydrogen compound (b) used in the fourth, fifth, ninth and tenth inventions is an active hydrogen compound having a structure in which AO is added to amines.

Examples of the amines include those exemplified in the first invention (reference invention) .

  These amines may be used in combination of two or more, preferably aliphatic amines and aromatic amines.

  AO to be added to the amines is preferably one having 2 to 8 carbon atoms, such as EO, PO, 1,2-, 1,3-, 1,4- and 2,3-BO, SO, and these Or a combination of two or more (block and / or random addition). Preferable is PO and a combination of PO and EO.

  Two or more active hydrogen compounds (b) may be used in combination, and the active hydrogen value (average) is usually 200 or more, preferably 250 to 1300, more preferably 300 to 1000. When the active hydrogen value is less than 200, the curability deteriorates and the swelling at the time of demolding is large. In particular, when the active hydrogen value is 300 to 1000, the curability of the foam is excellent, the swelling during demolding is small, and the foam strength is high.

  In the polyether polyol (a) used in the fourth, fifth, ninth and tenth inventions, 1 or more moles of 1,2-AO having 3 or more carbon atoms per mole of primary OH group is added to polyhydric alcohol. And / or one or more polyether polyols obtained by further adding EO to the polyol. The hydroxyl value (average) is usually 200 or more, preferably 250 to 1300, more preferably 300 to 1000. When the hydroxyl value is less than 200, the foam swells when demolded and the foam strength is low.

The average addition mole number x of active hydrogen per one EO of (a) is usually 2 or less, primary OH ratio y is Ru der usually 40% or more.

x is preferably 0.01 to 1.9, more preferably 0.1 to 1.8 Ru der.

When x and y are within the above normal range, the curability is good, and the foam at the time of demolding does not swell and the foam strength does not decrease. When x and y are within the above preferred ranges, the curability is particularly excellent, the swelling during demolding is small, and the foam strength is high.

Moreover, what satisfies the relationship of the expression (3) of requirement <3> in the second invention (reference invention) is preferable.

Examples of the polyhydric alcohol used to obtain (a) include those exemplified in the first invention (reference invention) .

Examples of 1,2-AO having 3 or more carbon atoms to be added to polyhydric alcohol by 1 mol or more per primary OH group include those exemplified in the first invention (reference invention) , preferably PO. is there.

Specific examples of (a) include those of the additional format described in the first invention (reference invention) . These may be used in combination.

  (A) usually has an average of 2 to 8, preferably an average of 2.5 to 8 hydroxyl groups from the viewpoint of curing speed and viscosity.

  (A1) used in the fourth and ninth inventions further includes a polyether polyol obtained by adding (A) one or more moles of AO having 3 or more carbon atoms per mole of primary OH group to a polyhydric alcohol. This is a case of a polyether polyol to which EO is added.

  In the fifth and tenth inventions, in order to ensure curability, together with (a), an active hydrogen compound (b) having an active hydrogen value of 200 or more obtained by adding AO having 2 or more carbon atoms to amines is used in combination. However, (b) is not necessarily required in the fourth and ninth inventions. This is because (a1) to be used contains an EO unit, so the compatibility with the organic polyisocyanate (B) is good, and the curability is good even without using (b).

  Among polyether polyols in which only EO is added to polyhydric alcohol, the average added mole number x of EO per active hydrogen and the primary OH conversion rate may be within the above ranges. However, in this case, although curability is good, problems such as large swelling at the time of demolding and low foam strength occur.

As a method of obtaining (a) and (a1), in the presence of the specific catalyst (α) described in the first invention (reference invention) in the polyhydric alcohol, the carbon number of 3 or more is obtained in the same manner. Examples include a method of adding 1,2-AO and further adding EO if necessary. The case where EO is added is (a1), and a polyol obtained by the same method as the polyether polyol of the first invention (reference invention) is used.

  In the active hydrogen compound (A) used in the production method of the ninth or tenth invention, in addition to (a) and (b) or (a1), if necessary, another polyol or monool (e) is used in combination. You can also

  Examples of (e) include polyether polyols, polyester polyols, modified polyols or monools, polyhydric alcohols, amines, and mixtures thereof other than (a) and (b). The preferred number of hydroxyl groups and hydroxyl value of (e) are the same as in (a).

  Examples of polyether polyols include AO adducts of active hydrogen compounds (polyhydric alcohols, amines, polyhydric phenols, polycarboxylic acids, etc.) that do not fall under any of (a) and (b). It is done.

  Examples of the polyhydric alcohol, amines, polyhydric phenol and polycarboxylic acid include those described above in the first invention (reference invention).

  Examples of AO added to the active hydrogen-containing compound include those exemplified as AO added to the amines.

  Examples of the polyester polyol include the above polyols (particularly, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; Polyols; or mixtures thereof with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane) and the above polycarboxylic acids or their anhydrides, lower alkyl (carbon number of alkyl group: 1 to 4) ester. An ester-forming derivative such as adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, or the like, or a condensation reaction product of the carboxylic anhydride and AO; , PO, etc.) addition reaction product; Ton polyols, such as those obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) using the polyol as an initiator; polycarbonate polyols, such as a reaction product of the polyol and a carbonic acid diester of a lower alcohol (such as methanol); Is mentioned.

  The modified polyol or monool is a polymer polyol, that is, a polymer obtained by polymerizing and stably dispersing a vinyl monomer such as acrylonitrile or styrene in the presence of a radical polymerization initiator in at least one of the above polyols; Polydiene polyols and hydrogenated products thereof; Hydroxyl-containing vinyl polymers such as acrylic polyols; Natural oil-based polyols such as castor oil; Modified products of natural oil-based polyols; Terminal radical polymerization described in EP 1 006 133 Active functional group-containing active hydrogen compounds (described in detail in the section of flexible polyurethane); and the like.

  Examples of the polyhydric alcohol and amines include those described above.

  In the fifth and tenth inventions, the content of (b) based on the sum of (a) and (b) in the active hydrogen compound (A) is preferably 5 to 80% by mass, more preferably 10 to 10% by mass. It is 75 mass%, Most preferably, it is 20-70 mass%. When (b) is within the above range, the curability is excellent and the demolding property is also good.

  Moreover, the ratio of (e) in (A) 100 parts by mass is usually 70 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

As the organic polyisocyanate (B) used in the ninth and tenth inventions, those conventionally used for polyurethane foams can be used. For example, the organic polyisocyanate (B) exemplified in the eighth invention (reference invention) relating to the resin composition described above can be used. The thing which was done is mentioned.

  Preferred as (B) is one or more organic polyisocyanates selected from TDI, MDI, crude TDI, crude MDI, sucrose-modified TDI, urethane-modified MDI, and carbodiimide-modified MDI.

