WO2015098035A1 - 半硬質ポリウレタンフォーム形成用組成物 - Google Patents
半硬質ポリウレタンフォーム形成用組成物 Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/16—Catalysts
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- C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
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- C08G2110/00—Foam properties
- C08G2110/0016—Foam properties semi-rigid
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- C08G2110/00—Foam properties
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- C08G2110/005—< 50kg/m3
Definitions
- the present invention relates to a composition for forming a semi-rigid polyurethane foam, and more particularly to a composition for forming a semi-rigid polyurethane foam suitable for an interior member such as a crash pad of a vehicle instrument panel.
- the above production method has a problem that the curing time is long and the moldability is insufficient.
- the production method described in Patent Document 2 by combining a polyol component composed of a polyol having a specific structure, a specific isocyanate component and a catalyst, the curing property and the moldability are improved and the productivity is improved. It has improved.
- An object of the present invention is to provide a composition for forming a semi-rigid polyurethane foam suitable for an automobile interior material that has low hardness, rebound, and is excellent in moldability and curing even when lightened (thinned). To do.
- the present inventor has intensively studied to solve these problems, and has found that moldability and curing properties are excellent by using a semi-rigid polyurethane foam-forming composition containing a specific polyol (composition).
- the present invention has been completed.
- the present invention comprises the following polyol (composition) (A), a foaming agent (C) containing water and a polyol mixture (P) containing a catalyst (D) and a polyisocyanate component (B).
- the content of the vinyl monomer polymer is 0 to 7% by weight based on the total weight of (A), and the following polyether polyol (A21) is contained in (A2).
- composition for forming a semi-rigid polyurethane foam of the present invention is excellent in moldability and curing properties when the thickness of the foam is thinned, and the semi-rigid polyurethane foam obtained by forming this has a soft feeling and a repulsive feeling, High tactile sensation.
- the polyol (composition) (A) used in the composition for forming a semi-rigid polyurethane foam of the present invention is a polymer obtained by polymerizing a vinyl monomer in the presence of a radical polymerization initiator in a polyether polyol (a).
- the polyol (A1) and / or the polyether polyol (A2) is contained, and the content of the vinyl monomer polymer is 0 to 7% by weight based on the total weight of (A).
- Ether polyol (A21) is contained, and the content of (A21) is 50 to 100% by weight based on the total weight of the polyether polyol in the polyol (composition) (A).
- the polyol (composition) (A) may be a single polyol or a mixture of two or more polyols.
- the polyol (composition) (A) in the present invention may be a polymer polyol (A1) alone, a polyether polyol (A2) alone, or a mixture of (A1) and (A2). From the viewpoint of properties, (A2) alone and a mixture of (A1) and (A2) are preferred, and a mixture of (A1) and (A2) is more preferred.
- Polyether polyols (a) and (A2) include ethylene oxide (hereinafter abbreviated as EO) of a compound containing 2 to 8 or more active hydrogens (polyhydric alcohol, polyhydric phenol and amine) and Examples include 1,2-propylene oxide (hereinafter abbreviated as PO) adducts, and two or more types may be used in combination.
- EO ethylene oxide
- PO 1,2-propylene oxide
- polyhydric alcohols include dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, , 6-hexanediol, neopentyl glycol, cyclohexanediol and cyclohexanedimethanol, etc.], alcohols having 3 to 8 or more carbon atoms with 3 to 12 carbon atoms [glycerin, trimethylolpropane, pentaerythritol, diglycerin, ⁇ -methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose, etc.] and combinations of two or more thereof.
- dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, 1,3
- Polyhydric phenols include monocyclic polyphenols (such as pyrogallol and hydroquinone), bisphenols (such as bisphenol A, bisphenol F, and bisphenol sulfone), and low formalin condensates (novolac resins and resole resins) of phenolic compounds (such as phenol and cresol). Intermediates) and combinations of two or more thereof.
- amines include those having 2 to 8 or more active hydrogens; ammonia; alkanolamines [monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, aminoethylethanolamine, etc.]; Alkylamines having 20 to 20 [methylamine, ethylamine, n-butylamine, octylamine and the like]; alkylenediamines having 2 to 6 carbon atoms [ethylenediamine and hexamethylenediamine and the like]; polyalkylene polyamines (the alkylene group having 2 to 6 carbon atoms) Dialkylenetriamine to hexaalkyleneheptamine) [diethylenetriamine and triethylenetetramine, etc.]; aromatic mono- or polyamines having 6 to 20 carbon atoms [aniline, phenylenediamine, diaminotoluene, xylylene Amines, methylene dianilines and diphenyl ether diamines,
- a polyhydric alcohol is preferable from the viewpoint of the hardness retention of the foam after heat aging and the liquid flow of the foam. More preferred are dihydric alcohols having 2 to 4 carbon atoms and tri to octavalent alcohols having 3 to 12 carbon atoms.
- the addition method of EO and PO may be block addition or random addition, but block addition is preferable, and EO is added to the terminal and, if necessary, inside. More preferred are those obtained by adding a block.
