JP2019157132A - Polyurethane slab foam forming composition, polyurethane slab foam, and production process therefor - Google Patents

Abstract

To provide: a polyurethane slab foam forming composition for automobile formed ceiling that has a low odor with low environmental load and a resiliency; and a polyurethane slab foam for automobile formed ceiling produced from said composition.SOLUTION: The problem is solved by a polyurethane slab foam forming composition for automobile formed ceiling which is a polyurethane slab foam forming composition for automobile formed ceiling comprising an organic polyisocyanate component (A) and a polyol mix (B), and in which, characterized, the polyol mix (B) contains a particular polyol component (b), a catalyst (C), a foaming agent (D), and a cell adjusting agent (E), a reactive catalyst having a boiling point of 200°C or higher is contained as the catalyst (C), and a water is contained as the foaming agent (D).SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane slab foam forming composition for automobile molded ceiling, a polyurethane slab foam obtained from the composition, and a method for producing the same.

  A polyurethane foam is produced by reacting a polyol and a polyisocyanate in the presence of a blowing agent and a catalyst.

  Conventionally, low-boiling organic compounds such as chlorofluorocarbons and hydrofluorocarbons such as chlorofluorocarbons and methylene chloride have been used as foaming agents for forming polyurethane foams. However, recent demands for defluorination, adverse environmental effects and toxicity have been pointed out, and a method of using water as a blowing agent has been proposed.

  It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane foam. These catalysts are roughly classified into foaming catalysts, resinification catalysts, and nurating catalysts. A tertiary amine compound is preferably used as the foaming catalyst, and a metal compound or a quaternary ammonium salt is preferably used in addition to the tertiary amine compound as the resination catalyst or the nurating catalyst.

  Among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability in the production of polyurethane foam using water as a blowing agent. However, when used in a large amount, the tertiary amine compound may cause an irritating odor or cause eye itchiness due to the catalyst vapor during the manufacturing operation, which is disadvantageous in terms of environmental hygiene.

  In order to eliminate these disadvantages, tertiary amine catalysts having a high boiling point such as 1,4-diazabicyclo [2.2.2] octane, N, N, N ′, N′-tetramethylhexamethylenediamine have been proposed. Although some effects are recognized, it is still not enough. In addition, since these tertiary amine catalysts are not taken into the polyurethane by chemical bonds during the urethanization reaction, they dissipate from the polyurethane and discolor the resin sheet used as the automobile interior material, There is a risk that the window glass may become cloudy.

  As an amine catalyst to be incorporated into polyurethane during the urethanization reaction, a tertiary amine catalyst having a hydroxyl group and an amino group that react with an isocyanate group in the molecule has been proposed.

  For example, a method using dimethylethanolamine as a catalyst has been disclosed as a method for producing a polyurethane slab foam having an open cell structure used as an automobile headliner (see Patent Document 1).

  However, in the polyurethane foam described in Patent Document 1, an unreacted catalyst remains in the foam, the boiling point of the catalyst is as low as 133 ° C., and it is difficult to say that the effect of improving odor is sufficient.

JP-A-4-21416

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to provide a polyurethane slab for an automobile molded ceiling that has a good balance between excellent flexibility and mechanical properties without causing odor problems and environmental problems. It is providing the foam formation composition, the polyurethane slab foam obtained from this composition, and its manufacturing method.

  That is, the present invention includes the following embodiments.

  [1] A composition for forming a polyurethane slab foam for automobile molded ceiling comprising an organic polyisocyanate component (A) and a polyol mix (B), wherein the polyol mix (B) comprises a polyol component (b), a catalyst ( C), a foaming agent (D), and a foam stabilizer (E). In the polyol component (b), 20 to 50% by mass of a polyol (b1) having a molecular weight per functional of 1500 or more per functional 40 to 70% by mass of the polyol (b2) having a molecular weight of 100 or more and less than 1500, and 1 to 10% by mass of the polyol (b3) having a molecular weight per function of less than 100, and having a boiling point of 200 ° C. or more as the catalyst (C) A composition for forming a polyurethane slab foam for automobile molded ceilings, comprising: a reactive catalyst, and water as a foaming agent (D).

  [2] The composition for forming a polyurethane slab foam for automobile molded ceiling according to the above [1], wherein the polyol mix (B) does not contain a polyester polyol.

