WO2012132912A1 - Polyol composition and polyurethane resin - Google Patents
Polyol composition and polyurethane resin Download PDFInfo
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- WO2012132912A1 WO2012132912A1 PCT/JP2012/056621 JP2012056621W WO2012132912A1 WO 2012132912 A1 WO2012132912 A1 WO 2012132912A1 JP 2012056621 W JP2012056621 W JP 2012056621W WO 2012132912 A1 WO2012132912 A1 WO 2012132912A1
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- polyol
- polyurethane resin
- molecule
- polyol composition
- amine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6594—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
Definitions
- the present invention relates to a polyol composition and a polyurethane resin.
- the present invention relates to a polyol composition used as a raw material of a polyurethane resin for protecting a steel material, and a polyurethane resin obtained by reacting the composition with a polyisocyanate compound.
- Patent Document 1 Japanese Patent Document 1
- Such a polyol composition is used, for example, in applications where it is mixed with a polyisocyanate compound immediately before use and applied to the surface of a steel material to form a protective material for a polyurethane resin on the surface of the steel material.
- such a polyol composition has a problem that a polyurethane resin produced using the composition has a relatively high impact resistance at a low temperature, but can be relatively easily deformed by an external force at a high temperature. That is, there is a problem that a polyurethane resin produced using such a polyol composition is not necessarily excellent in deformation resistance at a high temperature required for the use of a protective material for the steel material surface.
- the polyol composition according to the present invention comprises a polybutadiene polyol (a) having a polybutadiene structure and a plurality of hydroxyl groups in the molecule, and an amine polyol (a tertiary amine having a plurality of hydroxyl groups in the molecule). and b) and an alkylene diol (c) having two primary hydroxyl groups in the molecule and having a freezing point of ⁇ 20 ° C. or lower.
- the polyol composition according to the present invention preferably further contains a castor oil-based polyol (d).
- the polyol composition according to the present invention further contains an amine compound (e) having an active hydrogen-containing amino group in the molecule.
- the polyurethane resin according to the present invention is characterized in that the polyol composition is reacted with a polyisocyanate compound having a plurality of isocyanate groups in the molecule.
- the polyol composition according to the present invention has the effect of being able to produce a polyurethane resin that is relatively excellent in impact resistance at low temperatures and relatively suppressed in deformation at high temperatures. Moreover, the polyurethane resin according to the present invention has an effect that it is relatively excellent in impact resistance at a low temperature and is relatively prevented from being deformed at a high temperature.
- the polyol composition of the present embodiment comprises a polybutadiene polyol (a) having a polybutadiene structure and a plurality of hydroxyl groups in the molecule, an amine polyol (b) which is a tertiary amine having a plurality of hydroxyl groups in the molecule, and a molecule. And alkylene diol (c) having two primary hydroxyl groups and having a freezing point of -20 ° C. or lower.
- the polyol composition becomes a polyurethane resin by reacting with a polyisocyanate compound described later.
- the polyol composition is further characterized in that the polyurethane resin produced by reacting the polyol composition with a polyisocyanate compound described later is more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. It is preferable to contain a castor oil-based polyol or (e) an amine compound having an active hydrogen-containing amino group in the molecule. Further, the polyol composition preferably contains a powdery inorganic filler in that the polyurethane resin can be more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. .
- the polybutadiene polyol (a) may have a polybutadiene structure in which 1,3-butadiene is trans 1,4-bonded, or has a polybutadiene structure in which 1,3-butadiene is cis 1,4-bonded. Alternatively, it may have a polybutadiene structure in which 1,3-butadiene is bonded to 1,2. Moreover, you may have a polybutadiene structure in which these bonds were mixed.
- As said polybutadiene polyol what has a polybutadiene structure and two hydroxyl groups in a molecule
- the polybutadiene polyol has an average hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 20 to 250 mgKOH / g, and more preferably 45 to 105 mgKOH / g.
- Method A JIS K1557-1
- the average hydroxyl value of the polybutadiene polyol is 20 mgKOH / g or more
- the polyurethane resin can be more excellent in deformation resistance at high temperatures.
- the impact resistance in the low temperature of a polyurethane resin can become more excellent because it is 250 mgKOH / g or less.
- polybutadiene polyol examples include conventionally known general ones.
- the trade name “Poly bd R-45 HT” manufactured by Idemitsu Kosan Co., Ltd.
- trade name “Poly bd R-15 HT” (Idemitsu Kosan Co., Ltd.). (Commercially available) can be used.
- the polybutadiene polyol can be used singly or in combination of two or more.
- the polybutadiene polyol is preferably contained in the polyol composition in an amount of 15 to 30 parts by weight, more preferably 20 to 25 parts by weight.
- the polybutadiene polyol is contained in the polyol composition in an amount of 15 parts by weight or more, there is an advantage that the polyurethane resin can have more excellent impact resistance at low temperatures.
- the deformation resistance in the high temperature of the said polyurethane resin can become more excellent.
- the amine polyol (b) is a tertiary amine having a plurality of hydroxyl groups in the molecule, it has both the properties of the amine and the properties of the polyol.
- amine polyol examples include aromatic monoamines such as aniline, aromatic polyamines such as toluenediamine, diethyltoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, ethylenediamine, hexamethylenediamine, and diethylenetriamine. And those obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amine such as an aliphatic polyamine. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, butylene oxide and the like.
- the amine polyol is preferably one in which an alkylene oxide is added to the aromatic monoamine in that the polyurethane resin can be more excellent in strength, and an alkylene oxide is added to aniline. Is more preferable. Further, a product obtained by adding propylene oxide to aniline is more preferable.
- the amine polyol preferably has an average hydroxyl value determined in accordance with JIS K1557-1 (Method A) of 350 to 500 mgKOH / g.
- Method A JIS K1557-1
- the average hydroxyl value of the amine polyol is 350 mgKOH / g or more, there is an advantage that the strength of the polyurethane resin can be further improved.
- the elongation property of the said polyurethane resin ie, the softness
- the amine polyol can be used alone or in combination of two or more.
- the amine polyol is preferably contained in the polyol composition in an amount of 1 to 13 parts by weight, and more preferably 3 to 10 parts by weight.
- the amine polyol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the curability of the polyurethane resin and the impact resistance at a low temperature can be further improved. Further, the inclusion of 13 parts by weight or less has an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures.
- the alkylene diol (c) is a saturated hydrocarbon diol having two primary hydroxyl groups in the molecule and having a freezing point of ⁇ 20 ° C. or lower. That is, a diol having a freezing point of ⁇ 20 ° C. or lower and two saturated hydroxyl groups bonded to a saturated hydrocarbon.
- the alkylene diol is a compound represented by HO—H 2 C—R—CH 2 —OH, R is a linear or branched saturated hydrocarbon, and the freezing point is ⁇ 20. It is below °C.
- the freezing point of the alkylene diol (c) is measured at 1 atm by a method according to JIS K0065.
- alkylene diol (c) examples include alkylene diols having a branched saturated hydrocarbon, alkylene diols having a linear saturated hydrocarbon, and the like.
- examples of the alkylene diol having the branched saturated hydrocarbon include 2-methyl-1,3-propanediol (freezing point: -91 ° C.), 2-methyl-1,4-butanediol. (Freezing point: ⁇ 30 ° C. or lower), 3-methyl-1,5-pentanediol (freezing point: ⁇ 50 ° C. or lower), 2,4-diethyl-1,5-pentanediol (freezing point: ⁇ 30 ° C. or lower), etc. Can be mentioned.
- examples of the alkylene diol having the linear saturated hydrocarbon include 1,3-propanediol (freezing point: ⁇ 28 ° C.).
- the alkylene diol is preferably an alkylene diol having the above-mentioned branched saturated hydrocarbon in that the polyurethane resin has more excellent impact resistance at low temperatures, and 3-methyl-1,5-pentane is preferable. Diol or 2,4-diethyl-1,5-pentanediol is more preferable.
- the alkylene diol has a hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 300 to 1500 mgKOH / g, and more preferably 700 to 1000 mgKOH / g.
- Method A JIS K1557-1
- the hydroxyl value of the alkylene diol is 300 mgKOH / g or more
- the polyurethane resin can be more excellent in deformation resistance at high temperature.
- the impact resistance in the low temperature of the said polyurethane resin can become more excellent because it is 1500 mgKOH / g or less.
- the total number of carbon atoms in the molecule is not limited, but the total number of carbon atoms is preferably 4 to 10, and more preferably 6 to 9. That is, the alkylene diol is more preferably an alkylene diol having 6 to 9 carbon atoms and having a branched saturated hydrocarbon.
- the alkylene diols can be used singly or in combination of two or more.
- the alkylene diol is preferably contained in the polyol composition in an amount of 1 to 5 parts by weight, more preferably 1.5 to 2.0 parts by weight.
- the alkylene diol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures.
- the inclusion of 5 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
- the castor oil-based polyol (d) is a polyol having a castor oil fatty acid ester structure in the molecule. By using the castor oil-based polyol (d), it is possible to suppress a decrease in deformation resistance at high temperatures and impact resistance at low temperatures of the polyurethane resin while lowering the viscosity of the polyol composition.
- castor oil-based polyol (d) examples include castor oil, castor oil derivative polyol synthesized using castor oil or castor oil fatty acid, and the like.
- the castor oil derivative polyol examples include a polyol having a plurality of hydroxyl groups synthesized using castor oil and / or castor oil fatty acid. More specifically, as the castor oil derivative, for example, an ester exchange reaction product of castor oil and polyol, an esterification reaction product of castor oil fatty acid and polyol, the ester exchange reaction product or the esterification reaction product is alkylene. Examples include polyols to which oxides are added.
- the castor oil-based polyol preferably has an average hydroxyl value determined according to JIS K1557-1 (Method A) of 100 to 300 mgKOH / g.
- Method A JIS K1557-1
- the average hydroxyl value of the castor oil-based polyol is 100 mgKOH / g or more
- the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature.
- the said polyol composition becomes a thing of a lower viscosity by being 300 mgKOH / g or less.
- the castor oil-based polyol is preferably contained in the polyol composition in an amount of 10 to 20 parts by weight, more preferably 12 to 18 parts by weight.
- the castor oil-based polyol is contained in the polyol composition in an amount of 10 parts by weight or more, there is an advantage that the polyol composition has a lower viscosity.
- the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature.
- the amine compound (e) having an active hydrogen-containing amino group in the molecule has an active hydrogen-containing amino group represented by —NH 2 or ⁇ NH in the molecule.
- Examples of the amine compound (e) include an aliphatic amine compound having an aliphatic hydrocarbon and an active hydrogen-containing amino group in the molecule, or an aromatic hydrocarbon and an active hydrogen-containing amino group in the molecule.
- An aromatic amine compound etc. are mentioned.