- the number average molecular weights of (a) and (A2) are preferably 3000 to 25000, more preferably 4000 to 20000, and particularly preferably 5000 to 18000 from the viewpoints of foam hardness and liquid flowability of the mixed solution.
- the weight percentage of EO added to (a) and (A2) is preferably from the viewpoint of foam moldability and foam hardness.
- the hydroxyl value (mgKOH / g) of (a) and (A2) is preferably from 15 to 300, more preferably from 20 to 50, and particularly preferably from 24 to 50, from the viewpoint of foam hardness and liquid flowability of the mixed liquid. 35.
- the hydroxyl value in the present invention is determined according to JISK-1557-1. Moreover, the number average molecular weight in this invention is calculated
- the average number of functional groups of the polyether polyol means the average number of hydroxyl groups that the polyether polyol has in one molecule, and the average of the entire polyether polyols (a) and (A2) in the polyol (composition) (A).
- the number of functional groups is preferably 5.5 to 8, and more preferably 6 to 7.5. In the case of a mixture of a plurality of polyether polyols, for example, even if the number of individual functional groups is outside the range of 5.5 to 8, if the average number of weighted average functional groups is within the range of 5.5 to 8, the average functionality
- the radix is 5.5-8.
- the average number of functional groups of the polyether polyol (A21) contained as an essential component in the polyether polyol (A2) is 7.8 to 8.2. From the viewpoint of the resilience and liquid flow properties of the foam, 7.9 ⁇ 8.1 is preferred. When the average number of functional groups is less than 7.8, the impact resilience is low, and when it exceeds 8.2, the liquid flowability of the foam decreases.
- (A21) has a hydroxyl value (mgKOH / g) of 20 to 50, preferably 25 to 40 from the viewpoint of foam hardness.
- the total content of EO units of (A21) is 8 to 30% by weight based on the total weight of (A21), and is preferably 10 to 20% by weight from the viewpoint of foam curing time and foam liquid flow.
- the total content of EO units in (A21) is less than 8% by weight, the curing time of the foam becomes long, and when the total content of EO units exceeds 30% by weight, the curing time of the foam is short and the liquid flow of the foam becomes worse.
- the content of the terminal EO unit in (A21) is 5 to 25% by weight, and is preferably 10 to 20% by weight from the viewpoint of foam curing time and foam liquid flow.
- the content of the terminal EO unit in (A21) is less than 5% by weight, the curing time of the foam becomes long.
- the content of the terminal EO unit exceeds 25% by weight the curing time of the foam is short, and the liquid flow of the foam becomes worse.
- the number average molecular weight of (A21) is preferably 5000 to 25000, more preferably 8000 to 20000, and particularly preferably 12000 to 18000 from the viewpoints of foam hardness and liquid flowability of the mixed solution.
- the content of the polyether polyol (A21) is 50 to 100% by weight based on the total weight of the polyether polyol [(a) and / or (A2)] in the polyol (composition) (A). From the viewpoint of the resilience of the foam, 70 to 100% by weight is preferable. From the same viewpoint, it is preferably 70 to 90% by weight based on the weight of the polyol (composition) (A). When the content of (A21) in the polyether polyol in (A) is less than 50% by weight, the resilience of the foam is lowered.
- the polymer polyol (A1) in the present invention can be produced by polymerizing a vinyl monomer in a polyether polyol (a) in the presence of a radical polymerization initiator by an ordinary method.
- vinyl monomers examples include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl (2 to 5 carbon atoms) (meth) acrylate, and alkyl (1 to 5 carbon atoms) (meth) acrylate.
- acrylonitrile and styrene are preferable from the viewpoints of dispersion stability and foam hardness.
- the content of the vinyl monomer polymer is 0 to 7% by weight based on the total weight of (A) from the viewpoint of the hardness retention of the foam after heat aging and the resilience of the foam, and 0 to 6% by weight. 1 to 6% by weight is more preferable.
- radical polymerization initiator those that generate a free radical to initiate polymerization can be used.
- the polymer polyol (A1) contains a polymer polyol (A11) obtained by polymerizing a vinyl monomer in the presence of a radical polymerization initiator in the following polyether polyol (a1) from the viewpoint of hardness. Is preferred.
- Polyether polyol (a1) Polyoxyethylene polyoxypropylene polyol having an average functional group number of 2.8 to 4.2, a hydroxyl value of 15 to 38 (mg KOH / g), and the total number of EO units
- the average functional group number of (a1) is 2.8 to 4.2, preferably 3.8 to 4.1.
- the hydroxyl value (mgKOH / g) of (a1) is 15 to 38, preferably 20 to 35, from the viewpoints of foam hardness and liquid flowability of the mixed solution.
- the total content (% by weight) of EO units in (a1) is 5 to 40%, preferably 8 to 35%, particularly preferably 10 to 30%, from the viewpoint of foam moldability and foam hardness. It is.
- the number average molecular weight of (a1) is preferably 3000 to 20000, more preferably 4000 to 18000, and particularly preferably 5000 to 16000 from the viewpoints of the hardness of the foam and the liquid flowability of the mixed solution.