  [3] The composition for forming a polyurethane slab foam for automobile molded ceiling according to the above [1] or [2], wherein the polyol (b3) is a diol having a molecular weight per functional group of less than 100.

  [4] The composition for forming a polyurethane slab foam for automobile molded ceiling according to any one of the above [1] to [3], wherein the catalyst (C) contains 2-hydroxymethyltriethylenediamine.

  [5] Any one of [1] to [4] above, further comprising a salt of an organic acid and at least one metal ion selected from Na, Ca, and Zn as the auxiliary agent (F). A composition for forming polyurethane slab foam for automobile molded ceilings as described in 1.

  [6] A polyurethane slab foam for automobile molded ceiling obtained from the polyurethane slab foam-forming composition according to any one of [1] to [5].

  [7] A method for producing a polyurethane slab foam for automobile molded ceiling obtained by reacting and foaming an organic polyisocyanate component (A) and a polyol mix (B), wherein the polyol mix (B) is a polyol component. A polyol (b) containing a catalyst (C), a foaming agent (D), a foam stabilizer (E), and an auxiliary agent (F) and having a molecular weight per functional group of 1500 or more in the polyol component (b) ( 20 to 50% by weight of b1), 40 to 70% by weight of a polyol (b2) having a molecular weight of 100 to less than 1500, and 1 to 10% by weight of a polyol (b3) having a molecular weight of less than 100 per function Including a reactive catalyst having a boiling point of 200 ° C. or higher as the catalyst (C), water as the blowing agent (D), and an isocyanate group and a polyol in the organic polyisocyanate component (A). The molar ratio of the hydroxyl group in LUMIX (B), automotive molded ceiling method for producing polyurethane slab foam, characterized in that the foam as the isocyanate group / hydroxyl group = 0.9 to 1.5.

  [8] The method for producing a polyurethane slab foam for automobile molded ceiling according to the above [7], wherein the polyol mix (B) does not contain a polyester polyol.

  [9] The method for producing a polyurethane slab foam for automobile molded ceiling according to the above [7] or [8], wherein the polyol (b3) is a diol having a molecular weight per functional group of less than 100.

  [10] The method for producing a polyurethane slab foam for automobile molded ceiling according to any one of the above [7] to [9], wherein the catalyst (C) contains 2-hydroxymethyltriethylenediamine.

  [11] The above [7] to [10], wherein the auxiliary agent (F) contains a salt of an organic acid and at least one metal ion selected from Na, Ca, and Zn. The manufacturing method of the polyurethane slab foam for automotive molded ceiling of description.

  [12] A vehicle ceiling material using the polyurethane slab foam for automobile molded ceiling according to the above [6].

  According to the composition of the present invention, it is possible to form a polyurethane slab foam for automobile-molded ceilings, which has excellent mechanical properties typified by low odor, low environmental impact, excellent flexibility, and tensile strength.

  Hereinafter, the present invention will be described in detail.

  The polyurethane slab foam for automobile molded ceiling of the present invention is obtained from a composition for forming polyurethane foam for automobile molded ceiling, which comprises an organic polyisocyanate component (A) and a polyol mix (B).

<Organic polyisocyanate component (A)>
The organic polyisocyanate component (A) used in the present invention includes diphenylmethane diisocyanate (hereinafter referred to as MDI) (A1) having two benzene rings and two isocyanate groups in one molecule, and three benzene rings and isocyanate groups in one molecule. Polymeric MDI, which is a mixture of at least one diphenylmethane diisocyanate-based polynuclear condensate (A2), is included.

  MDI (A1) includes 4,4′-MDI, 2,4′-MDI, and 2,2′-MDI, and the ratio of 4,4′-MDI in MDI (A1) is 50% by mass or more. It is preferable that

  As a ratio of MDI (A1) in a polyisocyanate component (A), it is preferable that it is 40-80 mass%, More preferably, it is 70-80 mass%.

  When the ratio of MDI (A1) exceeds 80% by mass, the formed polyurethane slab foam may not have sufficient strength.

  On the other hand, when the ratio of MDI (A1) is less than 40% by mass, the formed polyurethane slab foam may not have sufficient flexibility. Moreover, since the viscosity of the polyisocyanate component excessively increases with an increase in the polymer body, there is a risk of adversely affecting the mixing property with the polyol component during foam foaming.

