JP2013189627A - Polyol component for manufacturing polyurethane resin, polyurethane resin, and molded product made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane resin containing in a high concentration a raw material of an organism origin which has a low environmental load and is a resource which can be regenerated.SOLUTION: A polyol component (Z) for manufacturing a polyurethane resin contains a polyol of an organism origin (a) which is at least one kind selected from a group consisting of an alkylene oxide adduct of glycerin of an organism origin (a1), an alkylene oxide adduct of sucrose (a2), and an alkylene oxide adduct of sorbitol (a3), and moreover has a number average molecular weight of 200-1200; castor oil (k); and carbonate of an organism origin (b); and, moreover, an organism origin ratio in a total weight is 50 wt.% or more. A polyurethane resin (C) is made by reaction between the polyol (Z) and a polyisocyanate component (Q) and the organism origin ratio is 36 wt.% or more. A polyurethane resin molded product is composed of the polyurethane resin (C).

Description

The present invention relates to a polyol component for producing a polyurethane resin containing a biological component at a high concentration, a polyurethane resin using the polyol component as a raw material, and a molded product thereof.

In recent years, from the viewpoint of reducing the environmental impact of plastics, development of resins using biological materials has attracted attention as an alternative to petroleum-derived resins. Examples thereof include use of a urethane resin obtained by reacting a plant-derived polyol, which is a biological polyol, and a biological carbonate filler such as shell powder. Biological polyols and biological carbonate fillers are those that incorporate carbon atoms of carbon dioxide in the environment when the organism grows from seeds. For this reason, even if organisms are burned to generate carbon dioxide or disposed of in the environment, the carbon atoms in the carbon dioxide that are discharged into the environment are those in which the organisms originally incorporated carbon atoms in the environment. Therefore, it does not affect the increase or decrease of the total amount of carbon dioxide in the environment. For this reason, it is called carbon neutral (carbon dioxide = neutral with respect to the amount of carbon cycle). Therefore, resins using biological materials can contribute to reducing the environmental load, and even if incineration or disposal is performed, there is little impact on the environment.

  Several urethane resins using biologically derived polyols that are plant-derived polyols and biologically-derived carbonate fillers have been reported so far. For example, as an example of a urethane resin using a plant-derived polyol, as a cushion material for a vehicle seat cushion or the like, a polyurethane foam having a suitable balance of hardness, rebound resilience, and durability is provided. It has been reported that a foam composition can be preferably used (Patent Document 1), has excellent low resilience, and is a plant obtained from a polyurethane foam composition suitable as a shock absorber, a sound absorber, and a vibration absorber. A polyurethane foam derived from the same has been reported (Patent Document 2). In addition, as an example of a urethane resin using a biological carbonate filler such as scallop shell powder, a polyurethane resin for insole in which the total amount of castor oil polyol and shell powder is 13 to 35% in the raw material has been reported. (Patent Document 3).

WO2007 / 020904 WO2007 / 020905 JP 2010-195870

However, in the methods disclosed in Patent Documents 1 and 2, since the polyol component is composed of a derivative polyol of a plant-derived molecule having a large molecular weight, it is difficult to increase the concentration of the biological component in the resin. is there. Further, in the method disclosed in Patent Document 3, since the amount of castor oil polyol cannot be increased due to the problem of resin physical properties, even if scallop shell powder, which is a biological material, is used at the same time, It was not possible to increase the ratio of the biological component of the above to a certain level.
The object of the present invention is to provide a urethane resin that can reduce the environmental burden from the viewpoint of carbon neutral, and can achieve the same physical properties as a commonly used urethane resin even when a high percentage of biological materials are used. It is to be.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is at least one selected from the group consisting of an alkylene oxide adduct (a1) of biologically derived glycerin, an alkylene oxide adduct (a2) of sucrose, and an alkylene oxide adduct (a3) of sorbitol. And a biologically-derived polyol (a) having a number average molecular weight of 200 to 1200, castor oil or castor oil derivative (k), and biologically-derived carbonate (b), and a proportion of biologically-derived components in the total weight thereof Polyol component (Z) for the production of a polyurethane resin having a content of 50% by weight or more; a polyurethane resin (C) obtained by reacting the polyol component (Z) with a polyisocyanate component (Q); containing the polyurethane resin (C) Polyurethane foam and polyurethane foam molding comprising the polyurethane foam A non-foamed polyurethane resin molded article comprising the polyurethane resin (C).