- the polyol (composition) (A) used in the present invention contains the polymer polyol (A11) in addition to the polyether polyol (A21), from the viewpoint of the hardness retention of the foam after heat aging, Particularly preferred are those in which the content of (A21) in A) is 70 to 90% by weight and the content of (A11) is 5 to 25% by weight.
- polyisocyanate component (B) used in the composition for forming a semi-rigid polyurethane foam of the present invention a polyisocyanate usually used in the production of polyurethane may be used, but for reasons such as improvement of productivity and improvement of work environment, What contains 1 or more types chosen from the group of diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and these modified products is preferable.
- the modified products include urethane-modified products, carbodiimide-modified products, allophanate-modified products, urea-modified products, burette-modified products, isocyanurate-modified products, and oxazolidone-modified products.
- the NCO content of (B) is preferably 20 to 30% by weight, more preferably 25 to 29% by weight, from the viewpoint of foam hardness / rebound resilience and liquid flow during foam production.
- water is an essential component, and water can be used alone or in combination with other foaming agents. From the viewpoint of moldability, it is preferable to use water alone.
- Examples of other foaming agents include liquefied carbon dioxide gas and low boiling point compounds having a boiling point of ⁇ 5 to 70 ° C.
- Low boiling point compounds include hydrogen atom-containing halogenated hydrocarbons and low boiling point hydrocarbons.
- Specific examples of hydrogen atom-containing halogenated hydrocarbons and low-boiling hydrocarbons include HCFC (hydrochlorofluorocarbon) ⁇ HCFC-123, HCFC-141b, HCFC-142b, etc. ⁇ ; HFC (hydrofluorocarbon) ⁇ HFC-152a, HFC -356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, etc. ⁇ , butane, pentane, cyclopentane and the like.
- the content of the foaming agent (C) is 1.5 to 2.5% by weight based on the weight of the polyol (composition) (A). From the viewpoint of moldability of the foam, the content is preferably 1.6 to 2.2% by weight, more preferably 1.7 to 2.1% by weight. When the content of (C) is less than 1.5% by weight, the liquid flowability at the time of foam production is deteriorated, and when it is more than 2.5% by weight, molding defects such as foam expansion occur.
- any catalyst that promotes any urethanization reaction commonly used in the art can be used, and triethylenediamine, triethylamine, triethanolamine.
- the amount of the catalyst (D) used is preferably from 1.0 to 3.5% by weight, more preferably from 1.5 to 3.5% by weight based on the weight of the polyol (composition) (A) from the viewpoint of moldability of the foam. 3.0% by weight.
- a foam stabilizer (E) can be used in the polyol mixture (P) if necessary.
- any of those used for the production of ordinary polyurethane foams can be used, and dimethylsiloxane foam stabilizers such as “SRX-253” and “PRX-607” manufactured by Toray Dow Corning Co., Ltd.
- the amount of the foam stabilizer used is preferably 0.1 to 5.0% by weight, more preferably, based on the weight of the polyol (composition) (A), from the viewpoints of polyurethane foam moldability and foam discoloration. 0.5 to 1.0% by weight.
- a crosslinking agent (F) can be used in the polyol mixture (P) if necessary.
- (F) all those used for the production of ordinary polyurethane foams can be used, and examples thereof include polyhydric alcohols, polyhydric phenols and amines.
- Polyhydric alcohols include dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butylene glycol, diethylene glycol.
- neopentyl glycol, etc. alcohols with 3 to 8 or more carbon atoms having 3 to 12 carbon atoms [glycerin, trimethylolpropane, pentaerythritol, diglycerin, ⁇ -methylglucoside, sorbitol, xylitol, mannitol, glucose , Fructose, sucrose, etc.].
- Polyhydric phenols include monocyclic polyhydric phenols (hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, etc.), formalin low condensates of phenolic compounds (phenol, cresol, etc.) (intermediates of novolac resins and resol resins), etc. Is mentioned.
- amines include alkanolamines [monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, aminoethylethanolamine, etc.]; alkylamines having 1 to 20 carbon atoms [methylamine, ethylamine, n-butylamine, octylamine, etc.]; Carbon 2-6 alkylene diamine [ethylene diamine and hexamethylene diamine, etc.]; polyalkylene polyamine (alkylene group having 2-6 carbon atoms, dialkylene triamine to hexaalkylene heptamine) [diethylene triamine, triethylene tetramine, etc.]; carbon Aromatic mono- or polyamines of 6 to 20 [aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyl ether diamine, etc.] C4-C15 alicyclic amines [isophoronediamine, cyclo
- an anti-aging agent such as an antioxidant (such as hindered phenol and hindered amine) and an ultraviolet absorber (such as triazole and benzophenone); an inorganic salt (such as calcium carbonate and barium sulfate) in the polyol mixture (P) if necessary.