  The organic polyisocyanate component (A) of the present invention may contain a polyisocyanate other than polymeric MDI as an optional component.

  Examples of polyisocyanates other than polymeric MDI include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine Ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-di Soshianeto 4 isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, and the like, may be used by mixing two or more of these. In addition, isocyanate-containing prepolymers by reaction of these polyisocyanates and polyols, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups, amide groups, imides) A modified product containing a group, a uretonimine group, a uretdione group or an oxazolidone group).

  The NCO content of the organic polyisocyanate component (A) is preferably 30 to 33% by mass, more preferably 31 to 33% by mass.

  The average number of functional groups of the organic polyisocyanate component (A) is preferably 2.0 to 3.0, more preferably 2.0 to 2.5.

<Polyol mix (B)>
The polyol mix (B) of the present invention contains a polyol component (b), a catalyst (C), a foaming agent (D), and a foam stabilizer (E).

<Polyol component (b)>
In the polyol component (b) of the present invention, the polyol (b1) having a molecular weight per unit functionality (MW / f) of 1500 or more is 20 to 50% by mass, and the polyol (b2) having a MW / f of 100 or more and less than 1500 is 40. -70 mass% and 1-10 mass% of polyol (b3) whose MW / f is less than 100 are included. Here, MW represents the number average molecular weight of the polyol, and f represents the number of functional groups of the polyol.

When (b1) is less than 20% by mass, the flexibility of the foam cannot be obtained, and when it exceeds 50% by mass, the foam strength is insufficient. When (b2) is less than 40% by mass, the foam strength tends to decrease, and when it exceeds 70% by mass, it is difficult to impart flexibility to the obtained foam. By introducing (b3) that functions as a chain extender into the polyol mix (B), mechanical properties represented by tensile strength can be imparted, and the bottom surface of the polyurethane slab foam has no air voids and is uneven or rough. It is possible to obtain a good surface property with less.
When the amount introduced exceeds 10% by mass, brittleness tends to develop in the resulting foam.

  The number average molecular weight of (b1) is preferably 3000 to 10000, more preferably 4000 to 6000, and most preferably 5000 to 6000.

  The hydroxyl value of (b1) is preferably 20 to 60 mgKOH / g, more preferably 25 to 40 mgKOH / g, and most preferably 30 to 35.

  The number average molecular weight of (b2) is preferably 150 to 3000, more preferably 200 to 1000, and most preferably 300 to 700.

  The hydroxyl value of (b2) is preferably 60 to 1000 mgKOH / g, more preferably 170 to 850 mgKOH / g, and most preferably 240 to 600.

  The molecular weight of (b3) is preferably 50 to 150, more preferably 60 to 150, and most preferably 90 to 120.

  The hydroxyl value of (b3) is preferably 700 to 3370 mgKOH / g, more preferably 750 to 1800 mgKOH / g, and most preferably 1000 to 1800.

  Examples of the polyols (b1) and (b2) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, animal and plant polyols, short molecular polyols that function as chain extenders, halogen-containing polyols, phosphorus-containing polyols, and phenol-based polyols. Etc.

  The polyether polyol can be produced by adding a cyclic ether to a compound having two or more active hydrogens as an initiator.

  Examples of the “compound having two or more active hydrogens” used for the production of the polyether polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 2,2-dimethyl-1,3. -Propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tetramethylene glycol, Short-chain diols such as hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol and bisphenol A; short-chain triols such as glycerin, hexanetriol and trimethylolpropane; 2,2,6 , 6-Teto Polyols having 5 to 8 OH groups such as kiss (hydroxylmethyl) cyclohexanol, sorbitol (glucitol), mannitol, dulcitol (galactitol), sucrose; low molecular polyamines such as diethylenetriamine and aniline; monoethanolamine, diethanolamine And low molecular amino alcohols such as triethanolamine can be used, and these can be used alone or in combination of two or more.

  Examples of the “cyclic ether” used for the production of the polyether polyol include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and the like. The above can be used in combination. Of these, ethylene oxide and propylene oxide are preferred, and by adjusting these ratios, the dispersibility between polyols having different molecular weights can be adjusted, and the breathability of the foam can be adjusted.

  The polyester polyol can be produced by reacting a polyhydric alcohol having two or more hydroxyl groups with a polybasic acid having two or more carboxyl groups by a known method.