- Examples of the aliphatic amine compound include an aliphatic monoamine compound having one active hydrogen-containing amino group in the molecule and an aliphatic polyamine compound having a plurality of active hydrogen-containing amino groups in the molecule.
- examples of the aliphatic polyamine compound include ethylenediamine, hexamethylenediamine, and diethylenetriamine.
- aromatic amine compound examples include an aromatic monoamine compound having one active hydrogen-containing amino group in the molecule and an aromatic polyamine compound having a plurality of active hydrogen-containing amino groups in the molecule.
- examples of the aromatic monoamine compound include aniline.
- Specific examples of the aromatic polyamine compound include toluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, and 3,5-diethyltoluenediamine.
- the amine compound is preferably the aromatic polyamine compound, more preferably 3,5-diethyltoluenediamine, in that the polyurethane resin can be more excellent in curability and deformation resistance at high temperatures.
- the amine compound is preferably contained in the polyol composition in an amount of 0.5 to 1.5 parts by weight, more preferably 0.8 to 1.0 parts by weight.
- the inorganic filler include powders such as calcium carbonate, quartz (crystalline silica), and alumina.
- the inorganic filler is preferably contained in the polyol composition in an amount of 40 to 70 parts by weight, and more preferably 45 to 60 parts by weight.
- 40 parts by weight or more of the filler in the polyol composition there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures.
- 70 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
- the polyol composition may contain a general catalyst for synthesizing a polyurethane resin in order to promote a reaction with a polyisocyanate compound described later. Further, the polyol composition may contain a plasticizer in order to improve compatibility with the polyisocyanate compound described later.
- the catalyst examples include a metal-based curing catalyst or an amine catalyst.
- the metal-based curing catalyst examples include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin dioctate, lead catalysts such as lead octylate, lead octenoate and lead naphthenate, bismuth octylate, bismuth neodecanoate. And bismuth catalyst.
- Examples of the amine catalyst include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N , N ′, N ′, N ′′ -pentamethyldiethylenetriamine, bis- (2-dimethylaminoethyl) ether, triethylenediamine, dimethylethanolamine, N-trioxyethylene-N, N-dimethylamine, N, N-dimethyl -N-hexanolamine and the like. The amount of the catalyst is appropriately adjusted.
- the polyol composition can be produced by mixing the above-described blending components by a conventionally known general method. Specifically, for example, it can be produced by mixing each compounding component by hand stirring or using a general mixing apparatus.
- the polyurethane resin of the present embodiment is obtained by reacting the polyol composition with a polyisocyanate compound having a plurality of isocyanate groups in the molecule.
- polyisocyanate compound conventionally known general compounds can be mentioned.
- examples of the polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
- Aliphatic polyisocyanates such as 2-methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
- polyisocyanate compound examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis (isocyanate methyl).
- polyisocyanate compound examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis (isocyanate methyl).
- polyisocyanate compound examples include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), and polymethylene polyphenyl polyisocyanate (polymeric).
- MDI 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate and the like, and aromatic polyisocyanates having an aromatic ring in the molecule. That.
- modified polyisocyanate compounds such as carbodiimide bodies, isocyanurate bodies, burette bodies, and adduct bodies of the above-described compounds can be used.
- the aromatic polyisocyanate is preferable, and the polymethylene polyphenyl polyisocyanate is more preferable in terms of excellent reactivity with the polyol composition.
- the polyisocyanate compound is preferably reacted so that an isocyanate group is 1.0 to 1.2 mol per 1 mol of active hydrogen groups in the polyol composition.
- an isocyanate group is 1.0 mol or more with respect to 1 mol of active hydrogen groups in the polyol composition.
- the isocyanate group is 1.2 mol or less, there is an advantage that the polyurethane resin is suppressed from foaming due to the reaction of excess isocyanate groups with moisture in the air.
- the polyurethane resin can be produced by a general method. Specifically, for example, the polyol composition and the polyisocyanate compound can be mixed and cured for production. More specifically, for example, a film-like polyurethane placed on a steel material by placing the polyol composition and the polyisocyanate compound in a two-component mixed spray coating machine and coating the plate-like steel material surface. Resin can be manufactured.
- the polyol composition or polyurethane resin of the above embodiment is as exemplified above, but the present invention is not limited to the above exemplified polyol composition or polyurethane resin. Moreover, the various aspects used in a general polyol composition or a polyurethane resin can be employ
- A Polybutadiene polyol (a-1) Polybutadiene polyol having an average hydroxyl value of 47 mg KOH / g (trade name “Poly bd R-45 HT” manufactured by Idemitsu Kosan Co., Ltd.) (A-2) Polybutadiene polyol having an average hydroxyl value of 103 mg KOH / g (trade name “Poly bd R-15 HT” manufactured by Idemitsu Kosan Co., Ltd.) (B) Amine polyol (b-1) Amine polyol obtained by adding 3 mol of propylene oxide to aniline (average hydroxyl value: 420 mgKOH / g) (B-2) Amine polyol obtained by adding 2 moles of butylene oxide to aniline (average hydroxyl value: 473 mgKOH / g) (C) an alkylene diol in which two primary hydroxyl groups are bonded via a saturated hydrocarbon and the number of carbon atoms connecting the two primary atom
- C-1 3-methyl-1,5-pentanediol (Hydroxyl value: 951 mg KOH / g Freezing point: ⁇ 50 ° C. or less)
- C-2) 2,4-diethyl-1,5-pentanediol (hydroxyl value: 700 mg KOH / g freezing point: -30 ° C.
- the polyol composition and the following polyisocyanate so that the isocyanate group of the polyisocyanate compound is 1.08 mol with respect to 1 mol of active hydrogen groups in the polyol composition produced in each example and each comparative example.
- the compound and the following catalyst were mixed to produce a polyurethane resin. Specifically, using a two-component mixed spray coating machine, a two-component mixture was applied to a plate-like steel material having a thickness of 5 mm to produce a polyurethane resin coating film having a thickness of 2.5 mm.
- Polyisocyanate compound Polymethylene polyphenyl polyisocyanate (free NCO group content: 31% by weight, Product name "Millionate MR-100" manufactured by Nippon Polyurethane Industry Co., Ltd.) Catalyst Dioctyltin dilaurate (0.02 parts by weight with respect to 100 parts by weight of polyol composition)
- the composition for polyurethane resin of the present invention is suitably used as a main component of a so-called two-component reactive polyurethane resin paint, for example.
- the polyurethane resin produced using the polyurethane resin composition of the present invention is excellent in impact resistance at low temperatures and suppressed in deformation at high temperatures.
- steel material protection for protecting steel materials such as steel pipes. It can be used in applications such as materials.
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Abstract
The present invention addresses the problem of providing a polyol composition and the like whereby it is possible to make a polyurethane resin which has superior relative impact resistance at low temperatures and for which deformation is suppressed at high temperatures. Provided are a polyol composition and the like, characterized in comprising: a polybutadiene polyol (a), the molecule of which has a polybutadiene structure and a plurality of hydroxyl groups; an amine polyol (b), which is a tertiary amine the molecule of which has a plurality of hydroxyl groups; and an alkylene diol (c), the molecule of which has two primary hydroxyl groups and which has a solidification point of at most -20°C.
Description
本発明は、ポリオール組成物及びポリウレタン樹脂に関する。具体的には、例えば、鋼材を保護するポリウレタン樹脂の原料として用いられるポリオール組成物、及び、該組成物とポリイソシアネート化合物とが反応されてなるポリウレタン樹脂に関する。
The present invention relates to a polyol composition and a polyurethane resin. Specifically, for example, the present invention relates to a polyol composition used as a raw material of a polyurethane resin for protecting a steel material, and a polyurethane resin obtained by reacting the composition with a polyisocyanate compound.
従来、この種のポリオール組成物としては、様々なものが知られており、具体的には、例えば、分子中にポリブタジエン構造及び複数の水酸基を有するポリブタジエンポリオールとひまし油とを含むものが知られている(特許文献1)。
Conventionally, various types of polyol compositions have been known. Specifically, for example, those containing polybutadiene polyol having a polybutadiene structure and a plurality of hydroxyl groups in the molecule and castor oil are known. (Patent Document 1).
斯かるポリオール組成物は、例えば、使用直前にポリイソシアネート化合物と混合されて鋼材表面に塗布され、鋼材表面にポリウレタン樹脂の保護材を形成する用途等において使用される。
Such a polyol composition is used, for example, in applications where it is mixed with a polyisocyanate compound immediately before use and applied to the surface of a steel material to form a protective material for a polyurethane resin on the surface of the steel material.
しかしながら、斯かるポリオール組成物は、該組成物を用いて製造されたポリウレタン樹脂が低温においては比較的耐衝撃性を有するものの、高温においては外力によって比較的容易に変形し得るという問題がある。即ち、斯かるポリオール組成物を用いて製造されたポリウレタン樹脂が、鋼材表面の保護材の用途等において要される高温における耐変形性に必ずしも優れたものでないという問題がある。
However, such a polyol composition has a problem that a polyurethane resin produced using the composition has a relatively high impact resistance at a low temperature, but can be relatively easily deformed by an external force at a high temperature. That is, there is a problem that a polyurethane resin produced using such a polyol composition is not necessarily excellent in deformation resistance at a high temperature required for the use of a protective material for the steel material surface.
本発明は、上記問題点等に鑑み、低温において比較的耐衝撃性に優れ且つ高温において変形が抑制されたポリウレタン樹脂を製造することができるポリオール組成物を提供することを課題とする。また、低温において比較的耐衝撃性に優れ且つ高温において変形が抑制されたポリウレタン樹脂を提供することを課題とする。
The present invention has been made in view of the above-mentioned problems and the like, and an object thereof is to provide a polyol composition capable of producing a polyurethane resin which is relatively excellent in impact resistance at low temperatures and whose deformation is suppressed at high temperatures. Another object of the present invention is to provide a polyurethane resin which is relatively excellent in impact resistance at low temperatures and whose deformation is suppressed at high temperatures.
上記課題を解決すべく、本発明に係るポリオール組成物は、分子中にポリブタジエン構造及び複数の水酸基を有するポリブタジエンポリオール(a)と、分子中に複数の水酸基を有する三級アミンであるアミンポリオール(b)と、分子中に2つの一級水酸基を有し且つ凝固点が-20℃以下であるアルキレンジオール(c)とを含むことを特徴とする。
In order to solve the above problems, the polyol composition according to the present invention comprises a polybutadiene polyol (a) having a polybutadiene structure and a plurality of hydroxyl groups in the molecule, and an amine polyol (a tertiary amine having a plurality of hydroxyl groups in the molecule). and b) and an alkylene diol (c) having two primary hydroxyl groups in the molecule and having a freezing point of −20 ° C. or lower.
また、本発明に係るポリオール組成物は、さらに、ひまし油系ポリオール(d)を含むことが好ましい。
The polyol composition according to the present invention preferably further contains a castor oil-based polyol (d).