- Fillers such as inorganic fibers (such as glass fibers and carbon fibers), whiskers (such as potassium titanate whiskers); flame retardants (such as phosphate esters), adhesives (such as modified polycaprolactone polyols); plasticizers (phthalic acid) Esters and the like); colorants (dyes and pigments); antibacterial agents; antifungal agents; and the like, conventionally known additives and auxiliaries can be used.
- ⁇ 100] is preferably 70 to 140, more preferably 75 to 130, and particularly preferably 80 to 120, from the viewpoint of the curing property of the foam and the moldability of the foam.
- the composition for forming a semi-rigid polyurethane foam of the present invention can be used for producing a semi-rigid polyurethane foam such as an automobile interior material.
- a method for producing a crash pad for an instrument panel for a vehicle comprising a step of injecting the foam composition for forming a semi-rigid polyurethane foam of the present invention into a mold for crash pad, and foaming and curing the mold. It is preferable to use for.
- compositions for forming a semi-rigid polyurethane foam of the present invention are as follows. First, a polyol (composition) (A), a foaming agent (C), a catalyst (D), and other additives / auxiliaries as required are mixed in predetermined amounts to prepare a polyol mixture (P). Next, the polyol mixture (P) and the polyisocyanate component (B) are rapidly mixed using a polyurethane foaming machine (low pressure or high pressure foaming machine, preferably a high pressure foaming machine) or a stirrer.
- a polyurethane foaming machine low pressure or high pressure foaming machine, preferably a high pressure foaming machine
- the obtained mixed solution is poured into a closed injection type crush pad mold (preferably the mold temperature is 25 to 50 ° C.) in which the skin and the base material are set on each side, foamed and cured, and predetermined. After time, demolding to obtain a semi-rigid polyurethane foam having a uniform density distribution.
- an additive, an auxiliary agent, etc. can also be mixed and used for the polyisocyanate component (B).
- the filling rate during injection [(density at the time of mold foaming / density at the time of free foaming) ⁇ 100] is preferably 100 to 400%, particularly preferably 150 to 350%.
- the method for producing a semi-rigid polyurethane foam according to the present invention has a cream time of 3 to 5 seconds when a mixture of a polyol mixture (P) and a polyisocyanate component (B) is foamed and cured at a liquid temperature of 25 ° C.
- a step of adjusting, a step of adjusting the gel time to 15 to 25 seconds, and a step of adjusting the rise time to 25 to 40 seconds According to the production method of the present invention, good liquid flowability is exhibited during molding.
- the amount of catalyst (D) used may be adjusted.
- the amount of amine catalyst preferably bis (N, N-dimethylaminoethyl) ether or N, N-dimethylaminopropyldipropanolamine may be increased.
- the amount of amine-based catalyst and / or organometallic compound, preferably a tertiary amine catalyst ("Kaorizer P-200" manufactured by Kao Corporation, triethylenediamine, etc.) may be increased.
- the production method of the present invention preferably further includes a step of adjusting the curing time within 60 seconds when foamed and cured in a mold for crash pad at 40 ° C. at a liquid temperature of 25 ° C.
- the curing time means the time from the start of injection of the raw material (polyurethane foam forming composition) to the start of mold opening when injected into the mold under the same conditions as the cream time. If the mold is opened with insufficient curing, the crash pad will be deformed.
- the amount of the catalyst (D) used may be adjusted.
- the amount of amine-based catalyst and / or organometallic compound, preferably a tertiary amine catalyst (“KAOLIZER P-200” manufactured by Kao Corporation, triethylenediamine, etc.) may be increased.
- a tertiary amine catalyst (“KAOLIZER P-200” manufactured by Kao Corporation, triethylenediamine, etc.)
- the semi-rigid polyurethane foam formed by injecting into the mold for crash pad under the above conditions using the semi-rigid polyurethane foam-forming composition of the present invention has a density of 0.20 to 0.25 g / cm 3.
- a polyurethane foam having a C hardness of 8 to 20 (preferably 8 to 16) and a rebound resilience of 28 to 35% (preferably 29 to 33%) can be obtained.
- Tables 1 and 2 show the measurement results of the moldability and physical property values of the obtained foams. In Tables 1 and 2, the amount of materials used is shown in parts by weight. The amount of the polyisocyanate component charged is indicated by an isocyanate index.
- Each component in Table 1 and Table 2 is as follows.
- D-1) Tertiary amine catalyst ["Kaorizer P-200” manufactured by Kao Corporation]
- D-2) 70% diethylene glycol solution of bis (N, N-dimethylamino-2-ethyl) ether [“TOYOCAT-ET” manufactured by Tosoh Corporation]
- D-3) Polyurethane catalyst ["DABCO NE300" manufactured by Air Products Japan Co., Ltd.]
- E-1) Organically modified polysiloxane preparation [Degussa Japan Co., Ltd. “Tegostarb B
- the reactivity evaluation method is as follows.
- Cream time In the urethanization reaction, when the liquid temperature of the raw material [polyol mixture (P) and polyisocyanate component (B)] immediately before the reaction is 25 ° C. and freely foamed in a wooden box of 20 cm ⁇ 20 cm ⁇ 30 cm, Time (seconds) from the time the raw material is injected to the time when foaming starts.