  Examples of the “polyhydric alcohol having two or more hydroxyl groups” used for the production of the polyester polyol include the short-chain diol and the short-chain triol. These may be used alone or in combination of two or more. Can be used.

  Examples of the “polybasic acid having two or more carboxyl groups” used for the production of polyester polyol include adipic acid, malonic acid, succinic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid, phthalic acid, and terephthalic acid. , Isophthalic acid, phthalic anhydride, azelaic acid, trimellitic acid, curtaconic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, hemimellitic acid 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenyl Sulfone dicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2 Diphenoxyethane-4 ′, 4 ″ -dicarboxylic acid, anthracene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, diphenylketone dicarboxylic acid and the like can be mentioned, and these can be used alone or in combination of two or more. However, when a polyester polyol is included in the polyol mix, the polyester polyol reacts with water in the polyol mix and tends to cause a decrease in the activity of the catalyst by generating an acid component, so it is not included in the polyol mix. It is preferable.

  A lactone polyester polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and methylvalerolactone may also be used.

  Examples of the polycarbonate polyol include those obtained by a dealcoholization reaction or a dephenol reaction between the short-chain diol, the short-chain triol and the like and a low-molecular carbonate such as ethylene carbonate, diethyl carbonate, and diphenyl carbonate.

  Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

  Examples of animal and plant-based polyols include castor oil-based polyols and silk fibroin.

  Examples of the polymer polyol include a polymer polyol obtained by reacting a polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

  Examples of the halogen-containing polyol include those obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, those obtained by adding alkylene oxide to a brominated polyhydric alcohol, and the like. it can.

  Examples of the phosphorus-containing polyol include those obtained by addition polymerization of alkylene oxide to phosphoric acid, phosphorous acid, organic phosphoric acid, and the like, and those obtained by adding alkylene oxide to polyhydroxypropylphosphine oxide.

  Examples of the phenol-based polyol include a novolak resin obtained from phenol and formalin, a polyol obtained by reacting an alkylene oxide with a resol resin, and a Mannich obtained by reacting an alkylene oxide with a product obtained by reacting a phenol with alkanolamine and formalin. A base polyol etc. can be mentioned.

  Examples of the polyol (b3) include short-chain diols, short-chain triols, low-molecular polyamines, low-molecular amino alcohols and the like having a molecular weight of 50 to 150 among the compounds exemplified as those used for the production of polyether polyols. Can do. Among these, as the state of the bottom surface of the polyurethane slab foam, a short-chain diol having a molecular weight of 50 to 150 that can obtain a good surface property with less unevenness and roughness is preferable. Although not particularly limited, for example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl And glycols such as -1,3-hexanediol.

<Catalyst (C)>
The catalyst (C) of the present invention contains a reactive catalyst having a boiling point of 200 ° C. or higher at normal pressure, such as N, N, N′-trimethylaminoethylethanolamine, N, N-dimethylaminohexanol, 2, (2-dimethylaminoethoxy) ethanol and the like can be mentioned. In the present invention, it is more preferable to use a reactive catalyst having a boiling point of 250 ° C. or higher at normal pressure, such as 2-hydroxymethyltriethylenediamine, N- (2- (2- (dimethylamino) ethoxy) ethyl). -N methyl-1,3-propanediamine, N, N-bis (3-methylaminopropyl) -N-isopropanolamine and the like can be mentioned. Of these, 2-hydroxymethyltriethylenediamine, which has a high effect of promoting the resinification reaction, is most preferable.

  The catalyst (C) of the present invention preferably contains 0.2 to 2% by mass, more preferably 0.4 to 1.5% by mass, with respect to 100% by mass of the polyol component (b). If the catalyst (C) is less than 0.2% by mass, the foam may not be cured and the foam may shrink due to insufficient curing. If it exceeds 2% by mass, the reaction may be too fast to obtain a good foam. There is.

  The catalyst (C) of the present invention includes, as an optional component, a catalyst other than a reactive catalyst having a boiling point of 200 ° C. or higher at normal pressure, a reactive catalyst having a boiling point of less than 200 ° C. at normal pressure, such as dimethylaminopropanol, or dibutyltin dichloride. A tin compound such as acetate and dibutyltin dilaurate, a metal complex compound such as acetylacetone metal salt, and the like may be included without departing from the gist of the present invention.