また、本発明に係るポリオール組成物は、さらに、分子中に活性水素含有アミノ基を有するアミン化合物(e)を含むことが好ましい。
Moreover, it is preferable that the polyol composition according to the present invention further contains an amine compound (e) having an active hydrogen-containing amino group in the molecule.
本発明に係るポリウレタン樹脂は、前記ポリオール組成物と、分子中に複数のイソシアネート基を有するポリイソシアネート化合物とが反応されてなることを特徴とする。
The polyurethane resin according to the present invention is characterized in that the polyol composition is reacted with a polyisocyanate compound having a plurality of isocyanate groups in the molecule.
本発明に係るポリオール組成物は、低温において比較的耐衝撃性に優れ且つ高温において比較的変形が抑制されたポリウレタン樹脂を製造することができるという効果を奏する。また、本発明に係るポリウレタン樹脂は、低温において比較的耐衝撃性に優れ且つ高温において比較的変形が抑制されているという効果を奏する。
The polyol composition according to the present invention has the effect of being able to produce a polyurethane resin that is relatively excellent in impact resistance at low temperatures and relatively suppressed in deformation at high temperatures. Moreover, the polyurethane resin according to the present invention has an effect that it is relatively excellent in impact resistance at a low temperature and is relatively prevented from being deformed at a high temperature.
以下、本発明に係るポリオール組成物の第一実施形態について説明する。
Hereinafter, a first embodiment of the polyol composition according to the present invention will be described.
本実施形態のポリオール組成物は、分子中にポリブタジエン構造及び複数の水酸基を有するポリブタジエンポリオール(a)と、分子中に複数の水酸基を有する三級アミンであるアミンポリオール(b)と、分子中に2つの一級水酸基を有し且つ凝固点が-20℃以下であるアルキレンジオール(c)とを含むものである。
The polyol composition of the present embodiment comprises a polybutadiene polyol (a) having a polybutadiene structure and a plurality of hydroxyl groups in the molecule, an amine polyol (b) which is a tertiary amine having a plurality of hydroxyl groups in the molecule, and a molecule. And alkylene diol (c) having two primary hydroxyl groups and having a freezing point of -20 ° C. or lower.
前記ポリオール組成物は、後述するポリイソシアネート化合物と反応することにより、ポリウレタン樹脂になる。
The polyol composition becomes a polyurethane resin by reacting with a polyisocyanate compound described later.
前記ポリオール組成物は、該ポリオール組成物を後述するポリイソシアネート化合物と反応させて製造したポリウレタン樹脂が低温においてより耐衝撃性に優れ高温においてより耐変形性に優れるという点で、さらに、(d)ひまし油系ポリオール、又は、(e)分子中に活性水素含有アミノ基を有するアミン化合物を含むことが好ましい。
また、前記ポリオール組成物は、前記ポリウレタン樹脂が、低温においてより耐衝撃性に優れ高温においてより耐変形性に優れたものになり得るという点で、粉体状の無機充填材を含むことが好ましい。 The polyol composition is further characterized in that the polyurethane resin produced by reacting the polyol composition with a polyisocyanate compound described later is more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. It is preferable to contain a castor oil-based polyol or (e) an amine compound having an active hydrogen-containing amino group in the molecule.
Further, the polyol composition preferably contains a powdery inorganic filler in that the polyurethane resin can be more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. .
また、前記ポリオール組成物は、前記ポリウレタン樹脂が、低温においてより耐衝撃性に優れ高温においてより耐変形性に優れたものになり得るという点で、粉体状の無機充填材を含むことが好ましい。 The polyol composition is further characterized in that the polyurethane resin produced by reacting the polyol composition with a polyisocyanate compound described later is more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. It is preferable to contain a castor oil-based polyol or (e) an amine compound having an active hydrogen-containing amino group in the molecule.
Further, the polyol composition preferably contains a powdery inorganic filler in that the polyurethane resin can be more excellent in impact resistance at low temperatures and more excellent in deformation resistance at high temperatures. .
前記ポリブタジエンポリオール(a)は、1,3-ブタジエンがトランス1,4結合したポリブタジエン構造を有するものであってもよく、1,3-ブタジエンがシス1,4結合したポリブタジエン構造を有するものであってもよく、1,3-ブタジエンが1,2結合したポリブタジエン構造を有するものであってもよい。また、これら結合が混在したポリブタジエン構造を有するものであってもよい。
前記ポリブタジエンポリオールとしては、分子中にポリブタジエン構造及び2つの水酸基を有するものが好ましく、鎖状のポリブタジエン構造の両端にそれぞれ水酸基を有するものがより好ましい。 The polybutadiene polyol (a) may have a polybutadiene structure in which 1,3-butadiene is trans 1,4-bonded, or has a polybutadiene structure in which 1,3-butadiene is cis 1,4-bonded. Alternatively, it may have a polybutadiene structure in which 1,3-butadiene is bonded to 1,2. Moreover, you may have a polybutadiene structure in which these bonds were mixed.
As said polybutadiene polyol, what has a polybutadiene structure and two hydroxyl groups in a molecule | numerator is preferable, and what has a hydroxyl group at the both ends of a chain | strand-shaped polybutadiene structure is more preferable, respectively.
前記ポリブタジエンポリオールとしては、分子中にポリブタジエン構造及び2つの水酸基を有するものが好ましく、鎖状のポリブタジエン構造の両端にそれぞれ水酸基を有するものがより好ましい。 The polybutadiene polyol (a) may have a polybutadiene structure in which 1,3-butadiene is trans 1,4-bonded, or has a polybutadiene structure in which 1,3-butadiene is cis 1,4-bonded. Alternatively, it may have a polybutadiene structure in which 1,3-butadiene is bonded to 1,2. Moreover, you may have a polybutadiene structure in which these bonds were mixed.
As said polybutadiene polyol, what has a polybutadiene structure and two hydroxyl groups in a molecule | numerator is preferable, and what has a hydroxyl group at the both ends of a chain | strand-shaped polybutadiene structure is more preferable, respectively.
前記ポリブタジエンポリオールは、JIS K1557-1(A法)に従って求めた平均水酸基価が20~250mgKOH/gであることが好ましく、45~105mgKOH/gであることがより好ましい。
前記ポリブタジエンポリオールの平均水酸基価が20mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、250mgKOH/g以下であることにより、ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The polybutadiene polyol has an average hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 20 to 250 mgKOH / g, and more preferably 45 to 105 mgKOH / g.
When the average hydroxyl value of the polybutadiene polyol is 20 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. Moreover, there exists an advantage that the impact resistance in the low temperature of a polyurethane resin can become more excellent because it is 250 mgKOH / g or less.
前記ポリブタジエンポリオールの平均水酸基価が20mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、250mgKOH/g以下であることにより、ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The polybutadiene polyol has an average hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 20 to 250 mgKOH / g, and more preferably 45 to 105 mgKOH / g.
When the average hydroxyl value of the polybutadiene polyol is 20 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. Moreover, there exists an advantage that the impact resistance in the low temperature of a polyurethane resin can become more excellent because it is 250 mgKOH / g or less.
前記ポリブタジエンポリオールとしては、従来公知の一般的なものが挙げられ、例えば、商品名「Poly bd R-45 HT」(出光興産社製)、商品名「Poly bd R-15 HT」(出光興産社製)などのような市販されているものを用いることができる。
Examples of the polybutadiene polyol include conventionally known general ones. For example, the trade name “Poly bd R-45 HT” (manufactured by Idemitsu Kosan Co., Ltd.) and the trade name “Poly bd R-15 HT” (Idemitsu Kosan Co., Ltd.). (Commercially available) can be used.
前記ポリブタジエンポリオールは、1種を単独で又は2種以上を混合して用いることができる。
The polybutadiene polyol can be used singly or in combination of two or more.
前記ポリブタジエンポリオールは、前記ポリオール組成物に15~30重量部含まれていることが好ましく、20~25重量部含まれていることがより好ましい。
前記ポリブタジエンポリオールが前記ポリオール組成物に15重量部以上含まれていることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。また、30重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。 The polybutadiene polyol is preferably contained in the polyol composition in an amount of 15 to 30 parts by weight, more preferably 20 to 25 parts by weight.
When the polybutadiene polyol is contained in the polyol composition in an amount of 15 parts by weight or more, there is an advantage that the polyurethane resin can have more excellent impact resistance at low temperatures. Moreover, when 30 weight part or less is contained, there exists an advantage that the deformation resistance in the high temperature of the said polyurethane resin can become more excellent.
前記ポリブタジエンポリオールが前記ポリオール組成物に15重量部以上含まれていることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。また、30重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。 The polybutadiene polyol is preferably contained in the polyol composition in an amount of 15 to 30 parts by weight, more preferably 20 to 25 parts by weight.
When the polybutadiene polyol is contained in the polyol composition in an amount of 15 parts by weight or more, there is an advantage that the polyurethane resin can have more excellent impact resistance at low temperatures. Moreover, when 30 weight part or less is contained, there exists an advantage that the deformation resistance in the high temperature of the said polyurethane resin can become more excellent.
前記アミンポリオール(b)は、分子中に複数の水酸基を有する三級アミンであることから、アミンが有する性質とポリオールが有する性質とを兼ね備えている。
Since the amine polyol (b) is a tertiary amine having a plurality of hydroxyl groups in the molecule, it has both the properties of the amine and the properties of the polyol.
前記アミンポリオールとしては、例えば、アニリンなどの芳香族モノアミン、トルエンジアミン、ジエチルトルエンジアミン、4,4’-ジアミノ-3,3’-ジエチルジフェニルメタンなどの芳香族ポリアミン、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミンなどの脂肪族ポリアミンなどのアミン類に、炭素数2~4のアルキレンオキサイドを付加させたもの等が挙げられる。
該炭素数2~4のアルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられる。 Examples of the amine polyol include aromatic monoamines such as aniline, aromatic polyamines such as toluenediamine, diethyltoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, ethylenediamine, hexamethylenediamine, and diethylenetriamine. And those obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amine such as an aliphatic polyamine.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, butylene oxide and the like.
該炭素数2~4のアルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられる。 Examples of the amine polyol include aromatic monoamines such as aniline, aromatic polyamines such as toluenediamine, diethyltoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, ethylenediamine, hexamethylenediamine, and diethylenetriamine. And those obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amine such as an aliphatic polyamine.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, butylene oxide and the like.
具体的には、前記アミンポリオールとしては、前記ポリウレタン樹脂がより強度に優れたものになり得るという点で、前記芳香族モノアミンにアルキレンオキサイドを付加させたものが好ましく、アニリンにアルキレンオキサイドを付加させたものがより好ましい。また、アニリンにプロピレンオキサイドを付加させたものがさらに好ましい。
Specifically, the amine polyol is preferably one in which an alkylene oxide is added to the aromatic monoamine in that the polyurethane resin can be more excellent in strength, and an alkylene oxide is added to aniline. Is more preferable. Further, a product obtained by adding propylene oxide to aniline is more preferable.