- Gel time The time (second) when the polyol mixture (P) and the polyisocyanate component (B) are mixed, and then the viscosity starts to increase and the gel strength begins to appear (resinization).
- Rise time Time (seconds) in which the rise of the foamed foam stops after the mixing of the polyol mixture (P) and the polyisocyanate component (B) is started.
- the formability evaluation methods in Tables 1 and 2 are as follows. Liquid flowability: Appearance when removed from the mold was confirmed and evaluated according to the following criteria. ⁇ : There is a lack of thickness. ⁇ : There is void or cell roughness at the end of the molded product. ⁇ : There is no void or cell roughness at the end of the molded product. Curing property: Take out the foam from the mold and weigh 5 kg against the foam. The degree of deformation of the foam when the load was applied for 3 seconds was confirmed and evaluated according to the following criteria. ⁇ : Deformation of 5 mm or more ⁇ : Deformation of 1 mm or more and less than 5 mm ⁇ Deformation of less than 1 mm ⁇ : No deformation
- compositions for forming semi-rigid polyurethane foams of Examples 1 to 14 were superior in both liquid flowability and curing properties as compared with Comparative Examples 1 to 5 in which the amount of polyol (composition) and foaming agent was changed.
- the semi-rigid polyurethane foam obtained by forming has a soft feeling, a repulsive feeling, and a high touch feeling.
- the automotive interior material produced using the composition for forming a semi-rigid polyurethane foam according to the present invention is superior in curing property and moldability as compared with the conventional method, and has a soft feeling and a rebound feeling. Since it is possible to obtain an automotive interior material that has a tactile sensation, it exhibits remarkable utility as an automotive interior material.
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Abstract
Description
ポリオール(組成物)(A):ポリエーテルポリオール(a)中でラジカル重合開始剤の存在下、ビニルモノマーが重合されて得られる重合体ポリオール(A1)及び/又はポリエーテルポリオール(A2)を含有し、ビニルモノマーの重合体の含有量が(A)の合計重量を基準として0~7重量%であり、(A2)中に下記ポリエーテルポリオール(A21)を含有しており、(A21)の含有量がポリオール(組成物)(A)中のポリエーテルポリオールの合計重量を基準として50~100重量%であるポリオール(組成物)。
ポリエーテルポリオール(A21):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が7.8~8.2であり、水酸基価が20~50(mgKOH/g)であり、末端オキシエチレン単位の含有量が5~25重量%であり、オキシエチレン単位の合計含有量が8~30重量%であるポリエーテルポリオール。
ポリエーテルポリオール(A21):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が7.8~8.2であり、水酸基価が20~50(mgKOH/g)であり、末端オキシエチレン単位の含有量が5~25重量%であり、オキシエチレン単位の合計含有量が8~30重量%であるポリエーテルポリオール。