The polyol component (Z) for producing the polyurethane resin of the present invention and the polyurethane resin (C) using the component can reduce the environmental load from the viewpoint of carbon neutral, and use a high proportion of the raw materials derived from living organisms. In addition, there is an effect that physical properties equivalent to those of a commonly used urethane resin can be realized.

The biological component in the present invention refers to a component (compound) obtained directly from a living organism, and when the biological component is further processed with a non-biological component, the processed portion is the proportion of the biological component. (Hereinafter, it may be described as a biological origin rate.) For example, in the case of a polyol obtained by addition polymerization of alkylene oxide to biological glycerin, the biological component corresponds only to glycerin, and the alkylene oxide portion does not correspond to the biological component.

The polyol component (Z) for producing the polyurethane resin of the present invention has a biological origin ratio (Xz) in the total weight of 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. When (Xz) is less than 50% by weight, the effect of reducing the environmental load cannot be sufficiently achieved from the viewpoint of carbon neutral.
The polyurethane resin (C) obtained by reacting (Z) with the polyisocyanate component (Q) has a biological origin (X _C ) in the total weight of 36% by weight or more, preferably 40% by weight or more. More preferably, it is 45% by weight or more. If (X _C ) is 36% by weight or more, (C) can sufficiently exhibit the effect that the environmental load can be reduced from the viewpoint of carbon neutral.

[Biological polyol (a)]
The biological polyol (a) in the present invention is selected from the group consisting of an alkylene oxide adduct (a1) of biological glycerin, an alkylene oxide adduct (a2) of sucrose, and an alkylene oxide adduct (a3) of sorbitol. And a polyol having a number average molecular weight of 200 to 1200.
Here, biologically derived glycerin, sucrose and sorbitol are all derived from living organisms. The number average molecular weight is usually calculated from the hydroxyl value of the polyol (a). The hydroxyl value in the present invention is measured by a method defined in JIS K0070 (1992 version).

The alkylene oxide adduct (a1) of biological glycerin is a compound obtained by adding alkylene oxide (hereinafter abbreviated as AO) to biological glycerin, and the added AO preferably has 2 to 8 carbon atoms. , Propylene oxide (hereinafter abbreviated as PO), ethylene oxide (hereinafter abbreviated as EO), butylene oxide (hereinafter abbreviated as BO), and the like. , And a mixture of PO and EO. As for the AO species added to (a2) and (a3), the same AO species as in (a1) can be used. The number of added moles of AO is not particularly limited as long as it does not deviate from the range of the number average molecular weight of (a), but is usually 1 to 20 moles, preferably 2 to 10 moles.
The alkylene oxide adduct (a2) of sucrose in the present invention is a compound obtained by adding AO to sucrose, and the number of moles of AO added is not particularly limited as long as it does not deviate from the range of the number average molecular weight of (a). However, it is 1-18 mol normally, Preferably it is 2-15 mol.
The sorbitol alkylene oxide adduct (a3) in the present invention is a compound obtained by adding AO to sorbitol, and the number of moles of AO added is not particularly limited as long as it does not deviate from the range of the number average molecular weight of (a). Usually, it is 1-13 mol, preferably 2-11 mol.

The number average molecular weight of the biological polyol (a) is usually 200 to 1200, preferably 250 to 1100, more preferably 300 to 1000. The average functional group number of (a) is usually 3-8, preferably 2-6. The average hydroxyl value of (a) is usually 120 to 900, preferably 150 to 700.
When the number average molecular weight of (a) exceeds 1200, the hydroxyl value becomes small, the equivalent amount of polyisocyanate (the amount of polyisocyanate required for the amount of hydroxyl group) decreases, and the strength decreases, which is not preferable. . When the number average molecular weight of (a) is less than 200, the equivalent amount of polyisocyanate is increased, the amount of (a) in the urethane resin is decreased, and the proportion of the biological structure is decreased, which is not preferable.
The viscosity at 25 ° C. of the biologically derived polyol (a) is preferably 100 to 20000 mPa · s, more preferably 100 to 10000 mPa · s / 25 ° C., from the viewpoints of moldability and mixing properties.