また、前記アミンポリオールは、JIS K1557-1(A法)に従って求めた平均水酸基価が350~500mgKOH/gであることが好ましい。
前記アミンポリオールの平均水酸基価が350mgKOH/g以上であることにより、前記ポリウレタン樹脂の強度がより優れたものになり得るという利点がある。また、500mgKOH/g以下であることにより、前記ポリウレタン樹脂の伸び性、即ち、柔軟性がより優れたものになるという利点がある。 The amine polyol preferably has an average hydroxyl value determined in accordance with JIS K1557-1 (Method A) of 350 to 500 mgKOH / g.
When the average hydroxyl value of the amine polyol is 350 mgKOH / g or more, there is an advantage that the strength of the polyurethane resin can be further improved. Moreover, there exists an advantage that the elongation property of the said polyurethane resin, ie, the softness | flexibility, becomes more excellent because it is 500 mgKOH / g or less.
前記アミンポリオールの平均水酸基価が350mgKOH/g以上であることにより、前記ポリウレタン樹脂の強度がより優れたものになり得るという利点がある。また、500mgKOH/g以下であることにより、前記ポリウレタン樹脂の伸び性、即ち、柔軟性がより優れたものになるという利点がある。 The amine polyol preferably has an average hydroxyl value determined in accordance with JIS K1557-1 (Method A) of 350 to 500 mgKOH / g.
When the average hydroxyl value of the amine polyol is 350 mgKOH / g or more, there is an advantage that the strength of the polyurethane resin can be further improved. Moreover, there exists an advantage that the elongation property of the said polyurethane resin, ie, the softness | flexibility, becomes more excellent because it is 500 mgKOH / g or less.
前記アミンポリオールは、1種を単独で又は2種以上を混合して用いることができる。
The amine polyol can be used alone or in combination of two or more.
前記アミンポリオールは、前記ポリオール組成物に1~13重量部含まれていることが好ましく、3~10重量部含まれていることがより好ましい。
前記アミンポリオールが前記ポリオール組成物に1重量部以上含まれていることにより、前記ポリウレタン樹脂の硬化性及び低温における耐衝撃性がより優れたものになり得るという利点がある。また、13重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。 The amine polyol is preferably contained in the polyol composition in an amount of 1 to 13 parts by weight, and more preferably 3 to 10 parts by weight.
When the amine polyol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the curability of the polyurethane resin and the impact resistance at a low temperature can be further improved. Further, the inclusion of 13 parts by weight or less has an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures.
前記アミンポリオールが前記ポリオール組成物に1重量部以上含まれていることにより、前記ポリウレタン樹脂の硬化性及び低温における耐衝撃性がより優れたものになり得るという利点がある。また、13重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。 The amine polyol is preferably contained in the polyol composition in an amount of 1 to 13 parts by weight, and more preferably 3 to 10 parts by weight.
When the amine polyol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the curability of the polyurethane resin and the impact resistance at a low temperature can be further improved. Further, the inclusion of 13 parts by weight or less has an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures.
前記アルキレンジオール(c)は、分子中に2つの一級水酸基を有し且つ凝固点が-20℃以下の飽和炭化水素ジオールである。即ち、凝固点が-20℃以下であり飽和炭化水素に2つの一級水酸基が結合したジオールである。
詳しくは、前記アルキレンジオールは、HO-H2C-R-CH2-OHで表される化合物であり、Rが直鎖状又は分岐鎖状の飽和炭化水素であり、且つ、凝固点が-20℃以下のものである。
前記アルキレンジオール(c)の凝固点は、JIS K0065に準じた方法によって1気圧下にて測定したものである。 The alkylene diol (c) is a saturated hydrocarbon diol having two primary hydroxyl groups in the molecule and having a freezing point of −20 ° C. or lower. That is, a diol having a freezing point of −20 ° C. or lower and two saturated hydroxyl groups bonded to a saturated hydrocarbon.
Specifically, the alkylene diol is a compound represented by HO—H 2 C—R—CH 2 —OH, R is a linear or branched saturated hydrocarbon, and the freezing point is −20. It is below ℃.
The freezing point of the alkylene diol (c) is measured at 1 atm by a method according to JIS K0065.
詳しくは、前記アルキレンジオールは、HO-H2C-R-CH2-OHで表される化合物であり、Rが直鎖状又は分岐鎖状の飽和炭化水素であり、且つ、凝固点が-20℃以下のものである。
前記アルキレンジオール(c)の凝固点は、JIS K0065に準じた方法によって1気圧下にて測定したものである。 The alkylene diol (c) is a saturated hydrocarbon diol having two primary hydroxyl groups in the molecule and having a freezing point of −20 ° C. or lower. That is, a diol having a freezing point of −20 ° C. or lower and two saturated hydroxyl groups bonded to a saturated hydrocarbon.
Specifically, the alkylene diol is a compound represented by HO—H 2 C—R—CH 2 —OH, R is a linear or branched saturated hydrocarbon, and the freezing point is −20. It is below ℃.
The freezing point of the alkylene diol (c) is measured at 1 atm by a method according to JIS K0065.
前記アルキレンジオール(c)としては、例えば、分岐鎖状飽和炭化水素を有するアルキレンジオール、直鎖状飽和炭化水素を有するアルキレンジオール等が挙げられる。
Examples of the alkylene diol (c) include alkylene diols having a branched saturated hydrocarbon, alkylene diols having a linear saturated hydrocarbon, and the like.
具体的には、上記の分岐鎖状飽和炭化水素を有するアルキレンジオールとしては、例えば、2-メチル-1,3-プロパンジオール(凝固点:-91℃)、2-メチル-1,4-ブタンジオール(凝固点:-30℃以下)、3-メチル-1,5-ペンタンジオール(凝固点:-50℃以下)、2,4-ジエチル-1,5-ペンタンジオール(凝固点:-30℃以下)等が挙げられる。
また、上記の直鎖状飽和炭化水素を有するアルキレンジオールとしては、例えば、1,3-プロパンジオール(凝固点:-28℃)が挙げられる。 Specifically, examples of the alkylene diol having the branched saturated hydrocarbon include 2-methyl-1,3-propanediol (freezing point: -91 ° C.), 2-methyl-1,4-butanediol. (Freezing point: −30 ° C. or lower), 3-methyl-1,5-pentanediol (freezing point: −50 ° C. or lower), 2,4-diethyl-1,5-pentanediol (freezing point: −30 ° C. or lower), etc. Can be mentioned.
In addition, examples of the alkylene diol having the linear saturated hydrocarbon include 1,3-propanediol (freezing point: −28 ° C.).
また、上記の直鎖状飽和炭化水素を有するアルキレンジオールとしては、例えば、1,3-プロパンジオール(凝固点:-28℃)が挙げられる。 Specifically, examples of the alkylene diol having the branched saturated hydrocarbon include 2-methyl-1,3-propanediol (freezing point: -91 ° C.), 2-methyl-1,4-butanediol. (Freezing point: −30 ° C. or lower), 3-methyl-1,5-pentanediol (freezing point: −50 ° C. or lower), 2,4-diethyl-1,5-pentanediol (freezing point: −30 ° C. or lower), etc. Can be mentioned.
In addition, examples of the alkylene diol having the linear saturated hydrocarbon include 1,3-propanediol (freezing point: −28 ° C.).
前記アルキレンジオールとしては、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになるという点で、上記の分岐鎖状飽和炭化水素を有するアルキレンジオールが好ましく、3-メチル-1,5-ペンタンジオール、又は2,4-ジエチル-1,5-ペンタンジオールがより好ましい。
The alkylene diol is preferably an alkylene diol having the above-mentioned branched saturated hydrocarbon in that the polyurethane resin has more excellent impact resistance at low temperatures, and 3-methyl-1,5-pentane is preferable. Diol or 2,4-diethyl-1,5-pentanediol is more preferable.
前記アルキレンジオールは、JIS K1557-1(A法)に従って求めた水酸基価が300~1500mgKOH/gであることが好ましく、700~1000mgKOH/gであることがより好ましい。
前記アルキレンジオールの水酸基価が300mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、1500mgKOH/g以下であることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The alkylene diol has a hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 300 to 1500 mgKOH / g, and more preferably 700 to 1000 mgKOH / g.
When the hydroxyl value of the alkylene diol is 300 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature. Moreover, there exists an advantage that the impact resistance in the low temperature of the said polyurethane resin can become more excellent because it is 1500 mgKOH / g or less.
前記アルキレンジオールの水酸基価が300mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、1500mgKOH/g以下であることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The alkylene diol has a hydroxyl value determined according to JIS K1557-1 (Method A) of preferably 300 to 1500 mgKOH / g, and more preferably 700 to 1000 mgKOH / g.
When the hydroxyl value of the alkylene diol is 300 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature. Moreover, there exists an advantage that the impact resistance in the low temperature of the said polyurethane resin can become more excellent because it is 1500 mgKOH / g or less.
前記アルキレンジオールは、分子中の総炭素数が限定されるものではないが、総炭素数が4~10であることが好ましく、総炭素数が6~9であることがより好ましい。即ち、前記アルキレンジオールとしては、総炭素数が6~9であり且つ分岐鎖状飽和炭化水素を有するアルキレンジオールがより好ましい。
The total number of carbon atoms in the molecule is not limited, but the total number of carbon atoms is preferably 4 to 10, and more preferably 6 to 9. That is, the alkylene diol is more preferably an alkylene diol having 6 to 9 carbon atoms and having a branched saturated hydrocarbon.
前記アルキレンジオールは、1種を単独で又は2種以上を混合して用いることができる。
The alkylene diols can be used singly or in combination of two or more.
前記アルキレンジオールは、前記ポリオール組成物に1~5重量部含まれていることが好ましく、1.5~2.0重量部含まれていることがより好ましい。
前記アルキレンジオールが前記ポリオール組成物に1重量部以上含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、5重量部以下含まれていることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The alkylene diol is preferably contained in the polyol composition in an amount of 1 to 5 parts by weight, more preferably 1.5 to 2.0 parts by weight.
When the alkylene diol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. In addition, the inclusion of 5 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
前記アルキレンジオールが前記ポリオール組成物に1重量部以上含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性がより優れたものになり得るという利点がある。また、5重量部以下含まれていることにより、前記ポリウレタン樹脂の低温における耐衝撃性がより優れたものになり得るという利点がある。 The alkylene diol is preferably contained in the polyol composition in an amount of 1 to 5 parts by weight, more preferably 1.5 to 2.0 parts by weight.
When the alkylene diol is contained in the polyol composition in an amount of 1 part by weight or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. In addition, the inclusion of 5 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
前記ひまし油系ポリオール(d)は、分子中にひまし油脂肪酸エステル構造を有するポリオールである。
前記ひまし油系ポリオール(d)を用いることにより、前記ポリオール組成物の粘度をより低いものにしつつ前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性の低下を抑制することができる。 The castor oil-based polyol (d) is a polyol having a castor oil fatty acid ester structure in the molecule.
