JP2012236910A - Polyurethane foam for flame lamination - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane foam for flame lamination, which exhibits high peeling strength while having physical properties required for the polyurethane foam for flame lamination by using a plant-derived polyol raw material as a polyurethane raw material-blended polyol component.SOLUTION: The polyurethane foam for flame lamination comprises a polyurethane raw material that contains polyol, polyisocyanate, a foaming agent, and a catalyst. The polyol contains a ricinoleic acid.

Description

  The present invention relates to a polyurethane foam for frame lamination, and more particularly to a polyurethane foam for frame lamination comprising a polyurethane raw material containing a polyol derived from castor oil.

  Laminates comprising a foam layer such as polyurethane and a surface layer disposed on at least one surface thereof are interior materials for vehicles, furniture / building materials, daily goods such as clothing / miscellaneous goods, sanitary products, medical care products It is widely used for cushioning materials such as vehicle seats / sofas. In the production of such a laminate, a frame lamination method, which is advantageous in terms of economy and ease of operation, is widely applied rather than a method in which a foam layer and a surface material layer are bonded using an adhesive. Has been. The flame lamination method uses heat fusion properties such as polyurethane to partially melt the surface of the foam by heat, and a surface material such as a sheet / film made of synthetic fiber or natural fiber is applied to the part. It is a method of pasting and curing and integrating the foam and the surface material.

  Therefore, blending the raw material of polyurethane foam using the frame lamination method has a great influence on the adhesion between the foam and the surface material, not to mention the physical properties such as hardness and compression residual strain. Techniques relating to blending systems for polyurethane foams are disclosed.

  For example, in Patent Document 1, a foam material containing a polyether ester polyol and an organophosphorus compound having active hydrogen is used for the purpose of improving the adhesive force and bonding speed between the foam and the fabric (surface material). A polyurethane foam obtained by foam curing is disclosed.

  Moreover, in patent document 2, a low-rebound resilience urethane foam is a polyether ester polyol and a polyol having a hydroxyl value of 200 to 300 for the purpose of solving the problem that the melted part due to flame is not sufficiently cured after bonding. Polyurethane foams having low rebound resilience obtained by foam-curing a foam material containing a phosphorus-containing compound are disclosed.

  In Patent Document 3, for the purpose of improving the adhesive strength, particularly the initial adhesive strength, using a general-purpose polyether polyol, polyoxyalkylene ether polyol, polyisocyanate, hydroxyl value is 300 to 700, the number of functional groups Is a polyurethane foam comprising 2 to 6 and a crosslinking agent comprising a polyol excluding the polyoxyalkylene ether polyol.

Japanese Patent Publication No.46-30309 JP-A-9-151234 JP-A-4-266919

  However, the polyurethane foam disclosed in Patent Documents 1 and 2 also acts as a plasticizer because it contains an ester component and an organophosphorus compound in the foam material, and since it contains an ester component, compression residual strain, hardness, In some cases, physical properties such as heat and humidity resistance are deteriorated, and adhesion to the surface layer member is not sufficient.

  Patent Documents 1 to 3 all disclose a polyurethane production technique using petroleum-derived raw materials. However, due to the problem of exhaustion of petroleum raw materials, utilization of polyurethane raw materials such as de-petroleum raw materials (plant-derived raw materials, etc.) is expected. Therefore, it is expected to develop not only a general-purpose polyurethane foam but also a polyurethane foam having functionality.

  Therefore, an object of the present invention is to use a plant-derived polyol raw material as a polyol component of a polyurethane raw material blending system, and have a physical property required for a polyurethane foam for frame lamination and exhibit a strong peel strength. It is to provide a polyurethane foam for lamination.

As a result of intensive studies to solve the above problems, the inventor of the present invention uses a polyol containing ricinoleic acid, which is a main component of castor oil, so that the polyurethane foam for frame lamination using the polyol has high peel resistance. It was found that the above object can be achieved, and the present invention has been completed.
That is, a polyurethane foam for frame lamination comprising a polyurethane raw material containing a polyol, a polyisocyanate, a foaming agent, and a catalyst, wherein the polyol contains ricinoleic acid is provided.
According to this, the polyurethane foam for frame lamination has the properties required for a polyurethane foam for frame lamination, and has high peel strength characteristics at the same amount compared to other polyols such as conventional ether ester polyols. The body can be provided.