Castor oil or castor oil derivative (k) in the present invention includes castor oil (k0), castor oil derivative (k1), and a mixture of (k0) and (k1).
Castor oil (k0) refers to a natural vegetable oil extracted from the seeds of Castorceae castor, which has been refined as an industrial raw material in order to reduce the inhibition of the urethane reaction and the occurrence of side reactions. The moisture content is preferably 0.1% or less, and the acid value is preferably 1.0 or less.
The castor oil derivative (k1) is a castor oil derivative obtained by reacting castor oil with another compound, and the number average molecular weight is preferably 1000 to 1500. The biological origin of (k1) is preferably 60 to 95%. Specific examples of (k1) include compounds obtained by adding the above AO to k0. AO preferably has 2 to 8 carbon atoms, and includes EO, PO, BO, etc., and two or more kinds may be used. (K0) is preferable because the molecular weight is small, the physical properties of the urethane resin are not lowered, and the biological ratio is not lowered.

[Biological carbonate (b)]
Biological carbonate (b) in the present invention refers to carbonate obtained from biological resources that inhabit modern times, for example, scallops, pearl oysters, oysters, tuna, swordfish, abalone shells, shrimp, crabs, etc. Calcium carbonate obtained from shellfish shells and eggshell powder. From the viewpoint of quality stability, availability stability, and price, calcium carbonate obtained from scallop shell powder is preferable. Some ore (limestone, etc.) mainly composed of calcium carbonate collected as an underground resource is made by depositing shells of organisms such as ancient foraminifera, cormorants and lime algae. Since it is not included in the carbon cycle that realizes the carbon offset, it is not included in the biological carbonate in the present invention.

Although it does not specifically limit about the volume average particle diameter (measurement value by a laser diffraction type particle size analyzer) of (b), Preferably it is 0.1-500 micrometers, More preferably, it is 1-300 micrometers. When the particle diameter of (b) is 0.1 to 500 μm, the appearance of the surface is not impaired even if the particles are located on the outer surface of the molded product, and there is little rise of fine dust during powder handling or product cutting. Therefore, it is preferable in the working environment.
The production method of (b) is not particularly limited as long as it is a commonly used production method. Usually, after the obtained shell is washed, the organic component is removed by incineration and classification by pulverization and firing (b) ) Powder can be obtained. In this production method, when the firing temperature for removing the organic components is 900 ° C. or higher, calcium carbonate is decomposed to become calcium oxide, and is usually fired at 80 ° C. to 300 ° C., preferably 100 ° C. to 250 ° C. Preferably it is.

Regarding the content weight% of (a), (b), (k) contained in the polyol component (Z) for producing the polyurethane resin, the content weight% of (a) is based on the weight of (Z). Preferably it is 5 to 60 weight%, More preferably, it is 10 to 50 weight%. When the content of (a) is 60% by weight or less, (b) which is the remaining component in (Z) has a biological percentage of 100% by weight, and (k) has a biological percentage of 100% by weight. Or, since it has a high biological origin rate, (Z) can realize a high biological origin rate, and when the content weight percentage of (a) is 5% by weight or more, high resin physical properties can be obtained. .

The content (%) of (b) is preferably 1 to 50% by weight, more preferably 10 to 30% by weight, based on the weight of (Z). When the content (%) of (b) is 50% by weight or less, (Z) can maintain fluidity and is easy to handle. When mixed and reacted with the polyisocyanate component (Q), it is miscible. When (b) is contained in an amount of 1% by weight or more, (b) is naturally derived from 100% by weight, so that the biological origin rate in (Z) can be increased.
The content (%) of (k) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the weight of (Z). When the content weight percentage of (k) is 60% by weight or less, high resin physical properties can be obtained. When the content weight percentage of (k) is 5% by weight or more, (k) has a bio-derived rate of 100%. % Or a high biological origin rate, the biological origin rate in (Z) can be increased.