By using the castor oil-based polyol (d), it is possible to suppress a decrease in deformation resistance at high temperatures and impact resistance at low temperatures of the polyurethane resin while lowering the viscosity of the polyol composition.
前記ひまし油系ポリオール(d)を用いることにより、前記ポリオール組成物の粘度をより低いものにしつつ前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性の低下を抑制することができる。 The castor oil-based polyol (d) is a polyol having a castor oil fatty acid ester structure in the molecule.
By using the castor oil-based polyol (d), it is possible to suppress a decrease in deformation resistance at high temperatures and impact resistance at low temperatures of the polyurethane resin while lowering the viscosity of the polyol composition.
前記ひまし油系ポリオール(d)としては、ひまし油、又は、ひまし油若しくはひまし油脂肪酸を用いて合成されたひまし油誘導体ポリオール等が挙げられる。
Examples of the castor oil-based polyol (d) include castor oil, castor oil derivative polyol synthesized using castor oil or castor oil fatty acid, and the like.
前記ひまし油誘導体ポリオールとしては、例えば、ひまし油及び/又はひまし油脂肪酸を用いて合成された複数の水酸基を有するポリオールが挙げられる。
より具体的には、前記ひまし油誘導体としては、例えば、ひまし油とポリオールとのエステル交換反応生成物、ひまし油脂肪酸とポリオールとのエステル化反応物、前記エステル交換反応生成物又は前記エステル化反応物にアルキレンオキサイドを付加させてなるポリオールなどが挙げられる。 Examples of the castor oil derivative polyol include a polyol having a plurality of hydroxyl groups synthesized using castor oil and / or castor oil fatty acid.
More specifically, as the castor oil derivative, for example, an ester exchange reaction product of castor oil and polyol, an esterification reaction product of castor oil fatty acid and polyol, the ester exchange reaction product or the esterification reaction product is alkylene. Examples include polyols to which oxides are added.
より具体的には、前記ひまし油誘導体としては、例えば、ひまし油とポリオールとのエステル交換反応生成物、ひまし油脂肪酸とポリオールとのエステル化反応物、前記エステル交換反応生成物又は前記エステル化反応物にアルキレンオキサイドを付加させてなるポリオールなどが挙げられる。 Examples of the castor oil derivative polyol include a polyol having a plurality of hydroxyl groups synthesized using castor oil and / or castor oil fatty acid.
More specifically, as the castor oil derivative, for example, an ester exchange reaction product of castor oil and polyol, an esterification reaction product of castor oil fatty acid and polyol, the ester exchange reaction product or the esterification reaction product is alkylene. Examples include polyols to which oxides are added.
前記ひまし油系ポリオールは、JIS K1557-1(A法)に従って求めた平均水酸基価が100~300mgKOH/gであることが好ましい。
前記ひまし油系ポリオールの平均水酸基価が100mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性がより優れたものになり得るという利点がある。また、300mgKOH/g以下であることにより、前記ポリオール組成物がより低粘度のものになるという利点がある。 The castor oil-based polyol preferably has an average hydroxyl value determined according to JIS K1557-1 (Method A) of 100 to 300 mgKOH / g.
When the average hydroxyl value of the castor oil-based polyol is 100 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature. Moreover, there exists an advantage that the said polyol composition becomes a thing of a lower viscosity by being 300 mgKOH / g or less.
前記ひまし油系ポリオールの平均水酸基価が100mgKOH/g以上であることにより、前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性がより優れたものになり得るという利点がある。また、300mgKOH/g以下であることにより、前記ポリオール組成物がより低粘度のものになるという利点がある。 The castor oil-based polyol preferably has an average hydroxyl value determined according to JIS K1557-1 (Method A) of 100 to 300 mgKOH / g.
When the average hydroxyl value of the castor oil-based polyol is 100 mgKOH / g or more, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature. Moreover, there exists an advantage that the said polyol composition becomes a thing of a lower viscosity by being 300 mgKOH / g or less.
前記ひまし油系ポリオールは、前記ポリオール組成物に10~20重量部含まれていることが好ましく、12~18重量部含まれていることがより好ましい。
前記ひまし油系ポリオールが前記ポリオール組成物に10重量部以上含まれていることにより、前記ポリオール組成物がより低粘度のものになるという利点がある。また、20重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性がより優れたものになり得るという利点がある。 The castor oil-based polyol is preferably contained in the polyol composition in an amount of 10 to 20 parts by weight, more preferably 12 to 18 parts by weight.
When the castor oil-based polyol is contained in the polyol composition in an amount of 10 parts by weight or more, there is an advantage that the polyol composition has a lower viscosity. Moreover, when 20 parts by weight or less is contained, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature.
前記ひまし油系ポリオールが前記ポリオール組成物に10重量部以上含まれていることにより、前記ポリオール組成物がより低粘度のものになるという利点がある。また、20重量部以下含まれていることにより、前記ポリウレタン樹脂の高温における耐変形性及び低温における耐衝撃性がより優れたものになり得るという利点がある。 The castor oil-based polyol is preferably contained in the polyol composition in an amount of 10 to 20 parts by weight, more preferably 12 to 18 parts by weight.
When the castor oil-based polyol is contained in the polyol composition in an amount of 10 parts by weight or more, there is an advantage that the polyol composition has a lower viscosity. Moreover, when 20 parts by weight or less is contained, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperature and impact resistance at low temperature.
前記分子中に活性水素含有アミノ基を有するアミン化合物(e)は、-NH2又は=NHで表される活性水素含有アミノ基を分子中に有するものである。
The amine compound (e) having an active hydrogen-containing amino group in the molecule has an active hydrogen-containing amino group represented by —NH 2 or ═NH in the molecule.
前記アミン化合物(e)としては、例えば、分子中に脂肪族炭化水素と活性水素含有アミノ基とを有する脂肪族アミン化合物、又は、分子中に芳香族炭化水素と活性水素含有アミノ基とを有する芳香族アミン化合物等が挙げられる。
Examples of the amine compound (e) include an aliphatic amine compound having an aliphatic hydrocarbon and an active hydrogen-containing amino group in the molecule, or an aromatic hydrocarbon and an active hydrogen-containing amino group in the molecule. An aromatic amine compound etc. are mentioned.
前記脂肪族アミン化合物としては、分子中に1つの活性水素含有アミノ基を有する脂肪族モノアミン化合物、分子中に複数の活性水素含有アミノ基を有する脂肪族ポリアミン化合物が挙げられる。
具体的には、前記脂肪族ポリアミン化合物としては、例えば、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミンなどが挙げられる。 Examples of the aliphatic amine compound include an aliphatic monoamine compound having one active hydrogen-containing amino group in the molecule and an aliphatic polyamine compound having a plurality of active hydrogen-containing amino groups in the molecule.
Specifically, examples of the aliphatic polyamine compound include ethylenediamine, hexamethylenediamine, and diethylenetriamine.
具体的には、前記脂肪族ポリアミン化合物としては、例えば、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミンなどが挙げられる。 Examples of the aliphatic amine compound include an aliphatic monoamine compound having one active hydrogen-containing amino group in the molecule and an aliphatic polyamine compound having a plurality of active hydrogen-containing amino groups in the molecule.
Specifically, examples of the aliphatic polyamine compound include ethylenediamine, hexamethylenediamine, and diethylenetriamine.
前記芳香族アミン化合物としては、分子中に1つの活性水素含有アミノ基を有する芳香族モノアミン化合物、分子中に複数の活性水素含有アミノ基を有する芳香族ポリアミン化合物が挙げられる。
Examples of the aromatic amine compound include an aromatic monoamine compound having one active hydrogen-containing amino group in the molecule and an aromatic polyamine compound having a plurality of active hydrogen-containing amino groups in the molecule.
具体的には、前記芳香族モノアミン化合物としては、例えば、アニリン等が挙げられる。
また、前記芳香族ポリアミン化合物としては、具体的には例えば、トルエンジアミン、4,4’-ジアミノ-3,3’-ジエチルジフェニルメタン、3,5-ジエチルトルエンジアミン等が挙げられる。 Specifically, examples of the aromatic monoamine compound include aniline.
Specific examples of the aromatic polyamine compound include toluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, and 3,5-diethyltoluenediamine.
また、前記芳香族ポリアミン化合物としては、具体的には例えば、トルエンジアミン、4,4’-ジアミノ-3,3’-ジエチルジフェニルメタン、3,5-ジエチルトルエンジアミン等が挙げられる。 Specifically, examples of the aromatic monoamine compound include aniline.
Specific examples of the aromatic polyamine compound include toluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, and 3,5-diethyltoluenediamine.
前記アミン化合物としては、前記ポリウレタン樹脂の硬化性及び高温における耐変形性がより優れたものになり得るという点で、前記芳香族ポリアミン化合物が好ましく、3,5-ジエチルトルエンジアミンがより好ましい。
The amine compound is preferably the aromatic polyamine compound, more preferably 3,5-diethyltoluenediamine, in that the polyurethane resin can be more excellent in curability and deformation resistance at high temperatures.
前記アミン化合物は、前記ポリオール組成物に0.5~1.5重量部含まれていることが好ましく、0.8~1.0重量部含まれていることがより好ましい。
前記アミン化合物が前記ポリオール組成物に0.5重量部以上含まれていることにより、前記ポリウレタン樹脂の硬化性及び高温における耐変形性がより優れたものになり得るという利点がある。また、1.5重量部以下含まれていることにより、前記ポリオール組成物が後述するポリイソシアネート化合物と反応するときの反応性が高くなり過ぎることが抑制され、斯かる反応後に得られたポリウレタン樹脂の表面がより平滑なものになり得るという利点がある。 The amine compound is preferably contained in the polyol composition in an amount of 0.5 to 1.5 parts by weight, more preferably 0.8 to 1.0 parts by weight.
By including 0.5 parts by weight or more of the amine compound in the polyol composition, there is an advantage that the curability of the polyurethane resin and the deformation resistance at high temperature can be further improved. Moreover, it is suppressed that the reactivity when the said polyol composition reacts with the polyisocyanate compound mentioned later by containing 1.5 weight part or less is too high, The polyurethane resin obtained after such reaction There is an advantage that the surface of the substrate can be smoother.
前記アミン化合物が前記ポリオール組成物に0.5重量部以上含まれていることにより、前記ポリウレタン樹脂の硬化性及び高温における耐変形性がより優れたものになり得るという利点がある。また、1.5重量部以下含まれていることにより、前記ポリオール組成物が後述するポリイソシアネート化合物と反応するときの反応性が高くなり過ぎることが抑制され、斯かる反応後に得られたポリウレタン樹脂の表面がより平滑なものになり得るという利点がある。 The amine compound is preferably contained in the polyol composition in an amount of 0.5 to 1.5 parts by weight, more preferably 0.8 to 1.0 parts by weight.