  The isocyanate index [(NCO group / active hydrogen atom-containing group equivalent ratio × 100)] in the production of the polyurethane foam is usually 70 to 800, preferably 90 to 600, and more preferably 95 to 300. Moreover, when not forming an isocyanurate foam, it is 95-115 especially preferably.

  As the foaming agent (C), it is preferable to use water. When only water is used alone in (C), the amount of water used is usually 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass per 100 parts by mass of (A). The amount of water used in combination with other foaming agents is preferably 0.1 to 10 parts by mass.

  In addition, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, liquefied carbon dioxide, etc. are used as necessary.

  Specific examples of the hydrogen atom-containing halogenated hydrocarbon foaming agent include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCFC-141b, HCFC-22, and HCFC-142b); HFC (hydrofluorocarbon) type (For example, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc).

  Among these, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc and a mixture of two or more thereof are preferred.

  The amount of hydrogen atom-containing halogenated hydrocarbon used is preferably 50 parts by mass or less, more preferably 5 to 45 parts by mass per 100 parts by mass of (A).

  The low boiling point hydrocarbon is usually a hydrocarbon having a boiling point of −5 to 50 ° C., and specific examples thereof include butane, pentane, cyclopentane, and mixtures thereof.

  The amount of low-boiling hydrocarbons used is preferably 40 parts by mass or less, more preferably 5 to 30 parts by mass per 100 parts by mass of (A).

  The amount of liquefied carbon dioxide used is preferably 30 parts by mass or less, more preferably 25 parts by mass or less per 100 parts by mass of (A).

The urethanization catalyst (D) used in the ninth and tenth inventions is a catalyst usually used for polyurethane reaction, for example, an amine catalyst [triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ', N'-tetramethylhexamethylenediamine, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7, bis (dimethylaminoethyl) ether (carboxylate) And / or metal catalysts (stannic octylate, dibutylstannic dilaurate, lead octylate, etc.) can be used. Further, the catalyst described in the eighth invention (reference invention) and the catalyst described in the section of the flexible polyurethane foam described later can also be used. The amount of the catalyst used is preferably 0.001 to 6 parts by mass per 100 parts by mass in total of (A).

  In the production methods of the ninth and tenth inventions, a commonly used additive (E) can be used as necessary.

(E) includes foam stabilizers (dimethylsiloxane foam stabilizers, polyether-modified dimethylsiloxane foam stabilizers, etc.); antioxidants (hindered phenols, hindered amines, etc.) and ultraviolet rays Anti-aging agent such as absorbent (triazole, benzophenone, etc.); inorganic salt (calcium carbonate, silica, barium sulfate, etc.), inorganic fiber (glass fiber, carbon fiber, ceramic fiber, etc.), whisker (potassium titanate whisker) Flame retardants (phosphate esters, halogenated phosphate esters, etc.); plasticizers (phthalates, etc.); adhesives (modified polycaprolactone polyols, etc.); colorants (dyes, dyes, etc.) pigment); antimicrobials; antifungal agents; polymerization inhibitor; radical polymerization initiator (azo compounds, such as peroxides eighth Akira such as those exemplified in (Reference Invention)); a chain transfer agent (such as alkyl mercaptans), and the like.

  Specific examples of the foam stabilizer (E1) include, for example, “SZ-1142”, “L-520”, “L-540”, “SZ-1105”, “L-5740M” and “L” as trade names. -5740S "(manufactured by Nihon Unicar)," SH-190 "," SH-193 "," SF-2936F "and" SRX-294A "(manufactured by Toray Dow Corning Silicone). Dimethylsiloxane-based foam stabilizer.

  (A) Regarding the usage-amount of these additives with respect to 100 mass parts, a foam stabilizer becomes like this. Preferably it is 10 mass parts or less, More preferably, it is 0.2-5 mass parts. The anti-aging agent is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. A flame retardant becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 1-15 mass parts. The plasticizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The above additives other than these are preferably 1 part by mass or less.

  An example of a method for producing a rigid polyurethane foam by the methods of the ninth and tenth inventions is as follows. First, (A), (C), (D) and, if necessary, an additive (E) such as a foam stabilizer (E1) are mixed in a predetermined amount. The mixture is then rapidly mixed with the organic polyisocyanate (B) using a polyurethane low pressure or high pressure injection foamer or stirrer. The obtained mixed solution (foaming stock solution) is poured into a sealed or open mold (made of metal or resin), subjected to urethanization reaction, cured for a predetermined time, and then demolded to obtain a rigid polyurethane foam. A polyurethane foam can also be obtained by spray foaming or continuous foaming.

The rigid polyurethane foams produced by the methods of the ninth and tenth inventions are excellent in curability, have low swelling during demolding, and have high foam strength, so that they are for civil engineering (building materials), transportation equipment, and home appliances. heat insulating material of use, Ru can be widely used as a structural material.

<< Invention on flexible polyurethane foam (reference invention) >>
Next, the thirteenth, fourteenth and eighteenth inventions (all of which are reference inventions) relating to the flexible polyurethane foam will be described.

In the thirteenth and fourteenth inventions (both are reference inventions) , the polyol (A1) comprises a polyether polyol (f1) and / or a polymer polyol. The polymer polyol means a polymer polyol obtained by polymerizing a vinyl monomer in the polyether polyol (f2). When (f1) and the polymer polyol are used in combination, (f1) and (f2) may be the same or different.

  As (f1) and (f2), a compound obtained by adding AO to an active hydrogen compound can be used.

  As the active hydrogen compound, the polyhydric alcohols, amines and the like can be used.

  The active hydrogen compound is preferably divalent or higher, but a monohydric alcohol or a monovalent amine can also be used in combination as part of the active hydrogen compound. As monohydric alcohol, C1-C20 monohydric alcohol, for example, methanol, ethanol, butanol, 2-ethylhexyl alcohol, decyl alcohol, etc. are mentioned. Examples of the monovalent amine include monovalent amines having 2 to 20 carbon atoms such as dimethylamine, diethylamine, methylethylamine, methylpropylamine, and dipropylamine.

  Preferred as the active hydrogen compound is a polyhydric alcohol, more preferably a dihydric or trihydric alcohol, and particularly preferably a trihydric alcohol.

As AO, PO, 1,2- or 2,3-BO, SO, an α-olefin oxide having 5 to 20 carbon atoms, and the like can be used alone or in combination. Furthermore, you may use EO together with these. Of these, preferred are PO, 1,2-BO, and a combination of these and EO, more preferred is a combination of PO and PO and EO, and particularly preferred is a combination of PO and EO. In the case of combined use, the addition format may be either block or random. A block is particularly preferable as the addition type, and a terminal EO block modified product of the PO adduct is preferred. The case where EO is used in combination corresponds to the polyether polyol of the third invention (reference invention) or the first invention (reference invention) .