In the present invention, the polyol component (Z) for producing a polyurethane resin can be produced using a general dispersion method such as mixing and stirring. The viscosity (25 ° C.) of the polyol component (Z) for producing the polyurethane resin in the present invention is preferably 1000 to 40000 mPa · s, more preferably 5000 to 35000 mPa · s. When (Z) has a viscosity of 40,000 mPa · s or less, the mixing property with the polyisocyanate component (Q) is good, and the deterioration of the resin physical properties and the molding failure due to poor mixing do not occur.

Polyisocyanate component (Q)
As the polyisocyanate component (Q) used in the production method of the present invention, any compound having two or more isocyanate groups in the molecule may be used, and any of those conventionally used in the production of polyurethane foams can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof. Moreover, (Q) can contain various additives, biological carbonate (b), etc. as needed.

The aromatic polyisocyanate includes 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same). Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI or polymeric MDI), and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI. The polyisocyanate (Q) in the present invention is preferably an aromatic polyisocyanate and a modified product thereof, and more preferably polymethylene polyphenylene isocyanate (crude MDI). As for the isocyanate group content rate of the whole polyisocyanate (Q) used for reaction, 10 to 35 weight% is preferable.

The polyol component (Z) for producing the polyurethane resin is a non-biological-derived polyol (d) generally used for producing a urethane resin, if necessary, as long as the bio-derived ratio in the total weight is 50% by weight or more. You may contain a urethanization catalyst (E), surfactant (F), a foaming agent (G), etc.

[Non-biogenic polyol (d)]
In the present invention, the non-biological-derived polyol (d) includes, for example, (1) polyoxyalkylene polyol non-biological starting materials (for example, polyhydric alcohols such as ethylene glycol, glycerin and propylene glycol, triethanolamine, ethylenediamine, AO is added to amines such as toluenediamine, polyhydric phenols such as bisphenol A and bisphenol F, and mixtures thereof), and the AO added to the above starting materials includes biological polyols (a) The same ones used above can be used.

(2) Polyester polyol The polyhydric alcohol [particularly, a dihydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; Polyether polyols (particularly diols); or mixtures thereof with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane] and the above polycarboxylic acids or ester-forming derivatives thereof [acid anhydrides, lower alkyls] (Carbon number of alkyl group: 1 to 4) ester, etc.] (for example, polyester polyol with adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate), or the carboxylic anhydride and AO Condensation products; their A Adducts (EO, PO, etc.); polylactone polyols, such as those obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) using the polyhydric alcohol as an initiator; polycarbonate polyols, such as the polyhydric alcohol and alkylene A reaction product with carbonate; and the like.

The non-biological-derived polyol (d) is a range of 0 to 20% by weight based on the weight of the polyurethane-producing polyol (Z), within a range where the biological-derived rate in the polyol (Z) for producing the polyurethane resin is 50% by weight or more. Preferably 0 to 10% by weight can be used in combination.
The number average molecular weight of the non-biogenic polyol (d) is usually 200 to 1200, preferably 250 to 1100, more preferably 300 to 1000. The average number of functional groups in (d) is usually 2-8, preferably 2-6. The average hydroxyl value of (d) is usually 120 to 900, preferably 150 to 700.

[Urethaneization catalyst (E)]
As the urethanization catalyst (E) in the present invention, all usual urethanization catalysts that promote the urethanation reaction can be used. Examples include triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N , N, N ′, N′-tetramethylhexamethylenediamine, tertiary amines such as PO adduct of N, N-dimethylaminopropylamine and carboxylates thereof, potassium acetate, potassium octylate, stannous octoate, etc. Organic metal compounds such as carboxylic acid metal salts and dibutyltin dilaurate.

[Surfactant (F)]
As the surfactant (F) in the present invention, any of those used in the production of ordinary polyurethane resins can be used. For example, a dimethylsiloxane surfactant [for example, “SRX manufactured by Toray Dow Corning Co., Ltd.” -253 "etc.], polyether-modified dimethylsiloxane surfactants [for example," L-5309 "manufactured by Momentive Co., Ltd.," SF-2969 "," SZ-1671 "manufactured by Toray Dow Corning Co., Ltd. Goldschmidt AG
"B-8462", "B-8474", etc. manufactured by the company are mentioned. The amount of (F) added is usually 0 to 6% by weight, preferably 0.5 to 3% by weight, based on (Z).