本発明におけるポリオール(組成物)(A)としては、重合体ポリオール(A1)単独でも、ポリエーテルポリオール(A2)単独でも、(A1)と(A2)との混合物でもよいが、フォームの液流れ性の観点から、(A2)単独及び(A1)と(A2)との混合物が好ましく、(A1)と(A2)との混合物がさらに好ましい。
多価フェノールとしては、単環多価フェノール(ピロガロール及びハイドロキノン等)、ビスフェノール(ビスフェノールA、ビスフェノールF及びビスフェノールスルホン等)、フェノール化合物(フェノール及びクレゾール等)のホルマリン低縮合物(ノボラック樹脂及びレゾール樹脂の中間体)及びこれらの2種以上の併用が挙げられる。
これらの中では、熱老化後のフォームの硬度保持率やフォームの液流れの観点から、多価アルコールが好ましい。更に好ましくは、炭素数2~4の2価アルコール、炭素数3~12の3~8価のアルコールである。
(a)及び(A2)の数平均分子量は、フォームの硬さ及び混合液の液流れ性の観点から、好ましくは3000~25000、さらに好ましくは4000~20000、特に好ましくは5000~18000である。
(a)及び(A2)の付加したEOの重量%〔すなわち、オキシエチレン単位(以下、EO単位と略記する)の含有量〕は、フォームの成形性及びフォームの硬さの観点から、好ましくは5~40%、さらに好ましくは8~35%、特に好ましくは10~30%である。
(a)及び(A2)の水酸基価(mgKOH/g)は、フォームの硬さ及び混合液の液流れ性の観点から、好ましくは15~300、さらに好ましくは20~50、特に好ましくは24~35である。
また、本発明における数平均分子量は、GPC(ゲル浸透クロマトグラフィー)により下記測定条件により求められる。
<GPCの測定条件>
カラム:TSK gel SuperH4000、TSK gel SuperH3000及びTSK gel SuperH2000(いずれも東ソー株式会社製)
カラム温度:40℃
検出器:RI
溶媒:テトラヒドロフラン
流速:0.6ml/分
試料濃度:0.25重量%
注入量:10μl
標準:ポリオキシエチレングリコール(東ソー株式会社製;TSK STANDARDPOLYETHYLENE OXIDE)
データ処理装置:SC-8020(東ソー株式会社製)
平均官能基数=[ポリエーテルポリオールの数平均分子量]×[水酸基価]/56100
ポリエーテルポリオール(a1):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が2.8~4.2であり、水酸基価が15~38(mgKOH/g)であり、EO単位の合計含有量が5~40重量%であるポリエーテルポリオール。
(a1)の水酸基価(mgKOH/g)は、フォームの硬さ及び混合液の液流れ性の観点から、15~38であり、好ましくは20~35である。
(a1)のEO単位の合計含有量(重量%)は、フォームの成形性及びフォームの硬さの観点から、5~40%であり、好ましくは8~35%、特に好ましくは10~30%である。
(a1)の数平均分子量は、フォームの硬さ及び混合液の液流れ性の観点から、好ましくは3000~20000、さらに好ましくは4000~18000、特に好ましくは5000~16000である。
低沸点化合物には、水素原子含有ハロゲン化炭化水素及び低沸点炭化水素等が含まれる。水素原子含有ハロゲン化炭化水素及び低沸点炭化水素の具体例としては、HCFC(ハイドロクロロフルオロカーボン){HCFC-123、HCFC-141b及びHCFC-142b等};HFC(ハイドロフルオロカーボン){HFC-152a、HFC-356mff、HFC-236ea、HFC-245ca、HFC-245fa及びHFC-365mfc等}、ブタン、ペンタン及びシクロペンタン等が挙げられる。
触媒(D)の使用量は、フォームの成形性の観点から、ポリオール(組成物)(A)の重量に基づいて、1.0~3.5重量%が好ましく、さらに好ましくは1.5~3.0重量%である。
多価フェノールとしては、単環多価フェノール(ハイドロキノン等)、ビスフェノール(ビスフェノールA、ビスフェノールF等)、フェノール化合物(フェノール及びクレゾール等)のホルマリン低縮合物(ノボラック樹脂及びレゾール樹脂の中間体)等が挙げられる。
アミンとしては、アルカノールアミン[モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、イソプロパノールアミン及びアミノエチルエタノールアミン等];炭素数1~20のアルキルアミン[メチルアミン、エチルアミン、n-ブチルアミン及びオクチルアミン等];炭素数2~6のアルキレンジアミン[エチレンジアミン及びヘキサメチレンジアミン等];ポリアルキレンポリアミン(アルキレン基の炭素数が2~6のジアルキレントリアミン~ヘキサアルキレンヘプタミン)[ジエチレントリアミン及びトリエチレンテトラミン等];炭素数6~20の芳香族モノ又はポリアミン[アニリン、フェニレンジアミン、ジアミノトルエン、キシリレンジアミン、メチレンジアニリン及びジフェニルエーテルジアミン等];炭素数4~15の脂環式アミン類[イソホロンジアミン、シクロヘキシレンジアミン等];炭素数4~15の複素環式アミン[アミノエチルピペラジン及び特公昭55-21044号公報記載のもの等]及びこれらの2種以上の併用等が挙げられる。
フォームのキュア性の観点から、アミンが好ましい。
次いでポリウレタン発泡機(低圧又は高圧発泡機、好ましくは高圧発泡機)又は攪拌機を使用して、ポリオール混合物(P)とポリイソシアネート成分(B)とを急速混合する。得られた混合液を、表皮と基材をそれぞれ片面ずつにセットしたクローズ注入タイプのクラッシュパッド用成形型(好ましくは成型型の温度が25~50℃)に注入し、発泡し硬化させ、所定時間後脱型して、均一な密度分布を有する半硬質ポリウレタンフォームを得る。なお、添加剤、助剤等は、ポリイソシアネート成分(B)に混合して用いることもできる。注入する際の充填率〔(モールド発泡時の密度/フリー発泡時の密度)×100〕は、100~400%であることが好ましく、特に150~350%が好ましい。