  The amount of EO used is preferably 30% by mass or less, more preferably 0.1 to 20% by mass, and particularly preferably 1 to 15% by mass based on the total mass of AO to be used. It is preferable that at least one of (f1) or (f2) is a terminal EO adduct.

  When the amount of EO used is 30% by mass or less, the cells are less likely to become closed cells when foaming polyurethane foam, and a better foam tends to be obtained.

  The hydroxyl value of (f1) is preferably 15 to 40 mgKOH / g, more preferably 20 to 38 mgKOH / g. When the hydroxyl value is 15 mgKOH / g or more, the viscosity does not increase and the handling workability is good, and when the hydroxyl value is 40 mgKOH / g or less, the resilience modulus of the resulting polyurethane foam is improved.

  The average number of hydroxyl groups per molecule of (f1) is preferably 2-4, more preferably 2.5-4. When the number of hydroxyl groups is 2 or more, the compressive residual strain ratio and wet heat compressive residual strain ratio tend to decrease and the impact resilience modulus tends to increase, and when it is 4 or less, the elongation tends to increase.

  The polymer polyol is a polymer obtained by polymerizing a vinyl monomer in the polyether polyol (f2).

  The hydroxyl value of (f2) and the average number of hydroxyl groups per molecule of (f2) are preferably in the same range as (f1).

  The polymer polyol is a vinyl monomer (preferably acrylonitrile and / or styrene) such as acrylonitrile, styrene, alkyl (1 to 24 carbon atoms) (meth) acrylate and vinylidene chloride in the presence of a radical initiator in (f2). Polymerized and stably dispersed can be used.

  The content of the vinyl polymer in the polymer polyol is preferably 15 to 60%, more preferably 20 to 50%.

  The polymer polyol can be easily produced by a known method, and examples thereof include a method described in US Pat. No. 3,383,351.

  The content of the polymer polyol in the polyol (A1) is not particularly limited, but is preferably 50% by mass or less, more preferably 0.1 to 40% by mass, and particularly preferably 1 to 4% by mass with respect to the mass of the polyol (A1). 30% by mass.

  Moreover, the content of the vinyl polymer in (A1) is preferably 40% by mass or less, more preferably 0.1 to 30% by mass.

In the thirteenth invention (reference invention) , the mass average value of the hydrophilic / hydrophobic balance (HLB) of (f1) and / or (f2) and the primary hydroxyl group of the terminal hydroxyl group of (f1) and / or (f2) The mass average value (%) of the conversion rate has a relationship represented by the formula (6).

(Mass average value of HLB) ≦ 0.1 × (mass average value of primary rate) −2 (6)

  The mass average value of HLB in (f1) and / or (f2) is preferably 7 or less, more preferably 6 or less.

  The mass average value of the HLB means that each mass fraction of each HLB (the mass of each polyether polyol divided by the sum of the masses of all the polyether polyols) of (f1) and / or (f2) ) Multiplied by ”is the value obtained by calculating for all the polyether polyols and summing them. That is, it is expressed by the following formula (14).

(Mass average value of HLB) = Σ (HLB × mass fraction) (14)

  In addition, HLB here is calculated by the method calculated | required from the ratio of the inorganic value of the compound which the above-mentioned Oda devised, and the organic value.

  The mass average value (%) of the primary ratio of the terminal hydroxyl group of (f1) and / or (f2) is at least 40%, preferably at least from the viewpoint of reactivity with isocyanate when producing a flexible polyurethane foam. 60%, more preferably at least 70%.

The mass average value of the terminal hydroxyl group primary ratio is (f1) and / or (f2) “the primary ratio of each terminal hydroxyl group is the respective mass fraction (the mass of each polyether polyol is all (Multiplied by the sum of the masses of the polyether polyols) is calculated for all the polyether polyols, and the values are obtained by summing them. That is, it is represented by the following formula (15).
(Mass average value of the primary ratio of terminal hydroxyl groups) = Σ (Primary ratio × mass fraction) (15)

In the fourteenth invention (reference invention) , (f1) and (f2) are the average added mole number x of ethylene oxide per active hydrogen described in the section of semi-rigid polyurethane foam is 20 or less, 1 with 3 or more carbon atoms satisfying the relationship of the formula (1) when the degree of OH conversion y is 40% or more and x is 10 to 20 and x is 10 or less, and the formula (2). Polyether polyol (c) formed by addition of alkylene oxide mainly composed of 2-alkylene oxide. (However, the preferred hydroxyl value is within the above range.)

y ≧ 0.328x + 90.44 (1)
y ≧ 42x ^0.47 (1-x / 41) (2)

  (C) is preferably (c1) formed by random and / or block addition of an alkylene oxide containing ethylene oxide mainly containing 1,2-alkylene oxide having 3 or more carbon atoms.

  When any one of the above polyols is used as (A1), a foam having a uniform density can be obtained without deterioration of moisture resistance.

In any of the thirteenth and fourteenth inventions (both are reference inventions) , (f1) and (f2) use the specific catalyst (α) described in the aforementioned International Publication WO00 / 02952. It can be easily produced by the method of the invention (reference invention) .

  In particular, when producing a flexible polyurethane foam with little heat deterioration, the total unsaturation degree of the polyether polyol contained in the polyol (A) is 0.05 meq / g or less (particularly 0.04 meq / g or less). Is preferred.

  The low total unsaturation (f1) and (f2) can be achieved, for example, in an active hydrogen-containing compound (G) in the presence of a catalyst such as cesium hydroxide or the like (eg, US Pat. No. 3,393,243). , AO (especially PO) is added, the catalyst is removed, AO is added in the presence of a catalyst such as trispentafluorophenylborane, and EO is added if necessary. Here, the total unsaturation is a value measured by the method described in JIS K-1557.

In the thirteenth and fourteenth inventions (both are reference inventions) , in the active hydrogen compound (A) comprising (A1), other than the polymer polyol comprising (f1) and (f2), if necessary, other A polyol or monool (e) can also be used in combination.

(E) includes polyether polyol (14th invention (reference invention) only), polyester polyol, modified polyol or monool, polyhydric alcohol, amines and mixtures thereof, (f1) and (f2) Other than that. Specific examples of (e) are the same as those described above.

  The proportion of (e) in 100 parts by mass of the active hydrogen compound is usually 70 parts by mass or less, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. The ratio of (f1) and / or (f2) is usually 30 parts by mass or more, preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 70 parts by mass or more.

  Among (e), when a terminal radical polymerizable functional group-containing active hydrogen compound (e1) described in EP 1 006 133 is used, it is possible to obtain a flexible polyurethane foam further excellent in foam hardness and wet heat compression residual strain. it can.

  In the production method of the present invention, the terminal radical polymerizable functional group (t) of (e1) is a terminal olefin type radical polymerizable functional group, and is a terminal olefin type radical polymerization represented by the following general formula (16). More preferred are functional groups.