  In addition, the reactive catalyst in this invention means the amine catalyst which has the hydroxyl group and amino group which react with an isocyanate group in a molecule | numerator.

<Foaming agent (D)>
Water is used as the foaming agent (D) of the present invention. In addition, you may use together a commercially available physical foaming agent, a chemical foaming agent, etc.

  Examples of physical blowing agents include chlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorofluorocarbons, hydrofluoroolefins, hydrofluorocarbons, perfluorocarbons, halogenated hydrocarbons having a low boiling point such as methylene chloride, pentane, and the like. , Hydrocarbons such as cyclopentane, gases such as air, nitrogen and carbon dioxide, or low-temperature liquids. Examples of the chemical blowing agent include water, organic acids, inorganic acids such as boric acid, alkali carbonates, cyclic carbonates, dialkyl carbonates, etc., and generate gas by being decomposed by reaction with polyurethane raw material or heat. And the like.

  Of these, hydrochlorofluoroolefins such as HCFO-1233zd and HFO-1336mzz, and hydrofluoroolefins are preferred because they have a small ozone depletion potential (ODP) and a small global warming potential (GWP).

  The foaming agent (D) of the present invention preferably contains 4 to 7% by mass, more preferably 5 to 6% by mass, with respect to 100% by mass of the polyol component (b). If (D) is less than 4% by mass, the foam density may be high and uneconomical. If it exceeds 7% by mass, internal heat storage due to the heat of reaction between water and isocyanate will increase, resulting in burning inside the foam. There is a possibility that it is likely to occur, and there is a possibility that the mechanical properties are lowered and the foam density is lowered.

<Foam stabilizer (E)>
In the present invention, the foam stabilizer (E) is contained for the purpose of forming a polyurethane slab foam having a good cell structure.

Examples of the foam stabilizer include conventionally known foam stabilizers in the polyurethane industry, and examples thereof include silicone foam stabilizers and fluorine-containing compound foam stabilizers.
Although it does not specifically limit as a foam stabilizer of this invention, For example, "L-540", "L-580", "L-818", "Y-10901C", "Y-10366", "L-3620" ”,“ L-3630 ”,“ L-3039 ”,“ L-5309 ”,“ L-5345 ”,“ L-5420 ”,“ L-6164 ”,“ L-6190 ”,“ L-6661 ”, “L-6900”, “L-6925”, “L-6970” (manufactured by Momentive), “B-8123”, “B-8409”, “B-8443”, “B-8450”, “B-8460”, “B-8462”, “B-8465”, “B-8466”, “B-8486”, “B-8487”, “B-8491”, “B-8495”, “B -8462 "," B-8534 "," B-8547 "," B-85 8 "," B-8871 "," BF-2370 "," BF-8715LF2 "," BF-8724LF2 "," BF-8734LF2 "," BF-8737LF2 "," BF-8742LF2 "," BF-8745LF2 " , “BF-8747LF2” (above, manufactured by Evonik).

  As the foam stabilizer, a foam stabilizer for foam communication may be used or used in combination.

  The foam stabilizer for foam communication is a foam stabilizer that can reduce the closed cell rate of the polyurethane slab foam to be formed, and has excellent mechanical properties such as tensile properties, flexibility and compression properties. A polyurethane slab foam having a high air permeability can be formed without impairing the above.

  As an example of the foam stabilizer for foam communication, it is preferable to use a block copolymer having a linear structure composed of a polysiloxane segment and a polyoxyalkylene segment. This linear structural block copolymer has a cell opening action.

  Examples of foam stabilizers for foam communication include “L-6164”, “L-6186”, “L-6189” (manufactured by Momentive Inc.); “B8934”, “B8935”, “TEGOSTAB VCO” (Above, manufactured by Evonik).

  Although the usage-amount of the foam stabilizer (E) of this invention is not restrict | limited in particular, It is preferable to contain 0.1-3 mass% with respect to 100 mass% of polyol components (b), and 0.1-1 mass% is contained. More preferably. When the foam stabilizer (E) is less than 0.1% by mass, there is a risk of causing deterioration of mechanical properties due to non-uniformity of the cell, and when it exceeds 3% by mass, it may be uneconomical.

<Auxiliary>
The present invention may further contain, for example, a breathability improver, a filler, a stabilizer, a colorant, a flame retardant, an antioxidant and the like as an auxiliary agent (F) as necessary.