By including 0.5 parts by weight or more of the amine compound in the polyol composition, there is an advantage that the curability of the polyurethane resin and the deformation resistance at high temperature can be further improved. Moreover, it is suppressed that the reactivity when the said polyol composition reacts with the polyisocyanate compound mentioned later by containing 1.5 weight part or less is too high, The polyurethane resin obtained after such reaction There is an advantage that the surface of the substrate can be smoother.
前記無機充填材としては、具体的には例えば、炭酸カルシウム、石英(結晶シリカ)、アルミナなどの各粉体が挙げられる。
Specific examples of the inorganic filler include powders such as calcium carbonate, quartz (crystalline silica), and alumina.
前記無機充填材は、前記ポリオール組成物に40~70重量部含まれていることが好ましく、45~60重量部含まれていることがより好ましい。
前記充填材が前記ポリオール組成物に40重量部以上含まれていることにより、前記ポリウレタン樹脂が、高温においてより耐変形性に優れたものになり得るという利点がある。また、70重量部以下含まれていることにより、ポリウレタン樹脂が、低温においてより耐衝撃性に優れたものになり得るという利点がある。 The inorganic filler is preferably contained in the polyol composition in an amount of 40 to 70 parts by weight, and more preferably 45 to 60 parts by weight.
By including 40 parts by weight or more of the filler in the polyol composition, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. In addition, the inclusion of 70 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
前記充填材が前記ポリオール組成物に40重量部以上含まれていることにより、前記ポリウレタン樹脂が、高温においてより耐変形性に優れたものになり得るという利点がある。また、70重量部以下含まれていることにより、ポリウレタン樹脂が、低温においてより耐衝撃性に優れたものになり得るという利点がある。 The inorganic filler is preferably contained in the polyol composition in an amount of 40 to 70 parts by weight, and more preferably 45 to 60 parts by weight.
By including 40 parts by weight or more of the filler in the polyol composition, there is an advantage that the polyurethane resin can be more excellent in deformation resistance at high temperatures. In addition, the inclusion of 70 parts by weight or less has an advantage that the polyurethane resin can be more excellent in impact resistance at low temperatures.
前記ポリオール組成物には、後述するポリイソシアネート化合物との反応を促進させるために、ポリウレタン樹脂合成用の一般的な触媒が含まれていてもよい。
また、前記ポリオール組成物には、後述するポリイソシアネート化合物との相溶性を向上させるために可塑剤が含まれていてもよい。 The polyol composition may contain a general catalyst for synthesizing a polyurethane resin in order to promote a reaction with a polyisocyanate compound described later.
Further, the polyol composition may contain a plasticizer in order to improve compatibility with the polyisocyanate compound described later.
また、前記ポリオール組成物には、後述するポリイソシアネート化合物との相溶性を向上させるために可塑剤が含まれていてもよい。 The polyol composition may contain a general catalyst for synthesizing a polyurethane resin in order to promote a reaction with a polyisocyanate compound described later.
Further, the polyol composition may contain a plasticizer in order to improve compatibility with the polyisocyanate compound described later.
前記触媒としては、例えば、金属系硬化触媒、又はアミン触媒等が挙げられる。
前記金属系硬化触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクテートなどの錫触媒、オクチル酸鉛、オクテン酸鉛、ナフテン酸鉛などの鉛触媒、オクチル酸ビスマス、ネオデカン酸ビスマスなどのビスマス触媒などが挙げられる。
前記アミン触媒としては、例えば、トリエチルアミン、トリプロピルアミン、トリブチルアミン、N-メチルモルホリン、N-エチルモルホリン、ジメチルベンジルアミン、N,N,N′,N′-テトラメチルヘキサメチレンジアミン、N,N,N′,N′,N″-ペンタメチルジエチレントリアミン、ビス-(2-ジメチルアミノエチル)エーテル、トリエチレンジアミン、ジメチルエタノールアミン、N-トリオキシエチレン-N,N-ジメチルアミン、N,N-ジメチル-N-ヘキサノールアミンなどが挙げられる。
なお、前記触媒の量は、適宜調整される。 Examples of the catalyst include a metal-based curing catalyst or an amine catalyst.
Examples of the metal-based curing catalyst include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin dioctate, lead catalysts such as lead octylate, lead octenoate and lead naphthenate, bismuth octylate, bismuth neodecanoate. And bismuth catalyst.
Examples of the amine catalyst include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N , N ′, N ′, N ″ -pentamethyldiethylenetriamine, bis- (2-dimethylaminoethyl) ether, triethylenediamine, dimethylethanolamine, N-trioxyethylene-N, N-dimethylamine, N, N-dimethyl -N-hexanolamine and the like.
The amount of the catalyst is appropriately adjusted.
前記金属系硬化触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクテートなどの錫触媒、オクチル酸鉛、オクテン酸鉛、ナフテン酸鉛などの鉛触媒、オクチル酸ビスマス、ネオデカン酸ビスマスなどのビスマス触媒などが挙げられる。
前記アミン触媒としては、例えば、トリエチルアミン、トリプロピルアミン、トリブチルアミン、N-メチルモルホリン、N-エチルモルホリン、ジメチルベンジルアミン、N,N,N′,N′-テトラメチルヘキサメチレンジアミン、N,N,N′,N′,N″-ペンタメチルジエチレントリアミン、ビス-(2-ジメチルアミノエチル)エーテル、トリエチレンジアミン、ジメチルエタノールアミン、N-トリオキシエチレン-N,N-ジメチルアミン、N,N-ジメチル-N-ヘキサノールアミンなどが挙げられる。
なお、前記触媒の量は、適宜調整される。 Examples of the catalyst include a metal-based curing catalyst or an amine catalyst.
Examples of the metal-based curing catalyst include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin dioctate, lead catalysts such as lead octylate, lead octenoate and lead naphthenate, bismuth octylate, bismuth neodecanoate. And bismuth catalyst.
Examples of the amine catalyst include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N , N ′, N ′, N ″ -pentamethyldiethylenetriamine, bis- (2-dimethylaminoethyl) ether, triethylenediamine, dimethylethanolamine, N-trioxyethylene-N, N-dimethylamine, N, N-dimethyl -N-hexanolamine and the like.
The amount of the catalyst is appropriately adjusted.
前記ポリオール組成物は、上述した各配合成分を従来公知の一般的な方法によって混合することにより製造することができる。具体的には、例えば、手撹拌や一般的な混合装置の使用によって各配合成分を混合することにより製造することができる。
The polyol composition can be produced by mixing the above-described blending components by a conventionally known general method. Specifically, for example, it can be produced by mixing each compounding component by hand stirring or using a general mixing apparatus.
次に、本発明のポリウレタン樹脂の一実施形態について説明する。
Next, an embodiment of the polyurethane resin of the present invention will be described.
本実施形態のポリウレタン樹脂は、前記ポリオール組成物と、分子中に複数のイソシアネート基を有するポリイソシアネート化合物とが反応されてなるものである。
The polyurethane resin of the present embodiment is obtained by reacting the polyol composition with a polyisocyanate compound having a plurality of isocyanate groups in the molecule.
前記ポリイソシアネート化合物としては、従来公知の一般的なものが挙げられる。
As the polyisocyanate compound, conventionally known general compounds can be mentioned.
具体的には、前記ポリイソシアネート化合物としては、例えば、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、2-メチルペンタン-1,5-ジイソシアネート、3-メチルペンタン-1,5-ジイソシアネート等の脂肪族ポリイソシアネートが挙げられる。
Specifically, examples of the polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Aliphatic polyisocyanates such as 2-methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
また、前記ポリイソシアネート化合物としては、例えば、イソホロンジイソシアネート、水添キシリレンジイソシアネート、4,4’-ジシクロヘキシルメタンジイソシアネート、1,4-シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、1,3-ビス(イソシアネートメチル)シクロヘキサン等の脂環族ポリイソシアネートが挙げられる。
Examples of the polyisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis (isocyanate methyl). Examples include alicyclic polyisocyanates such as cyclohexane.
また、前記ポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、2,2’-ジフェニルメタンジイソシアネート、2,4’-ジフェニルメタンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート(MDI)、ポリメチレンポリフェニルポリイソシアネート(ポリメリックMDI)、4,4’-ジベンジルジイソシアネート、1,5-ナフチレンジイソシアネート、キシリレンジイソシアネート、1,3-フェニレンジイソシアネート、1,4-フェニレンジイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α,α,α,α-テトラメチルキシリレンジイソシアネート等の、分子内に芳香環を有する芳香族ポリイソシアネートが挙げられる。
Examples of the polyisocyanate compound include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), and polymethylene polyphenyl polyisocyanate (polymeric). MDI), 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α , Α, α-tetramethylxylylene diisocyanate and the like, and aromatic polyisocyanates having an aromatic ring in the molecule. That.
さらに、前記ポリイソシアネート化合物としては、上述した各化合物のカルボジイミド体、イソシアヌレート体、ビューレット体、アダクト体等のポリイソシアネート化合物変性体などを用いることができる。
Furthermore, as the polyisocyanate compound, modified polyisocyanate compounds such as carbodiimide bodies, isocyanurate bodies, burette bodies, and adduct bodies of the above-described compounds can be used.
前記ポリイソシアネート化合物としては、前記ポリオール組成物との反応性により優れている点で、前記芳香族ポリイソシアネートが好ましく、前記ポリメチレンポリフェニルポリイソシアネートがより好ましい。
As the polyisocyanate compound, the aromatic polyisocyanate is preferable, and the polymethylene polyphenyl polyisocyanate is more preferable in terms of excellent reactivity with the polyol composition.
前記ポリイソシアネート化合物は、前記ポリオール組成物中の活性水素基1モルに対して、イソシアネート基が1.0~1.2モルになるように反応させることが好ましい。ポリオール組成物中の活性水素基1モルに対してイソシアネート基が1.0モル以上であることにより、ポリウレタン樹脂の硬化不良、耐水性不良、又は強度低下が抑制され得るという利点がある。また、イソシアネート基が1.2モル以下であることにより、過剰のイソシアネート基が空気中の水分と反応してポリウレタン樹脂が発泡することが抑制されるという利点がある。
The polyisocyanate compound is preferably reacted so that an isocyanate group is 1.0 to 1.2 mol per 1 mol of active hydrogen groups in the polyol composition. When the isocyanate group is 1.0 mol or more with respect to 1 mol of active hydrogen groups in the polyol composition, there is an advantage that poor curing of the polyurethane resin, poor water resistance, or strength reduction can be suppressed. Further, when the isocyanate group is 1.2 mol or less, there is an advantage that the polyurethane resin is suppressed from foaming due to the reaction of excess isocyanate groups with moisture in the air.