Furthermore, the polyol may contain 20 parts by weight or more of ricinoleic acid per 100 parts by weight of the polyol.
According to this, it is possible to provide a polyurethane foam for frame lamination having high physical properties required for a polyurethane foam for frame lamination and high peel strength characteristics.

Moreover, the polyurethane foam for frame lamination made of a polyurethane raw material containing a polyol derived from castor oil may satisfy the following formula.
((A × B) / C) × 100 ≧ 10
However, in the above formula, A is the number of added parts (parts) of a castor oil-derived polyol, B is the content (% by weight) of ricinoleic acid in the polyol derived from castor oil, and C is the total number of parts added to the polyurethane raw material ( Part).
According to this, it is possible to provide a polyurethane foam for frame lamination having high physical properties required for a polyurethane foam for frame lamination and high peel strength characteristics.

A laminate comprising the above-mentioned foam layer made of polyurethane foam for frame lamination, and a surface material layer bonded to at least a part of the surface of the foam layer, and molded from the laminate The interior material for vehicles made can be provided.
According to this, it is possible to provide a laminate and a vehicle interior material having high peel strength characteristics while having properties required for the laminate and the vehicle interior material.

  As described above, according to the present invention, the peel strength characteristics at the same addition amount as compared with other polyols such as a conventional ether ester polyol, while having the physical properties required for a polyurethane foam for frame lamination. It is possible to provide a polyurethane foam for high frame lamination.

Hereinafter, the present invention will be described in more detail.
The polyurethane foam according to the present invention comprises a polyurethane raw material containing a polyol, a polyisocyanate, a foaming agent and a catalyst, and is obtained by reacting a polyol with a polyisocyanate and foaming.

  This polyurethane foam is formed into, for example, a sheet shape, and at least one surface is formed with a laminate, for example, a sheet material, on which a surface material is laminated and bonded by heat fusion. For joining the surface material to the polyurethane foam, a frame lamination method is used from the viewpoint of local heating and ease of joining. The flame lamination method (flame bonding method) is a method in which a flame is applied to the surface of the polyurethane foam to melt the surface layer of the polyurethane foam, and the surface material is pressure-bonded to the surface to bond.

  The polyurethane foam for frame lamination according to the present invention forms a laminate by forming a surface material layer made of cloth or the like on at least one surface thereof, and the laminate is used as an interior material for vehicles, furniture / building materials, clothing / It is suitable for use as household goods such as miscellaneous goods, sanitary goods, medical care goods, cushion materials for vehicle seats / sofas and the like. The polyurethane foam for frame lamination is particularly suitable for seats and backrests in vehicle seats, child seats, cushions in furniture beds, mattresses, etc., and seats in seats such as chairs and sofas. Moreover, it is suitable as a constituent material for the backrest and pads. When the laminate of the present invention is applied to the above application, the peripheral edge and the like are stitched as necessary.

Next, the polyurethane raw material will be described.
In the polyol contained in the polyurethane raw material of the polyurethane foam for frame lamination according to the present invention, a polyether polyol or a polyester polyol is preferably used as a polyol other than a polyol derived from castor oil, which will be described later. If it is a compound which has two or more, it will not specifically limit, The well-known compound used for formation of a general polyurethane foam can be used.

  Examples of polyols other than castor oil-derived polyols include polyhydric alcohols, polyhydric phenols, alkanolamines having two or more hydroxyl groups, polyether polyols, polyether ester polyols, and polyester polyols. These polyols may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol include dihydric alcohols having 2 to 20 carbon atoms such as aliphatic diols such as alkylene glycol such as ethylene glycol and alicyclic diols such as cycloalkylene glycol such as cyclohexanediol; Trivalent alcohols having 3 to 20 carbon atoms such as aliphatic triols such as alkanetriols; 4 to 8 or more polyvalents having 5 to 20 carbon atoms such as aliphatic polyols such as alkane polyols such as pentaerythritol Alcohol etc. are mentioned.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol and hydroquinone; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone; and condensates of phenol and formaldehyde.

  Examples of the alkanolamine having two or more hydroxyl groups include diethanolamine, ethanolisopropanolamine, diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, and triethanolamine.

  As the polyether polyol, for example, at least one compound selected from the above-mentioned polyhydric alcohols, polyhydric phenols, and amine compounds containing the above alkanolamines may be selected from ethylene oxide, propylene oxide, 1,2-, 2 A compound obtained by adding (block and / or random addition) alkylene oxide such as 1,3- or 1,4-butylene oxide can be used.