  For example, in order to improve the breathability of the foam, a salt of a metal ion with an organic acid such as a higher fatty acid, a resin acid, or naphthenic acid may be contained as the breathability improver (F1). The metal is preferably selected from at least one selected from Na, Ca, and Zn. Specifically, as the air permeability improver (F1), for example, calcium stearate “Ca—St”, sodium stearate “sodium stearate”, zinc stearate “Zn—St”, calcium laurate “Cs-3”, Examples thereof include calcium 12-hydroxystearate “Cs-6CP” and calcium caprylate “C-08N” (Nitto Kasei Kogyo Co., Ltd.).

  Although the usage-amount of the air permeability improvement agent (F1) of this invention is not restrict | limited in particular, it is preferable to contain 0.001-1 mass% with respect to 100 mass% of polyol components (b), 0.005-0.5 More preferably, it is contained by mass%. If the air permeability improver (F1) is less than 0.001% by mass, the effect may not be exhibited. If it exceeds 1% by mass, there is a risk of sedimentation in the polyol mix, which may be uneconomical.

  Further, for example, an antioxidant (F2) may be contained in order to prevent heat accumulation during foaming inside the foam and scorch generation due to oxidation. Representative antioxidants include “I-3015”, “PUR-65”, “PUR-68”, “PUR-70” (above, manufactured by BASF).

  Although the usage-amount in particular of antioxidant (F2) of this invention is not restrict | limited, It is preferable that 0.1-10 mass% is included with respect to 100 mass% of polyol components (b), and 0.5-3 mass% is included. More preferably. When the amount of the antioxidant (F2) is less than 0.1% by mass, the effect may not be exhibited. When the amount exceeds 10% by mass, foam foam may be defective.

  These auxiliary agents (F) may be contained in either the organic polyisocyanate component (A) or the polyol component (B).

<Production method of polyurethane slab foam>
The method for producing a polyurethane slab foam in the present invention is not particularly limited, and a conventionally known method for producing a slab foam can be employed.

  If an example of a manufacturing method is shown here, organic polyisocyanate component (A) and a polyol component (b) will exist in presence of a catalyst (C), a foaming agent (D), and a foam stabilizer (E), A foaming mixture is prepared by mixing with a known agitating mixer, and this is injected into a mold in an open state on the top surface so as to be freely foamed, followed by curing and molding as a slab.

  As another example of the production method, the organic polyisocyanate component (A) and the polyol component (b) are publicly known in the presence of the catalyst (C), the foaming agent (D), and the foam stabilizer (E). There is also a method of preparing a foamable mixture by mixing with a stirring mixer, and continuously discharging the composition to a continuous line in a state where the top surface is open to allow free foaming and curing as a slab.

  From the viewpoint of workability and productivity, the polyol component (b) is organic as a polyol mix (B) in which components including a catalyst (C), a foaming agent (D), and a foam stabilizer (E) are mixed. It is more preferable to react and foam with polyisocyanate.

  The polyurethane slab foam thus produced can be used for various applications. Here, as a preferred mode of use, this slab foam is cut / sliced into a desired shape (planar shape and thickness) to produce a plate-like body, and this plate-like body is used as a liner and affixed to the inner surface of the automobile ceiling. The mode to attach can be mentioned.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

<Example 1>
Each of a polyol mix prepared according to the formulation shown in Table 1 below and a polyisocyanate component shown in the same table were prepared. Moreover, both were previously adjusted to 25 degreeC.

  A polyurethane raw material mixture obtained by stirring and mixing the polyol mixture and the polyisocyanate component at a stirring speed of 6000 rpm for 15 seconds so that the total weight of both is 3800 g at the blending mass ratio shown in Table 1, 50 It was poured into a top open container of × 50 × 50 cm and allowed to foam freely.

  A demolding operation was performed after 1 hour or more from the start time of the stirring and mixing operation to obtain a polyurethane slab foam.

<Examples 2-8, Comparative Examples 1-5>
As in Example 1, free foaming was performed in the same manner as in Example 1 with the formulation shown in Table 1 to obtain a polyurethane slab foam.