（但し、式中Ｒ⁷は水素、炭素数１〜１５のアルキル基または炭素数６〜２１のアリール基を表す。）

(In the formula, R ⁷ represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.)

  Specific examples of the group having the group represented by the general formula (16) include terminal unsaturated bond-containing groups such as acryloyl group, methacryloyl group, vinyl group, vinylbenzyl group, vinylphenyl group, and allyl ether group. Can be mentioned.

  Of these groups, acryloyl, methacryloyl and allyl ether groups are particularly preferred.

  The number of (t) in (e1) is usually 1 to 10, preferably 1 to 5.

  The active hydrogen-containing group (w) possessed by (e1) is not particularly limited. For example, one or more active hydrogens selected from a hydroxyl group, a mercapto group, a carboxyl group, a primary amino group, a secondary amino group, etc. A containing group.

  Preferred active hydrogen-containing groups are hydroxyl groups and mercapto groups, especially hydroxyl groups.

  The number of active hydrogen-containing groups in (e1) is usually 1 to 8, preferably 1 to 5.

  (E1) is more preferably represented by the following formula (17).

（但し、式中Ｒ⁷は水素、炭素数１〜１５のアルキル基または炭素数６〜２１のアリール基を表し、ＧはＯ、ＳまたはＮＨを、ｕ、ｖは正の整数を、Ｌは活性水素含有基を、Ｊは活性水素化合物からｕ＋ｖ個の活性水素含有基を除いた残基をそれぞれ示す。）

(Wherein R ⁷ represents hydrogen, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 21 carbon atoms, G represents O, S or NH, u and v represent positive integers, and L represents Active hydrogen-containing group, J represents a residue obtained by removing u + v active hydrogen-containing groups from an active hydrogen compound.)

R ⁷ is preferably hydrogen or an alkyl group, particularly hydrogen or methyl group, and G is preferably O. The value of u is preferably 1 to 7, more preferably 1 to 5, and the value of v is preferably 1 to 7, more preferably 1 to 4, particularly preferably 2 to 4. The value of u + v is preferably 2-8, more preferably 3-8. L is preferably a hydroxyl group.

  Specific examples of the above (e1) include the following (e11) to (e14), and two or more kinds may be used in combination.

  (E11) Polyols [polyhydric alcohols; polyhydric phenols; polyols obtained by adding alkylene oxide (AO) to them; polyols obtained by adding (AO) to amines; derived from polyhydric alcohols and polycarboxylic acids Unsaturated carboxylic acid partial ester such as polyester polyol.

(E12) Unsaturated carboxylic acid partial amidation of amines (e13) Unsaturated carboxylic acid partial thioester of polythiols (e14) Vinyl monomers having hydroxyl groups other than the above (e11) Polyols used for the production of Of these, examples of the polyhydric alcohol, polyhydric phenol, amines, and AO added thereto include those described in the section of the rigid polyurethane foam.

  Preferable AO to be added is one containing PO and / or EO as a main component and other AO of 20% by mass or less. The number of added moles of AO is preferably 1 to 70, more preferably 2 to 50.

  Among the polyols used in the production of (e11), examples of the polyester polyol include those described in the section of the rigid polyurethane foam.

  As the polyols used for the production of (e11), those having 2 to 8 (particularly 2 to 6) hydroxyl groups and having an OH equivalent of 30 to 1200 (particularly 31 to 250) are preferable.

  (E11) can be obtained by partially esterifying the polyols exemplified above with unsaturated carboxylic acids at an equivalent ratio such that at least one hydroxyl group remains unreacted in one molecule.

  Unsaturated carboxylic acids include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, anicotic acid, cinnamic acid, vinyl benzoic acid, and combinations of two or more of these [Here, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereinafter. Ester forming derivatives of these unsaturated carboxylic acids, such as halides [(meth) acrylic acid chlorides, etc.], acid anhydrides [maleic anhydride, itaconic anhydride, citraconic anhydride, etc.]; and these These two or more types are used in combination.

  Specific compounds of (e11) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, Examples thereof include glycerin mono (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol mono (meth) acrylate, pentaerythritol triacrylate, sorbitol di (meth) acrylate, and combinations of two or more thereof.

  (E12) is such that at least one amino group or hydroxyl group (in the case of alkanolamine) remains unreacted in one molecule of polyamine or alkanolamine and the unsaturated carboxylic acid among the amines. It is obtained by reacting at an equimolar ratio.

  Specific examples of the compound include (meth) acrylamide ethylamine, (meth) acrylamide hexylamine, and combinations of two or more thereof.

  The polythiols used for the production of (e13) are preferably those having 2 to 4 thiol groups and 2 to 18 carbon atoms, such as ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, tri Examples include methylolpropane tris (thioglycolate) thiocyanuric acid, di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and combinations of two or more thereof.

  (E13) can be obtained by reacting these unsaturated carboxylic acids with these polythiols at an equivalent ratio such that at least one thiol group remains unreacted in one molecule.

  Specific examples of the compound include acryloylthioethyl mercaptan, acryloylthiobutyl mercaptan, and combinations of two or more thereof.

  (E14) includes p-hydroxylstyrene, (meth) allyl alcohol, cinnamyl alcohol, crotonyl alcohol, and partially allyl etherified products of the above polyhydric alcohols (pentaerythritol triallyl ether, etc.). And those having these hydroxyl groups), the aforementioned alkylene oxide (AO) adducts (preferably 2 to 20 mol adducts) of these compounds, and combinations of two or more thereof.

  The number of radically polymerizable functional groups in (e14) is preferably 1 to 5, the number of active hydrogen-containing groups is preferably 1 to 5, and Mn is preferably 1000 or less.

  Among these, preferred are those having a low viscosity and a low viscosity when formed into a polyurethane-forming composition. Therefore, unsaturated carboxylic acid partial esters (e11) of polyols and vinyl monomers having a hydroxyl group (e14). (Especially allyl etherified products of polyhydric alcohols), particularly preferably unsaturated carboxylic acid partial esters of polyhydric alcohols or alkylene oxide adducts thereof.

  The molecular weight per active hydrogen-containing group (e1) is preferably 40 to 2500, more preferably 40 to 500, and particularly preferably 45 in consideration of the viscosity when a polyurethane-forming composition is used. ~ 400.

  The amount of (e1) used is preferably 20% by mass or less, more preferably 0.1 to 10 parts by mass in 100 parts by mass of (A).

It can also be used in the method of this reference invention, a chain extender and / or crosslinking agent necessary to (e2).

  As (e2), those which can be usually used for polyurethane can be used. For example, among the above-mentioned (e), carbon number 2 such as ethylene glycol, diethanolamine, triethanolamine, glycerin, trimethylolpropane and D-sorbite. -6 polyhydric alcohols and alkanolamines.