前記ポリウレタン樹脂は、一般的な方法によって製造することができる。具体的には、例えば、前記ポリオール組成物と前記ポリイソシアネート化合物とを混合することにより硬化させて製造することができる。より具体的には、例えば、前記ポリオール組成物と前記ポリイソシアネート化合物とを2液混合型スプレー塗装機に入れ、板状の鋼材表面に塗装することにより、鋼材上に配された膜状のポリウレタン樹脂を製造することができる。
The polyurethane resin can be produced by a general method. Specifically, for example, the polyol composition and the polyisocyanate compound can be mixed and cured for production. More specifically, for example, a film-like polyurethane placed on a steel material by placing the polyol composition and the polyisocyanate compound in a two-component mixed spray coating machine and coating the plate-like steel material surface. Resin can be manufactured.
上記の実施形態のポリオール組成物又はポリウレタン樹脂は、上記例示の通りであるが、本発明は、上記例示のポリオール組成物又はポリウレタン樹脂に限定されるものではない。
また、一般のポリオール組成物又はポリウレタン樹脂において用いられる種々の態様を、本発明の効果を損ねない範囲において、採用することができる。 The polyol composition or polyurethane resin of the above embodiment is as exemplified above, but the present invention is not limited to the above exemplified polyol composition or polyurethane resin.
Moreover, the various aspects used in a general polyol composition or a polyurethane resin can be employ | adopted in the range which does not impair the effect of this invention.
また、一般のポリオール組成物又はポリウレタン樹脂において用いられる種々の態様を、本発明の効果を損ねない範囲において、採用することができる。 The polyol composition or polyurethane resin of the above embodiment is as exemplified above, but the present invention is not limited to the above exemplified polyol composition or polyurethane resin.
Moreover, the various aspects used in a general polyol composition or a polyurethane resin can be employ | adopted in the range which does not impair the effect of this invention.
次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
以下に、ポリオール組成物を製造するための原料の詳細について説明する。
Hereinafter, details of raw materials for producing the polyol composition will be described.
(a)ポリブタジエンポリオール
(a-1) 平均水酸基価47mgKOH/gのポリブタジエンポリオール
(商品名「Poly bd R-45 HT」 出光興産社製)
(a-2) 平均水酸基価103mgKOH/gのポリブタジエンポリオール
(商品名「Poly bd R-15 HT」 出光興産社製)
(b)アミンポリオール
(b-1) アニリンにプロピレンオキサイドを3モル付加したアミンポリオール
(平均水酸基価:420mgKOH/g)
(b-2) アニリンにブチレンオキサイドを2モル付加したアミンポリオール
(平均水酸基価:473mgKOH/g)
(c)飽和炭化水素を介して2つの一級水酸基が結合し且つ該2つの一級水酸基をつないでいる炭素原子数が奇数であるアルキレンジオール
(c-1) 3-メチル-1,5-ペンタンジオール
(水酸基価:951mgKOH/g 凝固点:-50℃以下)
(c-2) 2,4-ジエチル-1,5-ペンタンジオール
(水酸基価:700mgKOH/g 凝固点:-30℃以下)
(d)ひまし油系ポリオール
(d-1) ひまし油誘導体ポリオール(ひまし油由来のポリエステルポリオール)
(商品名「URIC-Y403」 伊藤製油社製)
(水酸基価:160mgKOH/g)
(e)分子中に活性水素含有アミノ基を有するアミン化合物
(e-1) 3,5-ジエチルトルエンジアミン
・ その他の原料
1,3-ブタンジオール(一級水酸基が1つ)
(水酸基価:1247mgKOH/g 凝固点:-50℃以下)
1,6-ヘキサンジオール
(水酸基価:9950mgKOH/g 凝固点:42℃)
トリメチロールプロパン
(水酸基価:1256mgKOH/g 凝固点:58℃)
・ 無機充填材
石英(結晶シリカ)(商品名「鳥屋根珪石」 マルエス社製) (A) Polybutadiene polyol (a-1) Polybutadiene polyol having an average hydroxyl value of 47 mg KOH / g (trade name “Poly bd R-45 HT” manufactured by Idemitsu Kosan Co., Ltd.)
(A-2) Polybutadiene polyol having an average hydroxyl value of 103 mg KOH / g (trade name “Poly bd R-15 HT” manufactured by Idemitsu Kosan Co., Ltd.)
(B) Amine polyol (b-1) Amine polyol obtained by adding 3 mol of propylene oxide to aniline (average hydroxyl value: 420 mgKOH / g)
(B-2) Amine polyol obtained by adding 2 moles of butylene oxide to aniline (average hydroxyl value: 473 mgKOH / g)
(C) an alkylene diol in which two primary hydroxyl groups are bonded via a saturated hydrocarbon and the number of carbon atoms connecting the two primary hydroxyl groups is an odd number. (C-1) 3-methyl-1,5-pentanediol (Hydroxyl value: 951 mg KOH / g Freezing point: −50 ° C. or less)
(C-2) 2,4-diethyl-1,5-pentanediol (hydroxyl value: 700 mg KOH / g freezing point: -30 ° C. or less)
(D) Castor oil-based polyol (d-1) Castor oil derivative polyol (polyester polyol derived from castor oil)
(Product name “URIC-Y403” manufactured by Ito Oil Co., Ltd.)
(Hydroxyl value: 160 mgKOH / g)
(E) Amine compound having an active hydrogen-containing amino group in the molecule (e-1) 3,5-diethyltoluenediamine Other raw materials 1,3-butanediol (one primary hydroxyl group)
(Hydroxyl value: 1247 mg KOH / g Freezing point: -50 ° C or less)
1,6-hexanediol (hydroxyl value: 9950 mg KOH / g freezing point: 42 ° C.)
Trimethylolpropane (Hydroxyl value: 1256 mgKOH / g Freezing point: 58 ° C)
・ Inorganic filler Quartz (Crystalline silica) (Brand name “Bird roof quartzite” manufactured by Marues)
(a-1) 平均水酸基価47mgKOH/gのポリブタジエンポリオール
(商品名「Poly bd R-45 HT」 出光興産社製)
(a-2) 平均水酸基価103mgKOH/gのポリブタジエンポリオール
(商品名「Poly bd R-15 HT」 出光興産社製)
(b)アミンポリオール
(b-1) アニリンにプロピレンオキサイドを3モル付加したアミンポリオール
(平均水酸基価:420mgKOH/g)
(b-2) アニリンにブチレンオキサイドを2モル付加したアミンポリオール
(平均水酸基価:473mgKOH/g)
(c)飽和炭化水素を介して2つの一級水酸基が結合し且つ該2つの一級水酸基をつないでいる炭素原子数が奇数であるアルキレンジオール
(c-1) 3-メチル-1,5-ペンタンジオール
(水酸基価:951mgKOH/g 凝固点:-50℃以下)
(c-2) 2,4-ジエチル-1,5-ペンタンジオール
(水酸基価:700mgKOH/g 凝固点:-30℃以下)
(d)ひまし油系ポリオール
(d-1) ひまし油誘導体ポリオール(ひまし油由来のポリエステルポリオール)
(商品名「URIC-Y403」 伊藤製油社製)
(水酸基価:160mgKOH/g)
(e)分子中に活性水素含有アミノ基を有するアミン化合物
(e-1) 3,5-ジエチルトルエンジアミン
・ その他の原料
1,3-ブタンジオール(一級水酸基が1つ)
(水酸基価:1247mgKOH/g 凝固点:-50℃以下)
1,6-ヘキサンジオール
(水酸基価:9950mgKOH/g 凝固点:42℃)
トリメチロールプロパン
(水酸基価:1256mgKOH/g 凝固点:58℃)
・ 無機充填材
石英(結晶シリカ)(商品名「鳥屋根珪石」 マルエス社製) (A) Polybutadiene polyol (a-1) Polybutadiene polyol having an average hydroxyl value of 47 mg KOH / g (trade name “Poly bd R-45 HT” manufactured by Idemitsu Kosan Co., Ltd.)
(A-2) Polybutadiene polyol having an average hydroxyl value of 103 mg KOH / g (trade name “Poly bd R-15 HT” manufactured by Idemitsu Kosan Co., Ltd.)
(B) Amine polyol (b-1) Amine polyol obtained by adding 3 mol of propylene oxide to aniline (average hydroxyl value: 420 mgKOH / g)
(B-2) Amine polyol obtained by adding 2 moles of butylene oxide to aniline (average hydroxyl value: 473 mgKOH / g)
(C) an alkylene diol in which two primary hydroxyl groups are bonded via a saturated hydrocarbon and the number of carbon atoms connecting the two primary hydroxyl groups is an odd number. (C-1) 3-methyl-1,5-pentanediol (Hydroxyl value: 951 mg KOH / g Freezing point: −50 ° C. or less)
(C-2) 2,4-diethyl-1,5-pentanediol (hydroxyl value: 700 mg KOH / g freezing point: -30 ° C. or less)
(D) Castor oil-based polyol (d-1) Castor oil derivative polyol (polyester polyol derived from castor oil)
(Product name “URIC-Y403” manufactured by Ito Oil Co., Ltd.)
(Hydroxyl value: 160 mgKOH / g)
(E) Amine compound having an active hydrogen-containing amino group in the molecule (e-1) 3,5-diethyltoluenediamine Other raw materials 1,3-butanediol (one primary hydroxyl group)
(Hydroxyl value: 1247 mg KOH / g Freezing point: -50 ° C or less)
1,6-hexanediol (hydroxyl value: 9950 mg KOH / g freezing point: 42 ° C.)
Trimethylolpropane (Hydroxyl value: 1256 mgKOH / g Freezing point: 58 ° C)
・ Inorganic filler Quartz (Crystalline silica) (Brand name “Bird roof quartzite” manufactured by Marues)
(実施例1~5、比較例1~5)
表1に示す配合量に従い、無機充填材以外の各原料を混合した後、さらに無機充填材を添加して混合することによりポリオール組成物を製造した。 (Examples 1 to 5, Comparative Examples 1 to 5)
According to the blending amount shown in Table 1, after mixing raw materials other than the inorganic filler, a polyol composition was produced by further adding and mixing the inorganic filler.
表1に示す配合量に従い、無機充填材以外の各原料を混合した後、さらに無機充填材を添加して混合することによりポリオール組成物を製造した。 (Examples 1 to 5, Comparative Examples 1 to 5)
According to the blending amount shown in Table 1, after mixing raw materials other than the inorganic filler, a polyol composition was produced by further adding and mixing the inorganic filler.
<平均水酸基価の測定>
無機充填材以外の各原料を混合した後の混合物の平均水酸基価をJIS K1557-1(A法)に従って求めた。結果を表1に示す。 <Measurement of average hydroxyl value>
The average hydroxyl value of the mixture after mixing raw materials other than the inorganic filler was determined according to JIS K1557-1 (Method A). The results are shown in Table 1.