  Examples of the polyether ester polyol include polyalkylene polyols such as polyethylene glycol, polypropylene glycol, and propylene oxide adducts of glycerin, polycarboxylic acid anhydrides such as succinic anhydride, adipic anhydride, and phthalic anhydride, ethylene oxide, Examples thereof include compounds obtained by reacting a compound having a cyclic ether group such as propylene oxide.

  Examples of the polyester polyol include a condensed polyester polyol obtained by reacting a polycarboxylic acid such as adipic acid and phthalic acid with a polyol such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, a lactone polyester polyol, and a polycarbonate type. A polyol etc. are mentioned.

  Polyether polyols and polyester polyols such as those mentioned above are petrochemical products derived from petroleum, but in recent years there is a concern about the depletion of petroleum, and petrochemical products emit a large amount of carbon dioxide when discarded by incineration. Therefore, there are concerns about the burden on the global environment.

  Therefore, the polyol according to the present invention further includes a polyol containing ricinoleic acid. Preferably, the polyol preferably contains 20 parts by weight or more of ricinoleic acid per 100 parts by weight of polyol. That is, when the total of the polyol containing ricinoleic acid and other polyols is 100 parts by weight, it is preferable to contain 20 parts by weight or more of ricinoleic acid. By including more ricinoleic acid, the peel strength is improved.

  The ricinoleic acid contained in the polyol used as the polyurethane raw material of the polyurethane foam for frame lamination according to the present invention is contained in the polyol derived from castor oil. Castor oil is an ester of fatty acid and glycerin, usually about 90% of the fatty acid is ricinoleic acid. More specifically, castor oil is mainly composed of ricinoleic acid triglyceride, and other components include, for example, unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and saturated fatty acids such as palmitic acid and stearic acid. doing.

Preferably, in a polyurethane foam for frame lamination made of a polyurethane raw material containing a polyol derived from castor oil, the number of added parts of the polyol derived from castor oil is A, and the content (% by weight) of ricinoleic acid in the polyol derived from castor oil is B. When the total number of added parts of the polyurethane raw material is C, the plant-derived degree (P) is:
P = ((A × B) / C) × 100 ≧ 10
Meet.

  The polyurethane foam for frame lamination satisfying such a degree of plant origination is a polyurethane foam for frame lamination having high physical properties required for the polyurethane foam for frame lamination and high peel strength characteristics. In addition, producing such a polyurethane foam for frame lamination is effective for future oil supply problems. In addition, the amount of carbon dioxide emitted when a polyurethane foam containing a large amount of a polyol derived from such a plant (castor oil) is burned can be reduced, which is also effective for problems relating to the global environment.

In the present invention, as the castor oil, a commercially available product can be used regardless of whether it is edible or industrial. As such castor oil, for example, URIC H-30 (castor oil refined product, average functional group number 2.7, hydroxyl value of about 160 mg KOH / g, manufactured by Ito Oil Co., Ltd.), URIC H-52 (castor oil refined product, And an average functional group number of 3 and a hydroxyl value of about 200 mgKOH / g).
In the present invention, if necessary, other polyols can be blended with the polyol composition as long as the effects of the present invention are not impaired.

  The component of the polyisocyanate contained in the polyurethane raw material of the polyurethane foam for frame lamination according to the present invention is not particularly limited, and a known compound used for forming a general polyurethane foam can be used. For example, various aromatic, aliphatic and alicyclic isocyanate compounds, and further modified products of these isocyanate compounds, or bifunctional isocyanates having two isocyanate groups in one molecule Or a trifunctional or higher functional isocyanate having three or more isocyanate groups in one molecule, and these may be used alone or in combination.

  Examples of the aromatic isocyanate include diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI). And tolidine diisocyanate (TODI).

  Examples of the aliphatic isocyanate include hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), and lysine triisocyanate (LTI).

  Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), hydrogenated XDI (H6XDI), and hydrogenated MDI (H12MDI).

  Examples of the modified isocyanate include urethane-modified products, dimers, trimers, carbodiimide-modified products, allophanate-modified products, burette-modified products, urea-modified products, isocyanurate-modified products, and oxazolidone-modified products. And isocyanate group-terminated prepolymers. Preferably, 2,4- or 2,6-tolylene diisocyanate (TDI) is used.

  The blending ratio of the polyisocyanate is, for example, isocyanate index (the ratio of isocyanate groups to the active hydrogen groups of the premix (that is, active hydrogen such as hydroxyl groups and water as the blowing agent in the polyol composition for polyurethane foam) = polyurethane. NCO (mol) / OH (mol) × 100) in the raw material is, for example, 60 to 500, preferably 70 to 130, more preferably 95 to 120, and still more preferably 100 to 115.