  The amount of (e2) is preferably 10% by mass or less, more preferably 0.01 to 5 parts by mass in 100 parts by mass of (A).

  As the organic polyisocyanate (B), known ones usually used for polyurethane can be used, and examples thereof include those described in the section of the rigid polyurethane foam.

  Of those exemplified as (B), preferred are aromatic polyisocyanates, and more preferred are TDI alone and a mixture of TDI and modified MDI and / or crude MDI.

  As a foaming agent, what consists of water (C1) is preferable.

  In addition, the above-described hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, liquefied carbon dioxide, etc. are used as necessary.

  As the catalyst (D), known ones usually used for polyurethane, for example, metal salts of carboxylic acids, alkoxides of alkali metals or alkaline earth metals, phenoxides of alkali metals or alkaline earth metals, tertiary amines, quaternary Examples thereof include organometallic compounds containing metals such as ammonium salts, imidazole, tin, and antimony.

  Examples of the metal salt of carboxylic acid include sodium acetate, lead octoate, zinc octoate, tin octoate and cobalt naphthenate.

  Examples of the alkali metal or alkaline earth metal alkoxide include sodium methoxide and potassium ethoxide.

  Examples of alkali metal or alkaline earth metal phenoxides include sodium phenoxide and potassium phenoxide.

  Examples of the tertiary amine include triethylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, trimethylaminoethylpiperazine, tetramethylhexamethylenediamine, trisdimethylaminopropyl-s-triazine, and pyridine.

  Examples of the quaternary ammonium salt include tetraethylhydroxylammonium.

  Examples of imidazole include imidazole and 2-ethyl-4-methylimidazole.

  Examples of the organometallic compound include tetraphenyl tin and tributyl antimony oxide. Of these, tertiary amines are preferred.

  Examples of the foam stabilizer (E1) include those described above. Moreover, you may use said additives (E2) other than (E1). Specific examples and preferred use amounts of (E) are the same as those described in the section of the rigid polyurethane foam.

The amounts of (B), (C1), (D), and (E1) used in the present reference invention are as follows based on the amount of the active hydrogen compound (A) comprising (A1).

  The amount of (B) used is preferably such an amount that the isocyanate index is 80 to 120, more preferably 90 to 110, and particularly preferably 95 to 105. When the isocyanate index is 80 or more, the air permeability of the foam increases, the resilience modulus tends to increase, and the expansion ratio tends to increase. On the other hand, when the isocyanate index is 120 or less, the curing property tends to be improved.

Water (C1) used as a blowing agent is preferably at least 2.8 parts by mass, more preferably 3-8 parts by mass with respect to 100 parts by mass of (A) in order to obtain a flexible foam having a total density of 55 kg / m ³ or less. Part.

  The amount of (D) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of (A).

  As for the quantity of (E1), 10 mass parts or less are preferable with respect to 100 mass parts of (A), More preferably, it is 0.1-5 mass parts.

  A mixture of the components (A), (C1), (D), and (E1) and (B) are stirred and mixed by a usual method and foamed to obtain a flexible polyurethane foam.

The production method of the flexible polyurethane foam using the method of this reference invention, a conventionally known method, for example, slab method, hot curing method, but may be any method such as a cold cure method, a cold cure method is preferred.

For the first time by the production method of the thirteenth or fourteenth invention (both are reference inventions ), a flexible polyurethane having a core density of 20 to 33 kg / m ³ and a wet heat compression residual strain of 15% or less (particularly 13% or less). A form can be obtained.

The flexible polyurethane foam produced by the production method of the thirteenth or fourteenth invention (both are reference inventions) is suitably used for furniture cushions, bedding cushions, automotive cushions, cushioning materials, packing materials, and heat insulating materials. It is done. Among these furniture cushions, Ru further suitable der bedding cushion and cushion for automobiles.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the following, “part”, “%” and “ppm” are based on mass.
In addition, Examples 1-2 and Example 1'-2 'are reference examples, and Comparative Examples 1-2 and Comparative Examples 1'-2' are reference comparative examples.

<< Examples of Polyether >>
Example 1
In a stainless steel autoclave with a 200 ml stirring device and temperature controller, 57.0 g of “SANNICS GP-1000” (manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1000 glycerin PO adduct) and tris (pentafluorophenyl) borane 0 0.009 g was charged, and 86.4 g of PO was added dropwise over 10 hours while controlling the reaction temperature to be 65 to 75 ° C., followed by aging at 70 ° C. for 5 hours. After adding water and distilling at 105 to 110 ° C. for 4 hours under normal pressure, the temperature was kept at 90 to 100 ° C. and the pressure was kept at 30 to 50 torr. After stopping the introduction of water vapor, 0.1 g of potassium hydroxide was added, and the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. The primary hydroxylation rate of the terminal hydroxyl group of this product was 71%. Subsequently, 29.6 g of EO was added dropwise over 3 hours while controlling the reaction temperature to be 125 to 135 ° C., and then aged at 130 ° C. for 2 hours. 4.0 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 2.0 g of water were added and treated at 90 ° C. for 1 hour. After taking out from the autoclave, the mixture was filtered using a filter paper and dehydrated under reduced pressure to obtain 152.2 g of a liquid glycerin PO · EO adduct (Mn: 3000). The yield was 88%, the hydroxyl value was 56.5, the EO content was 16.7% by mass, and the terminal hydroxyl group primary conversion was 90%. The left side of the relational expression (3 ) of requirement <3> of the second invention (reference invention) is 3.7 and the right side is 7.5, which satisfies the requirement <3>. The right side of the formula (2) of the first invention (reference invention) is 70.7, which satisfies the relational expression of the formula (2).

Comparative Example 1
After 0.63 g of potassium hydroxide was used instead of tris (pentafluorophenyl) borane, PO86.0 g was added dropwise at a reaction temperature of 90 to 110 ° C. over 12 hours in the same reaction apparatus as in Example 1. Aged for 6 hours. The primary hydroxylation rate of this terminal hydroxyl group was 2%. Subsequently, 29.6 g of EO was added dropwise over 3 hours while controlling the reaction temperature to be kept at 120 to 140 ° C., followed by aging for 2 hours. Next, 3.0 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical Co., Ltd.) and 2 g of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter and then dehydrated to obtain 161.3 g of a liquid glycerin PO · EO adduct (Mn: 3000). The yield was 97%, the hydroxyl value was 56.4, the EO content was 16.5% by mass, and the terminal hydroxyl group primary conversion was 69%. The left side of relational expression (3) of requirement <3> is 3.7 and the right side is 2.4, which does not satisfy requirement <3>. Moreover, the right side of Formula (2) is 70.7, and does not satisfy the relational expression of Formula (2).