無機充填材以外の各原料を混合した後の混合物の平均水酸基価をJIS K1557-1(A法)に従って求めた。結果を表1に示す。 <Measurement of average hydroxyl value>
The average hydroxyl value of the mixture after mixing raw materials other than the inorganic filler was determined according to JIS K1557-1 (Method A). The results are shown in Table 1.
<貯蔵安定性の評価>
製造した各ポリオール組成物を-5℃で7日間静置し、白濁や析出がないものを○、白濁や析出が見られるものを×とした。結果を表1に示す。 <Evaluation of storage stability>
Each of the produced polyol compositions was allowed to stand at −5 ° C. for 7 days, where “O” indicates no cloudiness or precipitation, and “X” indicates that cloudiness or precipitation is observed. The results are shown in Table 1.
製造した各ポリオール組成物を-5℃で7日間静置し、白濁や析出がないものを○、白濁や析出が見られるものを×とした。結果を表1に示す。 <Evaluation of storage stability>
Each of the produced polyol compositions was allowed to stand at −5 ° C. for 7 days, where “O” indicates no cloudiness or precipitation, and “X” indicates that cloudiness or precipitation is observed. The results are shown in Table 1.
続いて、各実施例及び各比較例で製造したポリオール組成物中の活性水素基1モルに対してポリイソシアネート化合物のイソシアネート基が1.08モルとなるように、ポリオール組成物と下記のポリイソシアネート化合物と下記の触媒とを混合し、ポリウレタン樹脂を製造した。具体的には、2液混合型スプレー塗装機を用いて、5mm厚の板状鋼材に2液混合物を塗装し、膜厚2.5mmのポリウレタン樹脂の塗膜を製造した。
・ポリイソシアネート化合物
ポリメチレンポリフェニルポリイソシアネート
(遊離NCO基含有量:31重量%、
商品名「ミリオネートMR-100」 日本ポリウレタン工業社製)
・触媒
ジオクチルチンジラウレート
(ポリオール組成物100重量部に対して0.02重量部) Subsequently, the polyol composition and the following polyisocyanate so that the isocyanate group of the polyisocyanate compound is 1.08 mol with respect to 1 mol of active hydrogen groups in the polyol composition produced in each example and each comparative example. The compound and the following catalyst were mixed to produce a polyurethane resin. Specifically, using a two-component mixed spray coating machine, a two-component mixture was applied to a plate-like steel material having a thickness of 5 mm to produce a polyurethane resin coating film having a thickness of 2.5 mm.
Polyisocyanate compound Polymethylene polyphenyl polyisocyanate (free NCO group content: 31% by weight,
Product name "Millionate MR-100" manufactured by Nippon Polyurethane Industry Co., Ltd.)
Catalyst Dioctyltin dilaurate (0.02 parts by weight with respect to 100 parts by weight of polyol composition)
・ポリイソシアネート化合物
ポリメチレンポリフェニルポリイソシアネート
(遊離NCO基含有量:31重量%、
商品名「ミリオネートMR-100」 日本ポリウレタン工業社製)
・触媒
ジオクチルチンジラウレート
(ポリオール組成物100重量部に対して0.02重量部) Subsequently, the polyol composition and the following polyisocyanate so that the isocyanate group of the polyisocyanate compound is 1.08 mol with respect to 1 mol of active hydrogen groups in the polyol composition produced in each example and each comparative example. The compound and the following catalyst were mixed to produce a polyurethane resin. Specifically, using a two-component mixed spray coating machine, a two-component mixture was applied to a plate-like steel material having a thickness of 5 mm to produce a polyurethane resin coating film having a thickness of 2.5 mm.
Polyisocyanate compound Polymethylene polyphenyl polyisocyanate (free NCO group content: 31% by weight,
Product name "Millionate MR-100" manufactured by Nippon Polyurethane Industry Co., Ltd.)
Catalyst Dioctyltin dilaurate (0.02 parts by weight with respect to 100 parts by weight of polyol composition)
<ポリウレタン樹脂の塗膜の評価>
下記に示す方法によってポリウレタン樹脂の各塗膜を評価した。評価項目は、以下に示すように、硬化性、押し込みに対する変形性、耐衝撃性とした。評価結果を表2に示す。
・硬化性
塗装24時間後の塗膜表面を確認し、タックの有無を確認した。
・押し込みに対する変形性(60℃)
英国規格BS EN10290:2002に準じて評価し、60℃における押し込み長さが、膜厚に対して30%以下(0.75mm以下)であるものを○、30%を超えるものを×とした。
・耐衝撃性(-30℃)
-30℃下2時間静置したサンプルを英国規格BS EN10290:2020に準じて評価した。具体的には、サンプルに対して衝撃を与え、ホリデーディテクタ(ピンホール探知器)にて15kVでチェックして異常がないものを○、火花が見られたものを×とした。 <Evaluation of polyurethane resin coating film>
Each coating film of the polyurethane resin was evaluated by the method shown below. As shown below, the evaluation items were curability, deformability against indentation, and impact resistance. The evaluation results are shown in Table 2.
-Curability The surface of the coating film after 24 hours of coating was confirmed, and the presence or absence of tack was confirmed.
・ Deformability against indentation (60 ℃)
Evaluation was made according to the British standard BS EN10290: 2002, and the indentation length at 60 ° C. was 30% or less (0.75 mm or less) with respect to the film thickness, and the one exceeding 30% was rated as x.
・ Impact resistance (-30 ℃)
Samples that were allowed to stand at −30 ° C. for 2 hours were evaluated according to British Standard BS EN10290: 2020. Specifically, an impact was applied to the sample, and a check was made with a holiday detector (pinhole detector) at 15 kV.
下記に示す方法によってポリウレタン樹脂の各塗膜を評価した。評価項目は、以下に示すように、硬化性、押し込みに対する変形性、耐衝撃性とした。評価結果を表2に示す。
・硬化性
塗装24時間後の塗膜表面を確認し、タックの有無を確認した。
・押し込みに対する変形性(60℃)
英国規格BS EN10290:2002に準じて評価し、60℃における押し込み長さが、膜厚に対して30%以下(0.75mm以下)であるものを○、30%を超えるものを×とした。
・耐衝撃性(-30℃)
-30℃下2時間静置したサンプルを英国規格BS EN10290:2020に準じて評価した。具体的には、サンプルに対して衝撃を与え、ホリデーディテクタ(ピンホール探知器)にて15kVでチェックして異常がないものを○、火花が見られたものを×とした。 <Evaluation of polyurethane resin coating film>
Each coating film of the polyurethane resin was evaluated by the method shown below. As shown below, the evaluation items were curability, deformability against indentation, and impact resistance. The evaluation results are shown in Table 2.
-Curability The surface of the coating film after 24 hours of coating was confirmed, and the presence or absence of tack was confirmed.
・ Deformability against indentation (60 ℃)
Evaluation was made according to the British standard BS EN10290: 2002, and the indentation length at 60 ° C. was 30% or less (0.75 mm or less) with respect to the film thickness, and the one exceeding 30% was rated as x.
・ Impact resistance (-30 ℃)
Samples that were allowed to stand at −30 ° C. for 2 hours were evaluated according to British Standard BS EN10290: 2020. Specifically, an impact was applied to the sample, and a check was made with a holiday detector (pinhole detector) at 15 kV.
本発明のポリウレタン樹脂用組成物は、例えば、いわゆる2液反応型ポリウレタン樹脂塗料の主剤として好適に用いられる。また、本発明のポリウレタン樹脂用組成物を用いて製造されたポリウレタン樹脂は、低温において耐衝撃性に優れ且つ高温において変形が抑制されており、例えば、鋼管などの鋼材を保護するための鋼材保護材等の用途で使用され得る。
The composition for polyurethane resin of the present invention is suitably used as a main component of a so-called two-component reactive polyurethane resin paint, for example. In addition, the polyurethane resin produced using the polyurethane resin composition of the present invention is excellent in impact resistance at low temperatures and suppressed in deformation at high temperatures. For example, steel material protection for protecting steel materials such as steel pipes. It can be used in applications such as materials.
Claims (4)
- 分子中にポリブタジエン構造及び複数の水酸基を有するポリブタジエンポリオール(a)と、分子中に複数の水酸基を有する三級アミンであるアミンポリオール(b)と、分子中に2つの一級水酸基を有し且つ凝固点が-20℃以下であるアルキレンジオール(c)とを含むことを特徴とするポリオール組成物。 A polybutadiene polyol (a) having a polybutadiene structure and a plurality of hydroxyl groups in the molecule, an amine polyol (b) which is a tertiary amine having a plurality of hydroxyl groups in the molecule, and having two primary hydroxyl groups in the molecule and a freezing point And an alkylene diol (c) having a temperature of −20 ° C. or lower.
- さらに、ひまし油系ポリオール(d)を含む請求項1記載のポリオール組成物。 The polyol composition according to claim 1, further comprising a castor oil-based polyol (d).
- さらに、分子中に活性水素含有アミノ基を有するアミン化合物(e)を含む請求項1又は2記載のポリオール組成物。 Furthermore, the polyol composition of Claim 1 or 2 containing the amine compound (e) which has an active hydrogen containing amino group in a molecule | numerator.
- 請求項1~3のいずれか1項に記載のポリオール組成物と、分子中に複数のイソシアネート基を有するポリイソシアネート化合物とが反応されてなるポリウレタン樹脂。 A polyurethane resin obtained by reacting the polyol composition according to any one of claims 1 to 3 with a polyisocyanate compound having a plurality of isocyanate groups in the molecule.
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JP6621633B2 (en) * | 2015-09-30 | 2019-12-18 | 第一工業製薬株式会社 | Polyurethane resin-forming composition and polyurethane resin |
JP6653949B2 (en) * | 2015-09-30 | 2020-02-26 | 第一工業製薬株式会社 | Polyurethane resin-forming composition and polyurethane resin |
Citations (3)
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JPS59197466A (en) * | 1983-04-25 | 1984-11-09 | Dai Ichi Kogyo Seiyaku Co Ltd | Coating composition for metal |
JPS6013855A (en) * | 1983-07-04 | 1985-01-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Corrosion-resistant paint composition |
JP2010275425A (en) * | 2009-05-28 | 2010-12-09 | Dai Ichi Kogyo Seiyaku Co Ltd | Two-liquid reactive polyurethane resin composition and polyurethane resin obtained by curing the same |
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JPS59197466A (en) * | 1983-04-25 | 1984-11-09 | Dai Ichi Kogyo Seiyaku Co Ltd | Coating composition for metal |
JPS6013855A (en) * | 1983-07-04 | 1985-01-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Corrosion-resistant paint composition |
JP2010275425A (en) * | 2009-05-28 | 2010-12-09 | Dai Ichi Kogyo Seiyaku Co Ltd | Two-liquid reactive polyurethane resin composition and polyurethane resin obtained by curing the same |
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