  Moreover, the foaming agent in this invention is for making a polyurethane resin foam and making a polyurethane resin foam. This foaming agent is not specifically limited, A well-known thing can be used for polyurethane foams. For example, water that generates carbon dioxide gas as a foaming agent by reacting with the above polyisocyanate, hydrocarbons such as cyclopentane, isopentane, and normal pentane that function as a foaming agent by vaporizing with the reaction heat at the time of polyurethane formation, chloride Mixing halogen compounds such as methylene, trichlorofluoromethane, dichlorodifluoromethane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, pentafluoroethyl methyl ether, heptafluoroisopropyl methyl ether, and liquefied carbon dioxide into the raw material under high pressure For example, liquefied carbon dioxide that functions as a foaming agent when vaporized during foaming.

  Of these, water is preferable. For example, ion exchange water, tap water, distilled water, or the like can be used. In addition, the said foaming agent can use the said component individually by 1 type or in combination of 2 or more types.

  The blending ratio of the foaming agent is appropriately selected. When the foaming agent is water, the content of the foaming agent in the raw material of the foam is usually 1 to 10 weights when the polyol is 100 parts by mass. Part, preferably 2 to 5 parts by mass.

  The catalyst in the present invention is for accelerating the urethanization reaction between a polyol and a polyisocyanate. The catalyst is not particularly limited, and those known for polyurethane foams can be used. For example, amine catalysts such as triethylamine, triethylenediamine, and tetramethylguanidine, tin catalysts such as dibutyltin dilaurate and stannous octoate, and metal catalysts such as phenylmercurypropionate and lead octenoate are exemplified. The compounding amount of the catalyst is appropriately determined depending on the kind of the catalyst, but is generally about 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the polyol component. These catalysts can be used alone or in combination of two or more.

In addition, foam stabilizers, cross-linking agents, fillers, stabilizers, colorants, flame retardants, plasticizers, foam breakers, antifoaming agents, etc. are blended as necessary and as long as the effects of the present invention are not impaired. Is done.
The foam stabilizer is not particularly limited, and those known for polyurethane foams can be used. Examples thereof include silicone foam stabilizers such as siloxane-oxyalkylene block copolymers, and fluorine-containing compound foam stabilizers. And surfactants. These foam stabilizers can be used singly or in combination of two or more. The blending ratio of the foam stabilizer is, for example, 0.1 to 5.0 parts by weight, preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of the polyol.

  A polyurethane foam for frame lamination can be produced using the raw material of the foam. In the production of the polyurethane foam, a known apparatus can be used, and large-scale and stable production is possible. That is, a polyurethane foam for flame lamination can be produced by reacting polyol and polyisocyanate in the presence of a foaming agent, a catalyst and the like.

  When producing the polyurethane foam for frame lamination of the present invention, either the one-shot method or the prepolymer method may be employed. The one-shot method is a method in which a polyol and a polyisocyanate are directly reacted. In the prepolymer method, a polyol and a polyisocyanate are reacted in advance to obtain a prepolymer having an isocyanate group at the terminal. This is a method of reacting a polyol.

  Moreover, as a shaping | molding method, although any of a slab method and a mold method may be sufficient, a slab method is preferable. In the slab method, polyurethane raw material is discharged onto a belt conveyor, and while the belt conveyor moves, the raw material is naturally foamed and cured at room temperature and atmospheric pressure. The body is cured in a drying oven and cut into a predetermined shape. On the other hand, the molding method is to produce a foam by injecting a polyurethane raw material into a mold (molding die), foaming in the mold, and then demolding.

The polyurethane foam for frame lamination of the present invention preferably has elasticity, and the density according to JIS K7222 is preferably 15 to 60 Kg / m ³ , more preferably 20 to 40 Kg / m ³ . The 25% hardness (25% -ILD) according to JIS K6400-2 is preferably 50 to 300 N, more preferably 80 to 200 N, and the compressive residual strain according to JIS K6400-4 is preferably 17%. Below, more preferably 10% or less. The rebound resilience according to JIS K6400-3 is preferably 20 to 50%. These are components such as seats and backrests for vehicle seats, child seats, cushions for furniture beds and mattresses, seats and backrests for seats such as chairs and sofas, pads, etc. As such, it is suitable performance.