Example 2
In a stainless steel autoclave with a 200 ml stirring device and a temperature control device, 87.8 g of “SANNICS PP-1000” (manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1000 polypropylene glycol) and 0.02 g of tris (pentafluorophenyl) borane Was added dropwise over 12 hours while controlling the reaction temperature to maintain 60 to 70 ° C., and then aged at 65 ° C. for 3 hours. The primary hydroxylation rate of the terminal hydroxyl group of this product was 69%. Subsequently, 22.0 g of EO was added dropwise over 4 hours while controlling the reaction temperature to be kept at 50 to 60 ° C., and then aged at 60 ° C. for 4 hours. After neutralizing with an aqueous sodium hydroxide solution, 3.0 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 1.0 g of water were added and treated at 70 ° C. for 1 hour. After taking out from the autoclave, it was filtered through a 1-micron filter and dehydrated to obtain 156.8 g of a liquid polypropylene glycol EO adduct (Mn: 2000). The yield was 90%, the hydroxyl value was 55.9, the EO content was 12.5% by mass, and the terminal hydroxyl group primary conversion was 86%. The left side of the relational expression (3) of requirement <3> is 2.85 and the right side is 5.99, which satisfies requirement <3>. Further, the right side of the formula (2) is 63.9, which satisfies the relational expression of the formula (2).

Comparative Example 2
After 0.63 g of potassium hydroxide was used instead of tris (pentafluorophenyl) borane, 65.0 g of PO was dropped at a reaction temperature of 50 to 60 ° C. over 30 hours in the same reaction apparatus as in Example 1. Aged for 20 hours. The primary hydroxylation rate of the terminal hydroxyl group of this product was 1%. Subsequently, 22.0 g of EO was added dropwise over 15 hours while controlling the reaction temperature so as to maintain 50 to 60 ° C., followed by aging for 10 hours. Next, 3.0 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical Co., Ltd.) and 2 g of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1-micron filter and dehydrated to obtain 160.3 g of a liquid polypropylene glycol EO adduct (Mn: 3000). The yield was 96%, the hydroxyl value was 55.7, the EO content was 12.4% by mass, and the terminal hydroxyl group primary conversion was 62%. The left side of the relational expression (3) of requirement <3> is 2.83 and the right side is 1.59, which does not satisfy requirement <3>. Moreover, the right side of Formula (2) is 63.8, and does not satisfy the relational expression of Formula (2).

Example 1 '
434.9 g of glycerin POEO adduct (Mn: 3000) obtained in Example 1, 219.2 g of tolylene diisocyanate, 18.7 g of water, 0.57 g of stannous octate, 5.26 g of dioctyl phthalate, polyoxypropylene glycol ( (Mn: 2000) 5.3 g, triethylenediamine 0.33 g, N-methylmorpholine 2.2 g, and foam stabilizer (L-520, manufactured by Nippon Unica) 6.6 g were uniformly mixed. This mixed solution was uniformly poured into a 30 cm square container and foamed to produce a urethane foam.

  The foaming behavior at this time was 100% rise time of 50 seconds. Further, when the viscosity at the time of foaming was confirmed with a vibration viscometer, it was 30 seconds after mixing that the viscosity of the foamed resin reached 100,000 cps.

Comparative Example 1 '
Instead of the glycerin POEO adduct (Mn: 3000) obtained in Example 1, 434.9 g of the glycerin POEO adduct (Mn: 3000) obtained in Comparative Example 1 was used. A urethane foam was produced.

  The foaming behavior at this time was 100% rise time of 2 minutes. Further, when the viscosity at the time of foaming was confirmed with a vibration viscometer, it was 50 seconds after mixing that the viscosity of the foamed resin reached 100,000 cps.

Example 2 '
In a four-necked flask equipped with a 500 ml stirrer and a temperature controller, 11,5.2 g of 4,4′-diphenylmethane diisocyanate, 264.4 g of the polypropylene glycol EO adduct (Mn: 2000) obtained in Example 2, ethylene glycol 20 4 g was charged and reacted at 68 ° C. for 5 hours to obtain a polyurethane elastomer. The reaction rate (consumption rate) of the isocyanate groups during the reaction was 78% after 1 hour, 95% after 1.5 hours, and 100% after 2 hours.

  Table 1 shows Mn (by gel permeation chromatography), tensile breaking strength, breaking elongation, and water swelling rate of the obtained polyurethane elastomer. Measurement of tensile strength at break and elongation at break were in accordance with JIS K-7311. The water swelling rate was measured by measuring the mass increase rate after 24 hours of immersion in water at 25 ° C.

Comparative Example 2 ′
The same procedure as in Example 2 ′ except that the polypropylene glycol EO adduct (Mn: 2000) obtained in Comparative Example 2 was used instead of 264.4 g of the polypropylene glycol EO adduct (Mn: 2000) obtained in Example 2. Thus, a polyurethane elastomer was obtained.

  The reaction rate (consumption rate) of the isocyanate groups during the reaction was 55% after 1 hour, 81% after 2 hours, 95% after 3 hours, and 100% after 4 hours.

  Table 1 shows Mn :, tensile strength at break, elongation at break, and water swelling ratio of the obtained polyurethane elastomer.

Example 1 ', 2' and the comparative example 1 ', 2', as is apparent in comparison with polyether compounds of this reference invention, as compared with a conventional polyether compound, highly reactive toward isocyanate groups Have

Further, as shown in Table 1, a polyurethane elastomer using a polyether compound of this reference invention is compared with Comparative Example, high molecular weight, elongation at break while being equal, higher tensile strength, excellent resin that having a physical property.

<< Examples of rigid polyurethane foam >>
Examples 21-24 and Comparative Examples 21-25 (Manufacture of box-shaped heat insulating materials for refrigerators)
In accordance with the foaming formulations shown in Tables 2 and 3 , raw materials containing a predetermined amount other than (B) were charged into a polyol component tank of a high-pressure foaming machine, and (B) was charged into an isocyanate tank. For the refrigerator with 35kg / m ³ urethane foam density, paste the steel plate on the outer mold and the thermoplastic resin plate on the inner mold and inject it between the outer and inner walls. A box-shaped insulation was obtained.

  FIG. 1 is an overall view of a box-shaped heat insulating material. In FIG. 1, 1 is a box-shaped heat insulating material for refrigerators, 2 is an outer wall (made of galvanized steel), 3 is an inner wall (made of thermoplastic resin), and 4 is a rigid polyurethane foam between the inner wall and the outer wall. In FIG. 2, 1 is a cross section of the refrigerator box-shaped heat insulating material, 2 is an outer wall (made of galvanized steel plate), 3 is an inner wall (made of thermoplastic resin), and 4 is a rigid polyurethane foam between the inner wall and the outer wall.