[Foaming agent (G)]
Examples of the blowing agent (G) in the present invention include water that reacts with polyisocyanate to generate carbon dioxide, low-boiling hydrocarbons that vaporize and expand by reaction heat, and hydrogen atom-containing halogenated hydrocarbon-based blowing agents. . The low boiling point hydrocarbon is usually a hydrocarbon having a boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, cyclopentane, and mixtures thereof. When the low-boiling hydrocarbon is used, the amount (parts by weight) is preferably 30 parts or less, more preferably 20 parts or less, based on 100 parts of the polyol component (Z).
Specific examples of hydrogen atom-containing halogenated hydrocarbon-based blowing agents include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCFC-141b, HCFC-22, and HCFC-142b); those of the HFC (hydrofluorocarbon) type (For example, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc).

Various additives (H) can be contained in the polyol component (Z) and the polyisocyanate component (Q) for polyurethane production in the present invention, if necessary. (H) includes dehydrating agent (H1), lubricant (H2), plasticizer (H3), thixotropic agent (H4), filler (H6), ultraviolet absorber (H7), anti-aging agent (H8). , Antioxidants (H9), coloring agents (H10), flame retardants (H11), antifungal agents (H12), antibacterial agents (H13), hollow microspheres (H14), inorganics other than biological carbonates (b) One or two or more additives selected from the group consisting of a filler (H15) and a dispersant (anti-settling agent) (H16) can be mentioned, and the amount of each (H) added is (Z) and (Q), respectively. Is usually 30% by weight or less, preferably 20% by weight or less.

The polyol component (Z) for producing the polyurethane resin of the present invention can be reacted with the polyisocyanate component (Q) to produce the polyurethane resin (C). The reaction conditions for the urethanization reaction are not particularly limited, and known conditions are applied. The isocyanate index [(NCO group / active hydrogen atom-containing group equivalent ratio × 100)] in the production of the polyurethane resin is preferably 70 to 125, more preferably 75 to 120, and particularly preferably 85 to 115. The density of the polyurethane resin molded product in the present invention is usually 0.1 to 1.0 g / cm ³ , preferably 0.3 to 0.9 g / cm ³ in the foam. In a non-foam, it is 1.1-1.5 g / cm < ³ > normally, Preferably it is 1.2-1.4 g / cm < ³ >.
In the present invention, the polyurethane foam or foam refers to a urethane foam resin and a so-called polyurethane foam having elasticity. Non-foam refers to non-foamed urethane resin.

A specific example of the method for producing the polyurethane resin molded product of the present invention is as follows. First, a urethanization catalyst (E), a foam stabilizer (F), a foaming agent (G), an additive (H), etc. are mix | blended with a polyol component (Z) as needed. Simultaneously, an additive (H) etc. are mix | blended with a polyisocyanate component (Q) as needed. Next, using a polyurethane foaming machine or a stirrer, the polyol component blending liquid and the polyisocyanate component blending liquid are rapidly mixed while injecting gas into the liquid as necessary. The obtained mixed liquid is put into a predetermined container (mold) and taken out after resinification to obtain a urethane resin molded product. The density of the urethane resin molded product is determined by the amount of the foaming agent (G) added to the polyol component (Z) and / or the amount of gas injected into the reaction mixture. Can be easily changed.

The polyurethane resin (C) obtained by reacting the polyol component (Z), (Z) and the polyisocyanate component (Q) for producing the polyurethane resin of the present invention has a high biogenic rate, and is environmentally friendly from the viewpoint of carbon neutrality. There is an effect that it can be made smaller. In addition, shells typified by scallop shells are generated in a large amount of about 200,000 tons per year as industrial waste during food processing, so they are useful from the viewpoint of effective use of waste (pre-consumer material). It also corresponds to the corporate green purchasing policy. Furthermore, even if a biological material is used at a high ratio, the physical properties equivalent to those of a commonly used urethane resin can be realized, so that it can be used for a wide range of applications in which the urethane resin is used.