  Since the polyurethane foam for frame lamination of the present invention is produced from the above-mentioned foam raw material, it has excellent heat-fusibility. Therefore, the surface of the foam is melted by heat, and the melted portion is brought into contact with a synthetic fiber such as polyamide resin or polyester resin, or a cloth or leather containing natural fiber made of cotton or wood. Can be integrated (frame lamination method). You may press from the one side or both sides of a contact thing. Thereby, the laminated body provided with the foam layer which consists of a polyurethane foam for frame lamination of this invention, and the surface material layer which consists of cloth, leather, etc. can be manufactured efficiently.

  That is, the laminate of the present invention comprises a foam layer made of the above-mentioned polyurethane foam for frame lamination of the present invention, and a surface material layer bonded to at least a part of the surface of the foam layer. This surface material layer may be disposed only on one side of the foam layer, or may be disposed on both sides. When the surface material layers are arranged on both sides, the surface material layer on one surface side and the surface material layer on the other surface side may be made of the same material or different materials. Good.

  In addition, the thicknesses of the foam layer and the surface material layer are appropriately selected depending on the purpose and application. Generally, the thicknesses of the foam layer and the surface material layer are 2.0 to 20.0 mm and 0.1 to 4.0 mm, respectively.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples.
<Example 1>
Foam raw materials composed of polyol, polyisocyanate, foaming agent, foam stabilizer, catalyst and the like shown in Table 1 were prepared. Using this foam raw material, foaming was performed at normal temperature and atmospheric pressure, and then the reaction product was heated and reacted (cured) through a heating furnace to obtain a polyurethane foam for frame lamination.

Next, the obtained polyurethane foam for frame lamination was cut into a length of 200 mm, a width of 50 mm, and a thickness of 10 mm to produce a sheet-like polyurethane foam for frame lamination.
This foam is passed through a LP gas flame adjusted to a width of 100 mm and a height of 70 mm at a speed of 8 m / min to melt the surface. Thereafter, a nylon non-woven fabric was superposed on the surface as a surface material and pressure-bonded with a roll (frame lamination method) to obtain a laminate composed of a foam layer and a surface material layer.

The laminate was cut into a width of 50 mm and a length of 200 mm in the measurement of the initial peel strength, and a width of 25 mm and a length of 150 mm in the measurement of the final peel strength. The initial peel strength was 2 minutes after the nylon nonwoven fabric was pressed. The peel strength was measured according to JIS L1066, and the final peel strength was 24 hours after the nylon nonwoven fabric was pressed. Note that “*” in Table 1 means that the material was broken rather than interfacially peeled at the time of peeling in the peeling test. As for the normal state physical properties, the density (Kg / m ³ ), 25% ILD (N), rebound resilience (%), and compression residual strain (%) in each laminate were measured according to JIS K6401.

  The foam raw material in this example contains 60 parts of polyol A1, 40 parts by weight of polyol A3, 59.2 parts by weight of polyisocyanate B1, and has an isocyanate index of 112. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant-derived degree P is 24.3%.

As a result, the density was 29.3 kg / m ³ , 25% ILD was 100 N, impact resilience was 27%, compression residual strain was 7.5%, initial peel strength was 9.8, and final peel strength was 6.1. It is. In both cases, material destruction occurred during the peeling.

<Example 2>
The foam raw material in this example shown in Table 1 contains 60 parts of polyol A1, 40 parts by weight of polyol A3, 64.6 parts by weight of polyisocyanate B1, and has an isocyanate index of 110. Further, 4.4 parts by weight of foaming agent C1, 5 parts by weight of foaming agent C2, 1 part by weight of foam stabilizer D1, 0.2 part by weight of amine catalyst E1, and 0.2 part by weight of metal catalyst E2 are included. . Moreover, the plant origination degree P is 23.5%.

As a result, the density was 20.1 kg / m ³ , 25% ILD was 85 N, impact resilience was 25%, compression residual strain was 8.9%, initial peel strength was 8.2, and final peel strength was 5.7. It is. In both cases, material destruction occurred during the peeling.

<Example 3>
The foam raw material in this example shown in Table 1 contains 60 parts of polyol A1, 40 parts by weight of polyol A3, 59.8 parts by weight of polyisocyanate B1, and has an isocyanate index of 112. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant-derived degree P is 24.1%.

As a result, the density was 29.1 kg / m ³ , the 25% ILD was 102 N, the impact resilience was 27%, the compression residual strain was 6.8%, the initial peel strength was 12.3, and the final peel strength was 7.9. It is. In both cases, material destruction occurred during the peeling.