Examples 25-27 and comparative examples 26-30 (manufacture of heat insulation panel)
In accordance with the foaming formulation shown in Tables 4 and 5 , raw materials containing a predetermined amount other than (B) were charged into a polyol component tank of a high-pressure foaming machine, and (B) was charged into an isocyanate tank, and the temperature was adjusted to 20 ° C., respectively. 3,000 mm (length) x 500 mm (temperature adjusted to 40 ° C.) with a galvanized steel plate of 3000 mm (length) x 500 mm (width) x 0.3 mm (thickness) attached to the upper mold and lower mold in advance. It was poured into an aluminum mold having a width of 100 mm (height) to obtain a heat insulating panel having a urethane foam density of 34 kg / m ³ .

Examples 28-29 and Comparative Examples 31-34 (Production of synthetic wood)
In accordance with the foaming formulation shown in Tables 6 and 7 , raw materials containing a predetermined amount other than (B) were charged into a polyol component tank of a high-pressure foaming machine, and (B) was charged into an isocyanate tank. The mixture was injected into an aluminum mold of 200 mm (length) x 200 mm (width) x 100 mm (height) that was temperature-adjusted to 60 ° C. and synthesized with a urethane foam density of 0.35 kg / m ³ . Got wood.

<Explanation of used raw material symbols>
(A-1): In the same manner as described in Example 1, 9 mol of PO was added to 1 mol of sorbitol using tris (pentafluorophenyl) boron as a catalyst [amount of catalyst 50 ppm (based on reaction product), reaction temperature 75 ° C], 1 mol of EO was further added, and then the catalyst component was removed.
Mn = 748, hydroxyl value = 450, average number of moles of EO added per active hydrogen x = 0.167, primary OH conversion ratio y = 46 %.

(A-2): In the same manner as described in Example 1, 4.9 mol of PO was added to 1 mol of glycerol using tris (pentafluorophenyl) boron as a catalyst, and then the catalyst component was removed.
Mn = 376, hydroxyl value = 447, average number of added EO moles per active hydrogen x = 0, primary OH conversion rate y = 50 %.

(A-3): In the same manner as described in Example 1, 3.3 mol of PO was added to 1 mol of glycerin using tris (pentafluorophenyl) boron as a catalyst, 2 mol of EO was added, and then the catalyst component was added. It has been removed.
Mn = 371, hydroxyl value = 453, average number of added EO moles per active hydrogen x = 0.667, primary OH conversion rate y = 62 %.

(A-4): In the same manner as described in Example 1, 5.9 mol of PO was added to 1 mol of pentaerythritol using tris (pentafluorophenyl) boron as a catalyst, and 0.5 mol of EO was further added. The catalyst component is removed.
Mn = 500, hydroxyl value = 449, average EO addition mole number per active hydrogen x = 0.125, primary OH conversion ratio y = 75 %.

(A-5): In the same manner as described in Example 1, 4.8 mol of PO is added to 1 mol of pentaerythritol using tris (pentafluorophenyl) boron as a catalyst, and 2 mol of EO is added, and then the catalyst component is added. Is removed.
Mn = 502, hydroxyl value = 447, average EO addition mole number per active hydrogen x = 0.5, primary OH conversion rate y = 85 %.

(B-1): 1 mol of tolylenediamine is added with 2 mol of EO without catalyst, 5 mol of PO is further added with potassium hydroxide as a catalyst, and the catalyst is neutralized with glacial acetic acid.
Mn = 500, active hydrogen value = 449.

(B-2): 1 mol of monoethanolamine is added with 2 mol of PO without catalyst, 5.4 mol of PO is further added with potassium hydroxide as a catalyst, and the catalyst is neutralized with glacial acetic acid.
Mn = 374, active hydrogen value = 450.

(R-21): 9 mol of PO is added to 1 mol of sorbitol using potassium hydroxide as a catalyst, 1 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 749, hydroxyl value = 449, average EO addition mole number per active hydrogen x = 0.167, primary OH conversion rate y = 18 %.

(R-22): 2.5 mol of PO is added to 1 mol of sorbitol using potassium hydroxide as a catalyst, 9.6 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 749, hydroxyl value = 449, average number of EO addition moles per active hydrogen x = 1.6, primary OH conversion ratio y = 47 %.

(R-23): 4.9 mol of PO was added to 1 mol of glycerin using potassium hydroxide as a catalyst, and the catalyst was neutralized with glacial acetic acid.
Mn = 376, hydroxyl value = 447, average number of added EO moles per active hydrogen x = 0, primary OH conversion y = 2 %.

(R-24): 1 mol of glycerol is added with 1 mol of PO using potassium hydroxide as a catalyst, 5.1 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 374, hydroxyl value = 450, average EO addition mole number per active hydrogen x = 1.7, primary OH conversion rate y = 61 %.
This product does not fall under (a) because the number of moles of AO added with 3 or more carbon atoms per mole of primary OH group of glycerin is 0.5.

(R-25): PO2 mol is added to 1 mol of glycerol using potassium hydroxide as a catalyst, 3.5 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 374, hydroxyl value = 450, average number of moles of EO added per active hydrogen x = 1.167, primary OH conversion ratio y = 41 %.

(R-26): 5.9 mol of PO is added to 1 mol of pentaerythritol using potassium hydroxide as a catalyst, 0.5 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 502, hydroxyl value = 447, average number of added EO moles per active hydrogen x = 0.125, primary OH conversion rate y = 12 %.

(R-27): 2.5 mol of PO is added to 1 mol of pentaerythritol using potassium hydroxide as a catalyst, 5 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 506, hydroxyl value = 444, average number of added EO moles per active hydrogen x = 1.25, primary OH conversion rate y = 77 %.
This product does not correspond to (a) because the number of moles of AO added with 3 or more carbon atoms per mole of primary OH group of pentaerythritol is 0.625.

(R-28): 4.8 mol of PO is added to 1 mol of pentaerythritol using potassium hydroxide as a catalyst, 2 mol of EO is further added, and the catalyst is neutralized with glacial acetic acid.
Mn = 502, hydroxyl value = 447, average number of added EO moles per active hydrogen x = 0.5, primary OH conversion ratio y = 27 %.

(R-29): 1 mol of pentaerythritol was added with 2 mol of PO using potassium hydroxide as a catalyst, 5.6 mol of EO was further added, and the catalyst was neutralized with glacial acetic acid.
Mn = 498, hydroxyl value = 451, average number of EO addition moles per active hydrogen x = 1.4, primary OH conversion rate y = 83 %.
This product does not correspond to (a) because the number of moles of AO addition having 3 or more carbon atoms per mole of primary OH group of pentaerythritol is 0.5.