本発明の製造方法によれば、成形時に良好な液流れ性を示す。
本発明の製造方法において、クリームタイム、ゲルタイム、ライズタイムを調整するには、例えば、触媒(D)の使用量を調整すればよい。クリームタイム、ライズタイムを促進するには、アミン系触媒、好ましくはビス(N,N-ジメチルアミノエチル)エーテル、N,N-ジメチルアミノプロピルジプロパノールアミンの使用量を増加すればよい。ゲルタイムを促進するには、アミン系触媒及び又は有機金属化合物、好ましくは3級アミン触媒〔(株)花王製「カオライザーP-200」、トリエチレンジアミン等〕の使用量を増加すればよい。
キュア時間とは、前記のクリームタイムと同条件で、金型に注入した際の、原料(ポリウレタンフォーム形成用組成物)の注入開始から型開きを開始するまでの時間を意味する。硬化が不十分な状態で、型開きをおこなうと、クラッシュパッドが変形する。
本発明の製造方法において、キュア時間を調整するには、例えば、触媒(D)の使用量を調整すればよい。キュア時間を促進するには、アミン系触媒及び又は有機金属化合物、好ましくは3級アミン触媒〔(株)花王製「カオライザーP-200」、トリエチレンジアミン等〕の使用量を増加すればよい。
なお、クリームタイム、ゲルタイム、ライズタイム、キュア時間を確認したとき上記範囲内であり、各タイムを増減調整する必要が無い場合でも、各タイムを確認することで、調整する工程を有すると見なす。
高圧発泡機(PEC社製MiniRIM機)を用いて、表1及び表2に示すポリオール混合物(P)とポリイソシアネート成分(B)とを混合し、100×1200×6.8mmの金属製密閉モールドに注入成形した。モールドには、あらかじめ、厚さが0.8mmのポリウレタン製の表皮と、厚さが3mmのポリプロピレン製の基材とをそれぞれ片面ずつにセットした。以下に成形条件を示す。
<成形条件>
液温:(P)/(B)=25℃/25℃
金型温度:40℃
キュア時間:60秒
得られた各フォームの成形性及び物性値の測定結果を表1及び表2に示す。
なお、表1及び表2では、使用する材料の仕込量を重量部で示している。また、ポリイソシアネート成分の仕込量は、イソシアネート指数(インデックス)で示している。
(A21-1):ショ糖にPO・EOの順に付加したブロック付加物(水酸基価28、末端EO単位の含有量=20%、平均官能基数=8.0)。
(A2-2):グリセリンにPO・EOの順に付加したブロック付加物(水酸基価34、末端EO単位の含有量=20%、平均官能基数=3.0)。
(A2-3):グリセリンのPO付加物(水酸基価34、平均官能基数=3.0)。
(A2-4):グリセリンにPO・EOの順に付加したブロック付加物(水酸基価280、末端EO単位の含有量=10%、平均官能基数=3.0)。
(A2-5)〔(a1-1)〕:ペンタエリスリトールにPO・EOの順に付加したブロック付加物(水酸基価28、末端EO単位の含有量=14%、平均官能基数=4.0)。
(A11-1):ポリオール(a1-1)中でアクリロニトリルとスチレンを共重合させた重合体ポリオール(重合体含有量30%、アクリルニトリル/スチレン比(重量比)=65/35)。
(B-1):変性MDI〔日本ポリウレタン(株)製「CEF-263」、NCO含量=28.7%〕
(B-2):変性MDI〔日本ポリウレタン(株)製「CEI-264」、NCO含量=30.4%〕
(B-3):ポリメリックMDI〔日本ポリウレタン(株)製「MR-200」、NCO含量=31.3%〕
(D-1):3級アミン触媒〔(株)花王製「カオライザーP-200」〕
(D-2):ビス(N,N-ジメチルアミノ-2-エチル)エーテルの70%ジエチレングリコール溶液〔東ソー(株)製「TOYOCAT-ET」〕
(D-3):ポリウレタン触媒〔エアープロダクツジャパン(株)製「DABCO NE300」〕
(E-1):有機変性ポリシロキサンの調合剤〔デグサジャパン(株)製「テゴスターブB8715LF2」〕
(F-1):トリエタノールアミン
クリームタイム:ウレタン化反応において、反応直前の原料〔ポリオール混合物(P)とポリイソシアネート成分(B)〕の液温が25℃で、20cm×20cm×30cmの木箱中でフリー発泡したときに、原料を注入した時間から発泡が始まる時間までの時間(秒)。
ゲルタイム:ポリオール混合物(P)とポリイソシアネート成分(B)とを混合開始してから、増粘が起こってゲル強度が出始める(樹脂化)時間(秒)
ライズタイム:ポリオール混合物(P)とポリイソシアネート成分(B)とを混合開始してから、発泡フォームの上昇が停止する時間(秒)。
液流れ性:金型から脱型したときの外観を確認し、下記基準で評価した。
×:欠肉がある
△:成形品の端末にボイド又はセル荒れが存在する
○:成形品の端末にボイドおよびセル荒れが存在しない
キュア性:金型からフォームを取り出し、フォームに対して5kg重の荷重を3秒掛けたときのフォームの変形度合いを確認し、下記基準で評価した。
×:5mm以上の変形
△:1mm以上5mm未満の変形
○:1mm未満の変形
◎:変形なし
全密度(g/cm3 ):JIS K6401(全密度は、JIS規格で規定している「見掛け密度」を指す。)
C硬度:ショアーC硬度計により測定
熱老化後のC硬度保持率(%):100×〔130℃×100時間保持後のC硬度〕/〔初期のC硬度〕
反発弾性(%):JIS K6401(厚みはフォームを重ねて30mmとした)
引張強度(MPa):JIS K6401
伸び率(%):JIS K6401
Claims (9)
- 下記ポリオール(組成物)(A)、水を含有する発泡剤(C)及び触媒(D)を含有するポリオール混合物(P)とポリイソシアネート成分(B)とからなり、発泡剤(C)の含有量が(A)の合計重量を基準として1.5~2.5重量%である半硬質ポリウレタンフォーム形成用組成物。