The polyurethane foam or foam of the present invention is widely suitable for a wide range of industrial applications such as various core materials, structural materials, building materials, soundproof materials, heat insulating materials, cutting materials, abrasives, etc., in which urethane foam is generally used. However, it is suitably used as a cutting material, and the cutting material is cut and used as a master model, a (low strength) jig, a (low strength) mold, or the like.
Non-foamed polyurethane resin is also particularly suitably used as a cutting material, for example, and the cutting material is cut and used as a high-strength jig, a high-strength mold, or the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
The polyurethane resin raw materials in Examples and Comparative Examples are as follows.
Biological polyol (a)
(1) Biological glycerin derivative (a1-1): obtained by adding 2.7 mol of PO in the presence of potassium hydroxide to 1 mol of biological glycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., purified glycerin). Polyol having an average functional group number of 3.0, a number average molecular weight of 250 and a hydroxyl value of about 670. Biological origin rate 36.8%, viscosity 950 mPa · s
(2) Sucrose derivative (a2-1): obtained by adding 5.6 mol of PO in the presence of potassium hydroxide to 1 mol of sucrose, the average number of functional groups is 8, the number average molecular weight is about 1070, the hydroxyl value A PO adduct of sucrose that is about 420. Biological origin rate 31.9%, viscosity 20000 mPa · s
(3) Sorbitol derivative (a3-1): PO adduct of sorbitol having an average functional group number of about 6, a number average molecular weight of about 700, and a hydroxyl value of 490. Biological origin 24.3%, viscosity 16000 mPa · s (manufactured by Sanyo Chemical Industries, Sannix SP-750)

(4) Biologically derived glycerin derivative (a1-2): average obtained by adding 15.7 mol of PO in the presence of potassium hydroxide to 1 mol of biologically derived glycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., purified glycerin) A PO adduct of biologically derived glycerin having a functional group number of 3, a number average molecular weight of 1,000, and a hydroxyl value of about 168. Biological origin 9.2%, viscosity 260mPa · s
(5) Castor oil (k-1): refined castor oil with an average functional group number of 2.7, a number average molecular weight of 950 and a hydroxyl value of about 160 [castor oil SL from Ito Oil Co., Ltd.] 100% biological origin, viscosity of 680 mPa · s
(6) Biological carbonate filler (b-1): Scallop powder having an average particle size of about 5 μm [manufactured by Nippon Riken Kogyo Co., Ltd., scallop powder] Biogenic rate 100%
(7) Biological carbonate filler (b-2): eggshell powder having an average particle diameter of about 11 μm (Cal Hope, Cal Hope) Biological origin rate of 100%

Non-biological material (8) Petroleum-derived glycerin derivative (d-1): average functional group number 3 obtained by addition polymerization of 2.7 mol of PO in the presence of potassium hydroxide to 1 mol of petroleum-derived (epichlorohydrin-derived) glycerin 0.0, number average molecular weight 400, hydroxyl group value about 420 PO adduct of petroleum-derived glycerin, biological origin rate 0%
(9) Urethane catalyst: “Neostan U-600” manufactured by Nitto Kasei Co., Ltd. Biogenic rate 0%
(10) Surfactant: Toray Dow Corning Co., Ltd. “SZ-1671” biological origin rate 0%
(11) Filler: Talc “Soapstone A” with a median diameter of 4 μm [manufactured by Nippon Mytron Co., Ltd.] Biogenic rate 0%
(12) Dehydrating agent: "Molecular sieve 3A-B powder" manufactured by Union Showa
(13) Polyisocyanate (Q-1): Polymeric MDI isocyanate having an isocyanate group content of 31% by weight. [BASF Japan Co., Ltd. Lupranate M-20S] Biogenic rate 0%.

Examples 1-13 and Comparative Examples 1-4
Using a mechanical froth foaming machine, “MF-350 type mechanical froth foaming device” manufactured by Toho Machine Industry, the polyol component and polyisocyanate component in parts by weight shown in Table 1 and nitrogen as necessary are continuously mixed together. The mixture was discharged.
At this time, the rotation speed of the mechanical floss head is 300 RPM, the nitrogen flow rate is 1.5 L / min when the density of the molded product is 0.8 g / cm ³ , and no nitrogen injection is required when the density is 1.3 g / cm ³ (Non-foaming). The polyol component premix solution and the isocyanate premix solution were fed so that the isocyanate index was 105, and the feeding rate was 1 L / min. Since the liquid mixed in the mixer unit is continuously supplied from the discharge port, a metal mold is attached to the discharge port in advance, the supplied mixed solution is received, and the received mixed solution is sent to the curing furnace. The polyurethane foam molded product and the polyurethane resin (non-foamed) molded product were obtained by curing at 110 ° C. for 10 hours.