Various raw materials in Table 1 are as follows.
Polyol b1: Polyether polyol having a molecular weight of 6000 with addition of propylene oxide and ethylene oxide to glycerin and having 3 functional groups (trade name: NJ-360N, manufactured by JURONG NINGWU), molecular weight per functional 2000
Polyol b2-1: Polyether polyol having a molecular weight of 700 and a functional group number of 3 obtained by adding propylene oxide to glycerin (trade name: G-700, manufactured by Kaika Chemical Co., Ltd.), molecular weight of 233 per function
Polyol b2-2: Polyether polyol having a molecular weight of 300 obtained by adding propylene oxide to glycerin and having 3 functional groups (trade name: G-300, manufactured by Kaika Chemical Co., Ltd.), molecular weight of 100 per function
Polyol b2-3: Polyether polyol having a molecular weight of 600 obtained by adding ethylene oxide to glycerin and a functional group number of 3 (trade name: GE-600, manufactured by Sanyo Chemical Industries, Ltd.), molecular weight per functional group of 100
Polyol b3-1: 1,4-butanediol (Mitsubishi Chemical Corporation), molecular weight 45 per functionality
Polyol b3-2: Glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), molecular weight per functionality 31
-Foam stabilizer E-1: Brand name L-6168 (made by Momentive)
-Foam stabilizer E-2: Brand name B-8462 (Evonik)
・ Foam stabilizer E-3: Product name L-6186 (Mormotive)
・ Auxiliary agent F1-1: Product name Sodium stearate (Breathability improver, Nitto Kasei Kogyo)
-Auxiliary agent F1-2: Trade name Zn-St (Breathability improver, Nitto Kasei Kogyo)
・ Auxiliary agent F2-1: Product name PUR-68 (Antioxidant, manufactured by BASF)
・ Catalyst C-1: Reactive catalyst based on 2-hydroxymethyltriethylenediamine (trade name: RZETA manufactured by Tosoh Corporation), boiling point 250 ° C. or higher ・ Catalyst C-2: N, N, N′-trimethylaminoethyl Ethanolamine (trade name: TOYOCAT-RX5, manufactured by Tosoh Corporation), boiling point 200 ° C. or higher, catalyst C-3: N, N-dimethyl-2-aminoethanol (Tokyo Chemical Industry Reagent), boiling point 133 ° C.
Catalyst C-4: N, N, N ′, N′-tetramethylhexamethylenediamine (trade name: KAOLIZER NO.1, manufactured by Kao Corporation), boiling point 198 ° C.
-Polymeric MDI containing 68% by mass of MDI (A1) in which the ratio of isocyanate A-1: 4,4′-MDI is 71% by mass, NCO content 32% by mass
-Polymeric MDI containing 79% by mass of MDI (A1) in which the ratio of isocyanate A-2: 4,4′-MDI is 62% by mass, NCO content 32% by mass.

<Evaluation>
<Reactivity>
Cream time (CT), gel time (GT), health bubble time (HBT), and rise time (RT) were measured as reaction times in the foaming / curing molding process.
Cream time (CT): foaming start time, and the time for starting foaming was measured visually.
Gel time (GT): It is the time when the polyurethane foam begins to harden, and the time when the stringing phenomenon occurs when a thin rod-like object is stabbed into the foamed foam and pulled out, or the time when resistance was felt when stabbed was measured.
Health bubble time (HBT): The time when bubble holes appear on the foam surface was measured visually.
Rise time (RT): The time for the polyurethane foam to stop rising was measured visually.

<Foam density>
The obtained polyurethane slab foam has a side face of 15 cm cut in the foaming direction, the foamed upper and lower faces are cut off by 5 cm, the center part is cut into 20 cm vertically and horizontally, the height direction is divided into three equal parts, and the density is measured from the weight and volume. The average value of the upper, middle and lower three points was calculated.

<Odor>
Twelve 3x3x3cm samples were cut out from the center of the foam, and after curing in a glass bottle for 1 week at room temperature, the odor in the glass bottle was sniffed by five people and the odor intensity was evaluated. The number of people who evaluated that the odor was not worried was 4 or more, and 3 or less.

<Flexibility>
Evaluate the state when the foam density is measured from the top, middle, and bottom three-point foam sliced to 5mm thickness and bent.
Can't break: ○, can break: ×.

<Air permeability>
The air permeability of the slice foam evaluated for flexibility was measured according to JIS K6400-7.
Air permeability: 1.0 cm ³ / cm ² / sec or more can be said to be good.