<Example 4>
The foam raw material in this example shown in Table 1 contains 40 parts of polyol A1, 60 parts by weight of polyol A3, 62.4 parts by weight of polyisocyanate B1, and has an isocyanate index of 112. Further, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.22 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant-derived degree P is 35.8%.

As a result, the density was 29.5 kg / m ³ , 25% ILD was 70 N, impact resilience was 20%, compression residual strain was 8.0%, initial peel strength was 12.9, and final peel strength was 8.5. It is. In both cases, material destruction occurred during the peeling.

<Example 5>
The foam raw material in this example shown in Table 1 contains 20 parts of polyol A1, 80 parts by weight of polyol A3, 61.9 parts by weight of polyisocyanate B1, and has an isocyanate index of 105. Further, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.25 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 47.9%.

As a result, the density was 29.8 kg / m ³ , the 25% ILD was 62 N, the impact resilience was 15%, the compression residual strain was 12.3%, the initial peel strength was 13.2, and the final peel strength was 9.5. It is. In both cases, material destruction occurred during the peeling.

<Example 6>
The foam raw material in this example shown in Table 1 contains 100 parts by weight of polyol A3, 62.2 parts by weight of polyisocyanate B1, and has an isocyanate index of 100. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.35 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 59.7%.

As a result, the density was 29.8 kg / m ³ , 25% ILD was 51 N, impact resilience was 8%, compression residual strain was 16.4%, initial peel strength was 14.5, and final peel strength was 10.8. It is. In both cases, material destruction occurred during the peeling.

<Example 7>
The foam raw material in this example shown in Table 1 contains 80 parts of polyol A1, 20 parts by weight of polyol A3, 56.6 parts by weight of polyisocyanate B1, and has an isocyanate index of 115. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 12.4%.

As a result, the density was 29.5 kg / m ³ , the 25% ILD was 110 N, the impact resilience was 29%, the compression residual strain was 6.0%, the initial peel strength was 6.5, and the final peel strength was 5.1. It is. At the time of peeling, material destruction occurred only during the final peel strength test.

<Comparative Example 1>
The foam raw material in this comparative example shown in Table 1 contains 60 parts of polyol A1, 40 parts by weight of polyol A2, 52.9 parts by weight of polyisocyanate B1, and has an isocyanate index of 112. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 0%.

As a result, the density was 29.1 kg / m ³ , the 25% ILD was 135 N, the impact resilience was 34%, the compression residual strain was 6.7%, the initial peel strength was 4.1, and the final peel strength was 5.5. It is. At the time of peeling, material destruction occurred only during the final peel strength test.

<Comparative example 2>
The foam raw material in this comparative example shown in Table 1 contains 100 parts of polyol A1, 52.9 parts by weight of polyisocyanate B1, and has an isocyanate index of 120. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 0%.

As a result, the density was 29.3 kg / m ³ , the 25% ILD was 131 N, the impact resilience was 34%, the compressive residual strain was 6.4%, the initial peel strength was 0.8, and the final peel strength was 1.2. It is. In the case of peeling, neither material destruction occurred.

<Comparative Example 3>
The foam raw material in this comparative example shown in Table 1 contains 60 parts of polyol A1, 40 parts by weight of polyol A4, 52.9 parts by weight of polyisocyanate B1, and has an isocyanate index of 115. Furthermore, 3.8 parts by weight of foaming agent C1, 1 part by weight of foam stabilizer D1, 0.35 parts by weight of amine-based catalyst E1, and 0.2 parts by weight of metal catalyst E2 are included. Moreover, the plant origination degree P is 23.4%.

As a result, the density was 29.5 kg / m ³ , the 25% ILD was 101 N, the impact resilience was 25%, the compressive residual strain was 7.2%, the initial peel strength was 1.1, and the final peel strength was 1.0. It is. In the case of peeling, neither material destruction occurred.

<Comparative example 4>
The foam raw material in this comparative example shown in Table 1 contains 85 parts of polyol A1, 15 parts by weight of polyol A3, 56.7 parts by weight of polyisocyanate B1, and has an isocyanate index of 115. Furthermore, 3.8 parts by weight of the foaming agent C1, 1 part by weight of the foam stabilizer D1, 0.2 parts by weight of the amine catalyst E1, and 0.2 parts by weight of the metal catalyst E2 are included. Moreover, the plant origination degree P is 9.3%.