The physical properties of the obtained polyurethane foam molded product and polyurethane resin (non-foamed) molded product were measured by the following measuring method. The measurement results of each example and each comparative example are shown in Tables 1 and 2.
Shore D hardness:
A rectangular parallelepiped shaped product was measured five times with a Type D durometer in accordance with JIS K6253 to obtain an average value, and this was designated as Shore D hardness.
Linear expansion coefficient:
After adjusting the test pieces cut at a length × width × thickness = 10 × 4 × 4 mm from the one end and the center of the rectangular parallelepiped shaped product, respectively, at 25 ° C. and 55% RH for 12 hours, Measurement was performed according to JIS K7197 using a linear expansion coefficient measuring device [model name “TMA / SS6100”, manufactured by Seiko Instruments Inc.]. The dimensional change in 25-80 degreeC was measured, and the average dimensional change rate per 1 degreeC in 30-60 degreeC was calculated among them. This measurement was performed on three end portions and three central portions of each test piece, and an average value was obtained. Furthermore, the average value of each of the three test pieces was determined and used as the linear expansion coefficient of the molded product.
Thermal deformation temperature (HDT):
The produced molded article was cut into 127 × 12.7 × 12.7 mm to form a test piece,
The measurement was performed according to JIS K6911.
The measurement was performed using a load deflection temperature tester [model S3-FH] manufactured by Toyo Seiki Seisakusho.

ポリオール成分とポリイソシアネート成分の配合量は重量部である。

The blending amount of the polyol component and the polyisocyanate component is parts by weight.

Polyurethane resin molded products containing biological components listed in Examples 1 to 13 in high concentration (Examples 1, 3, and 5 to 13 are polyurethane foam molded products, and Examples 2 and 4 are non-foamed polyurethane resin molded products. ) Is a polyurethane resin molded product of Comparative Examples 1 to 4 which is a polyurethane resin molded product using the same amount of polyisocyanate based on petroleum-derived raw materials except that the same scallop shell powder is used as a filler (comparison) It was found that the physical properties equivalent to those of Examples 1, 3, and 4 were achieved as compared with the polyurethane foam molded article and Comparative Example 2 as the non-foamed polyurethane resin molded article.
In particular, the density, the filler component, and the amount of polyisocyanate used were almost the same in each comparison between Example 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 8 and Comparative Example 3, Example 9 and Comparative Example 4. It was confirmed that equivalent physical properties were realized under the same conditions.

Polyurethane resin is generally used for the polyurethane resin production product of the polyol (Z) for producing the polyurethane resin of the present invention, the polyurethane resin (C) using the component, and the polyurethane resin molded article formed by the (C). It can be widely used in a wide range of industrial applications such as various core materials, structural materials, building materials, soundproof materials, heat insulating materials, cutting materials, and abrasives.

Claims (8)

Biologically derived glycerin alkylene oxide adduct (a1), sucrose alkylene oxide adduct (a2), and sorbitol alkylene oxide adduct (a3), and at least one selected from the group consisting of a number average molecular weight A polyurethane containing a biological polyol (a), castor oil or castor oil derivative (k), which is 200 to 1200, and a biological carbonate (b) and having a biological percentage in the total weight of 50% by weight or more Polyol component (Z) for resin production. The polyol component (Z) according to claim 1, wherein the biological carbonate (b) is scallop shell powder. A polyurethane resin (C) obtained by reacting the polyol component (Z) for producing a polyurethane resin according to claim 1 or 2 and the polyisocyanate component (Q). The polyurethane resin (C) according to claim 3, wherein the bio-derived ratio in the polyurethane resin (C) is 36% by weight or more. A polyurethane foam comprising the polyurethane resin (C) according to claim 3 or 4. A polyurethane foam molded article comprising the polyurethane foam according to claim 5. The polyurethane foam molded article according to claim 6, which is a polyurethane foam molded article for machining. A non-foamed polyurethane resin molded article comprising the polyurethane resin (C) according to claim 3 or 4.