(B-21): Crude MDI, organic polyisocyanate with NCO% = 31.
(C-21): Water (C-22): Cyclopentane (C-23): HCFC-141b
(D-21): “U-cat1000” (tetramethylhexamethylenediamine) manufactured by San Apro Co., Ltd.
(D-22): “TOYOCAT-ET” manufactured by Tosoh Corporation [mixture of bis (dimethylaminoethyl) ether and dipropylene glycol]
(D-23): “Minicol L-1020” manufactured by Nippon Emulsifier Co., Ltd. (mixture of triethylenediamine and dipropylene glycol)
(D-24): “Neostan U-100” (dibutyltin dilaurate) manufactured by Nitto Kasei Co., Ltd.
(E-21): “B-8462” (dimethylsilicone foam stabilizer) manufactured by Goldschmidt
(E-22): “SF-2936F” (dimethylsilicone foam stabilizer) manufactured by Toray Dow Corning Silicone Co., Ltd.
(E-23): “SH-193” (dimethylsilicone foam stabilizer) manufactured by Toray Dow Corning Silicone Co., Ltd.

Test example Testing of box-shaped insulation for refrigerators
<1>: Thickness of molded product (mm) when demolded 4 minutes after injection
<2>: Molded product thickness (mm) when removed from the mold 7 minutes after injection
<3>: Foam compressive strength (kgf / cm ² ) after 1 day of the molded product demolded 7 minutes after injection, measurement method, JIS A9511
In addition, the internal dimension of the type | mold of the part which measured <1>-<3> is 50 mm.

Insulation panel testing
<4>: Molded product thickness (mm) when the mold is removed 8 minutes after injection
<5>: Thickness of molded product (mm) when demolded 12 minutes after injection
<6>: Foam compressive strength (kgf / cm ² ) after 1 day of the molded product that was demolded 12 minutes after injection, measurement method, JIS A9511
In addition, the internal dimension of the type | mold of the part which measured <4>-<6> is 100 mm.

Synthetic wood testing
<7>: Thickness of molded product (mm) when demolded 10 minutes after injection
<8>: Molded product thickness (mm) when demolded 13 minutes after injection
<9>: Foam compressive strength (kgf / cm ² ) after 1 day of the molded product demolded 13 minutes after injection, measurement method, JIS A9511
In addition, the internal dimension of the type | mold of the part which measured <7>-<9> is 100 mm.

According to the method for producing a rigid polyurethane foam of the present invention, as compared with the conventional, excellent curability, and, blister during demolding small, Ru can be produced a large rigid polyurethane foam foam strength.

Since achieve the above effects, rigid polyurethane foam obtained by the process of the present invention, Ru very useful der refrigerators, freezers, as thermal insulation for construction materials.

It is a perspective view of the box-shaped heat insulating material for refrigerators after inject | pouring the raw material in Examples 21-24 and Comparative Examples 21-25. Examples 21 to 24, the refrigerator box-like insulation material after the injection material in Comparative Example 21 to 25, Ru sectional view der in broken line in FIG.

Explanation of symbols

1 Box-shaped heat insulating material for refrigerator 2 Outer wall (made of galvanized steel)
3 Inner wall (made of thermoplastic resin)
4 inner wall and the rigid polyurethane follower over-time between the outer wall

Claims (9)

In the polyhydric alcohol, each primary OH group is converted to a catalyst represented by the following general formula (8), (9) or (10) (α) having 1 or more moles of 1,3-alkylene oxide in each primary OH group (α ) In the presence of a polyether polyol added with ethylene oxide, having a hydroxyl value of 200 or more and an average added mole number x of ethylene oxide per active hydrogen of 2 For production of rigid polyurethane foam comprising a polyether polyol (a1) having a primary OH conversion rate y of 40% or more and a primary OH conversion rate of terminal hydroxyl groups of ethylene oxide non-added products of 40% or more Active hydrogen compound.

X-(-R ³ ) ₃ (8)

[In the formulas (8) to (10), X represents a boron atom or an aluminum atom; R ³ represents a (substituted) phenyl group represented by the following general formula (11) and / or the following general formula (12 ) represents a tertiary alkyl group represented by, when there are a plurality of R ^3, a plurality of R ³ may be the same or different. ]

[In Formula (11), T represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different. k represents the number of 0-5. ^R 4 in the formula ^{(12), R 5, R} 6 each independently represent an alkyl group having 1 to 4 carbon atoms and may be the same or different. ] Alkylene oxide having 2 or more carbon atoms in the amine is being added, active water iodine value of 200 or more active hydrogen compound (b), polyhydric alcohol primary OH groups to 1 mole per mole or more carbon atoms 3 The polyether polyol obtained by adding the above 1,2-alkylene oxide in the presence of the catalyst (α) represented by the following general formula (8), (9), or (10), and / or the polyol Furthermore, it comprises a polyether polyol to which ethylene oxide is added, has a hydroxyl value of 200 or more, an average added mole number x of ethylene oxide per active hydrogen of 2 or less, and a primary OH conversion ratio y of 40%. The hard polyurethane comprising the polyether polyol (a) having a primary OH conversion rate of 40% or more of the terminal hydroxyl group of the ethylene oxide non-added product as described above Omu producing active hydrogen components.
X-(-R ³ ) ₃ (8)

[In the formulas (8) to (10), X represents a boron atom or an aluminum atom; R ³ represents a (substituted) phenyl group represented by the following general formula (11) and / or the following general formula (12 ) represents a tertiary alkyl group represented by, when there are a plurality of R ^3, a plurality of R ³ may be the same or different. ]

[In Formula (11), T represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different. k represents the number of 0-5. ^R 4 in the formula ^{(12), R 5, R} 6 each independently represent an alkyl group having 1 to 4 carbon atoms and may be the same or different. ]   A rigid polyurethane foam is produced by adding an active hydrogen compound (A), an organic polyisocyanate (B), a foaming agent (C), a urethanization catalyst (D), and, if necessary, an additive (E) and curing the foam. A method for producing a rigid polyurethane foam, wherein (A) comprises the active hydrogen compound according to claim 1. A rigid polyurethane foam is produced by adding an active hydrogen compound (A), an organic polyisocyanate (B), a foaming agent (C), a urethanization catalyst (D), and, if necessary, an additive (E) and curing the foam. The method for producing a rigid polyurethane foam comprising (A) the active hydrogen component according to claim 2.   The method for producing a rigid polyurethane foam according to claim 4, wherein the content of (b) based on the sum of (a) and (b) is 5 to 80% by mass. Building materials made of the obtained rigid polyurethane foams in claim 3 Symbol mounting method for manufacturing a heat insulating material for home appliances or for transport. The heat insulating material for building materials, household appliances, or a transport machine which consists of a rigid polyurethane foam obtained by the manufacturing method in any one of Claims 4-5. Building materials made of the obtained rigid polyurethane foams in claim 3 Symbol mounting method for manufacturing a structural material for home appliances or for transport.   A structural material for building materials, home electric appliances or transportation equipment, comprising the rigid polyurethane foam obtained by the production method according to any one of claims 4 to 5.

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