As a result, the density was 29.8 kg / m ³ , the 25% ILD was 131 N, the impact resilience was 30%, the compression residual strain was 7.2%, the initial peel strength was 4.5, and the final peel strength was 3.2. It is. In the case of peeling, neither material destruction occurred.

(Content of ricinoleic acid contained in polyol A3 derived from castor oil)
Examples 1 to 7 include a polyol A3 derived from castor oil containing ricinoleic acid, and in all examples, 20 parts by weight or more of polyol A3 with respect to 100 parts by weight of all polyols. Since this polyol has a plant-derived degree of 100%, it contains 20 parts by weight or more of ricinoleic acid. On the other hand, Comparative Examples 1 to 3 do not contain castor oil-derived ricinoleic acid, and Comparative Example 4 contains 15 parts by weight of castor oil-derived ricinoleic acid with respect to 100 parts by weight of the total polyol.

  In Examples 1-7, material destruction occurred in all during the final peel strength measurement, whereas in Comparative Examples 1-4, material failure occurred only in Comparative Example 1, whereas in Comparative Examples 2-4 Material destruction did not occur. Further, when the initial peel strength was measured, no material destruction occurred in Example 7, but material destruction occurred in Examples 1 to 6, and no material destruction occurred in all of Comparative Examples 1 to 4.

  As the added part by weight of polyol A3 increases, the initial peel strength and the final peel strength tend to be improved. In Example 7, which contains 20 parts by weight of polyol A3, material breakage occurs in the final peel strength measurement. In Comparative Example 4 containing only 15 parts by weight, in view of the fact that no material breakage occurred in the final peel strength measurement, the polyol A3 is contained in an intermediate value of 17.5 parts by weight or more, preferably 20 parts by weight or more. In this case, it can be seen that the film has high peel strength characteristics while having properties required for a polyurethane foam for frame lamination.

  In Examples 1 to 3 and Comparative Examples 1 and 3 containing 60 parts by weight of polyol A1 (polyoxyalkylene ether polyol), Examples 1 to 3 contain polyol A3 (castor oil). Comparative Example 1 is a polyol. A2 (polyoxyalkylene ether / polyester block copolymer polyol) and Comparative Example 3 contain polyol A4 (soybean oil-derived polyol). In all of Examples 1 to 3, material failure occurred in both the initial peel strength measurement and the final peel strength measurement.

  On the other hand, although material destruction occurred in the final peel strength measurement of Comparative Example 1, no material breakage occurred in the initial peel strength measurement of Comparative Example 1, the initial peel strength measurement and the final peel strength measurement of Comparative Example 3. The final peel strength of Comparative Example 1 is 5.5, which is lower than 6.1 of Example 1, 5.7 of Example 2, and 7.9 of Example 3. In view of such results, it goes without saying that petroleum-derived polyols are not merely improved in peel strength even if they are derived from plants, and are required for polyurethane foams for flame lamination by including polyols derived from castor oil. It can be seen that it has high peel strength characteristics while having physical properties.

(Degree of plant origin)
The plant-derived degree of Examples 1-7 is 12.4 or more of Example 7, while the plant-derived degree of Comparative Example 4 is 9.3. Accordingly, it can be seen that when the degree of plant origination is 10 or more, the film exhibits good peel strength and has high peel strength characteristics while having the physical properties required for a polyurethane foam for frame lamination. The degree of plant origination is preferably 10.9 or more, which is an intermediate value between 12.4 of Example 7 and 9.3 of Comparative Example, and more preferably 12.4 or more of Example 7.