ポリオール(組成物)(A):ポリエーテルポリオール(a)中でラジカル重合開始剤の存在下、ビニルモノマーが重合されて得られる重合体ポリオール(A1)及び/又はポリエーテルポリオール(A2)を含有し、ビニルモノマーの重合体の含有量が(A)の合計重量を基準として0~7重量%であり、(A2)中に下記ポリエーテルポリオール(A21)を含有しており、(A21)の含有量がポリオール(組成物)(A)中のポリエーテルポリオールの合計重量を基準として50~100重量%であるポリオール(組成物)。
ポリエーテルポリオール(A21):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が7.8~8.2であり、水酸基価が20~50(mgKOH/g)であり、末端オキシエチレン単位の含有量が5~25重量%であり、オキシエチレン単位の合計含有量が8~30重量%であるポリエーテルポリオール。 - ポリオール(組成物)(A)中の、ポリエーテルポリオール(a)及びポリエーテルポリオール(A2)全体の平均官能基数が5.5~8である請求項1に記載の半硬質ポリウレタンフォーム形成用組成物。
- 重合体ポリオール(A1)中に、下記ポリエーテルポリオール(a1)中でラジカル重合開始剤の存在下、ビニルモノマーが重合されて得られる重合体ポリオール(A11)を含有し、(A)中の(A21)の含有量が70~90重量%、(A11)の含有量が5~25重量%である請求項1又は2に記載の半硬質ポリウレタンフォーム形成用組成物。
ポリエーテルポリオール(a1):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が2.8~4.2であり、水酸基価が15~38(mgKOH/g)であり、オキシエチレン単位の合計含有量が5~40重量%であるポリエーテルポリオール。 - ポリイソシアネート成分(B)が、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート及びこれらの変性物の群から選ばれる1種以上を含有し、(B)のNCO含量が20~30重量%である請求項1~3のいずれかに記載の半硬質ポリウレタンフォーム形成用組成物。
- 下記ポリオール(組成物)(A)、水を含有する発泡剤(C)及び触媒(D)を含有するポリオール混合物(P)とポリイソシアネート成分(B)とから形成される半硬質ポリウレタンフォームの製造方法であって、(P)と(B)の混合液を25℃の液温で発泡、硬化させたときのクリームタイムを3~5秒に調整する工程、ゲルタイムを15~25秒に調整する工程、及びライズタイムを25~40秒に調整する工程を有する半硬質ポリウレタンフォームの製造方法。
ポリオール(組成物)(A):ポリエーテルポリオール(a)中でラジカル重合開始剤の存在下、ビニルモノマーが重合されて得られる重合体ポリオール(A1)及び/又はポリエーテルポリオール(A2)を含有し、ビニルモノマーの重合体の含有量が(A)の合計重量を基準として0~7重量%であり、(A2)中に下記ポリエーテルポリオール(A21)を含有しており、(A21)の含有量がポリオール(組成物)(A)中のポリエーテルポリオールの合計重量を基準として50~100重量%であるポリオール(組成物)。
ポリエーテルポリオール(A21):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が7.8~8.2であり、水酸基価が20~50(mgKOH/g)であり、末端オキシエチレン単位の含有量が5~25重量%であり、オキシエチレン単位の合計含有量が8~30重量%であるポリエーテルポリオール。 - ポリオール(組成物)(A)中の、ポリエーテルポリオール(a)及びポリエーテルポリオール(A2)全体の平均官能基数が5.5~8である請求項5に記載の半硬質ポリウレタンフォームの製造方法。
- 重合体ポリオール(A1)中に、下記ポリエーテルポリオール(a1)中でラジカル重合開始剤の存在下、ビニルモノマーが重合されて得られる重合体ポリオール(A11)を含有し、(A)中の(A21)の含有量が70~90重量%、(A11)の含有量が5~25重量%である請求項5又は6に記載の半硬質ポリウレタンフォームの製造方法。
ポリエーテルポリオール(a1):ポリオキシエチレンポリオキシプロピレンポリオールであって、平均官能基数が2.8~4.2であり、水酸基価が15~38(mgKOH/g)であり、オキシエチレン単位の合計含有量が5~40重量%であるポリエーテルポリオール。 - 25℃の液温で、40℃のクラッシュパッド用成形型内で発泡・硬化させたときのキュア時間を60秒以内に調整する工程を有する請求項5~7のいずれかに記載の半硬質ポリウレタンフォームの製造方法。
- 請求項5~8のいずれかに記載の製造方法で得られた半硬質ポリウレタンフォームであって、クラッシュパッド用成形型に注入し、密度0.20~0.25g/cm3で発泡・硬化させたときに、C硬度が8~20であり、反発弾性率が28~35%であるポリウレタンフォーム。
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EP3941955B1 (en) * | 2019-03-19 | 2023-12-13 | Basf Se | Polyol component and use thereof for producing rigid polyurethane foams |
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CN105873971A (zh) | 2016-08-17 |
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