<Bottom condition>
The position of 15 cm from the side surface of the obtained polyurethane slab foam was cut in the foaming direction, and the height from the bottom of the air void seen at the bottom of the cut surface and the amount of foam rising from the bottom of the cut surface were measured.
・ Both air void and foam deformation are less than 1cm from the bottom: ○
・ At least one of air void and foam deformation is 1 cm or more and less than 3 cm from the bottom: Δ
-At least one of air void and foam deformation is 3 cm or more from the bottom: x.

<Tensile strength, elongation>
Sliced to 5mm thickness from the top, middle, and bottom 3 foams where the foam density was measured, according to the Chinese national standard GB9641-88, the average value of the values measured at each position 6 points.
Tensile strength: 15 N / cm ² or more is good.
Elongation: 10% or more can be said to be good.

Claims (12)

  A composition for forming a polyurethane slab foam for automobile molded ceiling comprising an organic polyisocyanate component (A) and a polyol mix (B), wherein the polyol mix (B) comprises a polyol component (b), a catalyst (C), The polyol component (b) contains a foaming agent (D) and a foam stabilizer (E), and the polyol (b1) having a molecular weight of 1,500 or more per function is 20 to 50% by mass and the molecular weight per function is Reactivity having a boiling point of 200 ° C. or more as a catalyst (C), comprising 40 to 70 mass% of polyol (b2) of 100 or more and less than 1500 and 1 to 10 mass% of polyol (b3) having a molecular weight of less than 100 per functional group. A composition for forming a polyurethane slab foam for automobile molded ceiling, comprising a catalyst and water as a foaming agent (D).   The composition for forming a polyurethane slab foam for automobile molded ceiling according to claim 1, wherein the polyol mix (B) does not contain a polyester polyol.   The composition for forming a polyurethane slab foam for automobile molded ceiling according to claim 1 or 2, wherein the polyol (b3) is a diol having a molecular weight per functional group of less than 100.   The composition for forming a polyurethane slab foam for automobile molded ceiling according to any one of claims 1 to 3, wherein the catalyst (C) contains 2-hydroxymethyltriethylenediamine.   The automobile molded ceiling according to any one of claims 1 to 4, further comprising a salt of an organic acid and at least one metal ion selected from Na, Ca, and Zn as the auxiliary agent (F). Composition for forming polyurethane slab foam.   A polyurethane slab foam for automobile molded ceiling obtained from the composition for forming a polyurethane slab foam for automobile molded ceiling according to any one of claims 1 to 5.   A method for producing a polyurethane slab foam for automobile molded ceiling obtained by reacting and foaming an organic polyisocyanate component (A) and a polyol mix (B), wherein the polyol mix (B) is a polyol component (b). , A catalyst (C), a foaming agent (D), a foam stabilizer (E), and an auxiliary agent (F), and a polyol (b1) having a molecular weight per functional of 1500 or more in the polyol component (b). 20 to 50% by weight, polyol (b2) having a molecular weight per function of 100 to less than 1500 to 40 to 70% by weight, 1 to 10% by weight of polyol (b3) having a molecular weight per function of less than 100, and catalyst (C) includes a reactive catalyst having a boiling point of 200 ° C. or higher, includes water as a foaming agent (D), and isocyanate groups and polyols in the organic polyisocyanate component (A). The molar ratio of the hydroxyl group in the box (B), characterized by foaming the isocyanate group / hydroxyl group = 0.9 to 1.5, polyurethane slab foam production method for a motor vehicle molded roof.   The method for producing a polyurethane slab foam for automobile molded ceiling according to claim 7, wherein the polyol mix (B) does not contain a polyester polyol.   The method for producing a polyurethane slab foam for automobile molded ceiling according to claim 7 or 8, wherein the polyol (b3) is a diol having a molecular weight per functional group of less than 100.   The method for producing a polyurethane slab foam for automobile molded ceiling according to any one of claims 7 to 9, wherein the catalyst (C) contains 2-hydroxymethyltriethylenediamine.   The auxiliary agent (F) contains a salt of an organic acid and at least one metal ion selected from Na, Ca, and Zn, for automobile molded ceilings according to any one of claims 7 to 10. A method for producing polyurethane slab foam.   A vehicle ceiling material using the polyurethane slab foam for automobile molded ceiling according to claim 6.