なお、表１における、略称は以下のとおりである。
・ポリオールＡ１：
ポリオキシアルキレンエーテルポリオール。ポリオキシエチレン／オキシプロピレンエーテルポリオールＥＯ／ＰＯ付加体
平均分子量：３０００、官能基数：３、水酸基価：５６．１
・ポリオールＡ２：
ポリオキシアルキレンエーテル／ポリエステルブロック共重合体ポリオール
平均分子量：３０００、水酸基価：５６．１、商品名「Ｌ−５０」、三井武田ケミカル社製。
・ポリオールＡ３：
ヒマシ油（リシノレイン酸トリグリセロール）
平均分子量：１０００、官能基数：２．７、水酸基価：１６０、植物由来化度：１００％、商品名：「ＵＲＩＣ−Ｈ３０」、伊藤製油株式会社製
・ポリオールＡ４：
大豆油由来ポリオール
リノール酸を主成分とした不飽和脂肪酸トリグリセリドをエポキシ化し、ヒドロキシル化によって合成
平均分子量：２０００、官能基数：２、水酸基価：５６．１、商品名：「ＢｉＯＨ５０００」、（株）Ｃａｒｇｉｌｌ製。
・ポリイソシアネートＢ１：
トリレンジイソシアネート（２，４−ＴＤＩと２，６−ＴＤＩとが８０：２０の割合であるＴＤＩ）
商品名「ＴＤＩ−８０」、日本ポリウレタン工業株式会社製
・発泡剤Ｃ１： 水
・発泡剤Ｃ２： 塩化メチレン
・整泡剤Ｄ１：
シリコーン整泡剤、商品名「ＳＺ−１１３６」、東レダウコーニング社製。
・アミン系触媒Ｅ１：
トリエチレンジアミン３３ｗｔ％ ジプロピレングリコール溶液、エアプロダクツ株式会社製。
・金属触媒Ｅ２：
スタナスオクトエート、商品名：「ＭＲＨ１１０」、城北化学株式会社製。
・添加剤Ｆ１：
ポリオキシアルキレンエーテルポリオール。ＰＯ付加体
平均分子量：２００、官能基数：２、水酸基価：５６１、商品名「ＰＰ２００」、三洋化成工業株式会社製。

The abbreviations in Table 1 are as follows.
Polyol A1:
Polyoxyalkylene ether polyol. Polyoxyethylene / oxypropylene ether polyol EO / PO adduct Average molecular weight: 3000, number of functional groups: 3, hydroxyl value: 56.1
Polyol A2:
Polyoxyalkylene ether / polyester block copolymer polyol Average molecular weight: 3000, hydroxyl value: 56.1, trade name “L-50”, manufactured by Mitsui Takeda Chemical Co., Ltd.
Polyol A3:
Castor oil (triglycerol ricinoleate)
Average molecular weight: 1000, number of functional groups: 2.7, hydroxyl value: 160, degree of plant-derived: 100%, trade name: “URIC-H30”, manufactured by Ito Oil Co., Ltd.—Polyol A4:
Soybean oil-derived polyol Epoxylated unsaturated fatty acid triglyceride based on linoleic acid and synthesized by hydroxylation Average molecular weight: 2000, number of functional groups: 2, hydroxyl value: 56.1, trade name: “BiOH5000”, Inc. Made by Cargill.
-Polyisocyanate B1:
Tolylene diisocyanate (TDI in which 2,4-TDI and 2,6-TDI are in a ratio of 80:20)
Trade name “TDI-80”, manufactured by Nippon Polyurethane Industry Co., Ltd. ・ Foaming agent C1: Water ・ Foaming agent C2: Methylene chloride ・ Foam stabilizer D1:
Silicone foam stabilizer, trade name “SZ-1136”, manufactured by Toray Dow Corning.
・ Amine catalyst E1:
Triethylenediamine 33 wt% dipropylene glycol solution, manufactured by Air Products Co., Ltd.
-Metal catalyst E2:
Stanus octoate, trade name: “MRH110”, manufactured by Johoku Chemical Co., Ltd.
Additive F1:
Polyoxyalkylene ether polyol. PO adduct average molecular weight: 200, number of functional groups: 2, hydroxyl value: 561, trade name “PP200”, manufactured by Sanyo Chemical Industries, Ltd.

  In addition, this invention is not limited to the illustrated Example, The implementation by the structure of the range which does not deviate from the content described in each item of a claim is possible.

Claims (5)

In the polyurethane foam for frame lamination made of polyurethane raw material containing polyol, polyisocyanate, foaming agent, catalyst,
A polyurethane foam for flame lamination, wherein the polyol contains ricinoleic acid.   The polyurethane foam for flame lamination according to claim 1, wherein the polyol contains 20 parts by weight or more of the ricinoleic acid per 100 parts by weight of the polyol. A polyurethane foam for frame lamination comprising a polyurethane raw material containing a polyol derived from castor oil and satisfying the following formula (1):
((A × B) / C) × 100 ≧ 10 (1)
However, in the formula (1), A is the number of parts (parts) of the castor oil-derived polyol, B is the content (% by weight) of ricinoleic acid in the castor oil-derived polyol, and C is the total addition of the polyurethane raw material Indicates the number of copies.   A laminate comprising: a foam layer made of the polyurethane foam for frame lamination according to any one of claims 1 to 3; and a surface layer bonded to at least a part of a surface of the foam layer. body.   The interior material for vehicles shape | molded by the laminated body of Claim 4.