JP2007326971A - Polyurethane foam for frame laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane foam for frame laminate, which can exhibit an excellent adhesive strength and can prevent discoloration. <P>SOLUTION: This polyurethane foam for the frame laminate, produced by reacting, foaming and curing polyurethane foam raw materials comprising a polyol, a polyisocyanate, a foaming agent and a catalyst, is characterized by compounding at least one organic compound selected from benzothiazole-based compounds and dithiocarbamate-based compounds and an endothermic agent in the polyurethane foam raw materials. The organic compound has preferably a decomposition temperature of 170 to 220°C and is preferably compounded in an amount of 0.1 to 2.0 pts.mass per 100 pts.mass of the polyol. The endothermic agent is preferably a sulfate hydrate and is preferably compounded in an amount of 3.0 to 20.0 pts.mass per 100 pts.mass of the polyol. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyurethane foam for a frame laminate used when a skin is covered by a frame laminating method in a manufacturing process of a cushion used for, for example, an automobile seat.

  The polyurethane foam for frame laminating is bonded to the fabric by melting the surface of the foam by applying a flame (frame) in order to bond it to the fabric, and developing adhesiveness at that portion. Such polyurethane foam is a low-density soft polyurethane foam, and further reduction in density is required for the purpose of weight reduction and the like. In that case, when only the foaming agent is water, it is necessary to increase the amount of water added in order to reduce the density. Therefore, the foaming reaction is promoted and the exothermic temperature at the time of foaming reaches 170 ° C. or more. For this reason, oxidation deterioration (scorch) of polyurethane occurs, and the resulting soft polyurethane foam changes color. In order to avoid such a situation, a technique is known in which methylene chloride or liquefied carbon dioxide gas is added as a foaming aid with the conventional amount of water added.

  However, methylene chloride is one of the substances that adversely affect the environment and its use is regulated. On the other hand, foaming with liquefied carbon dioxide requires special equipment for supplying the liquefied carbon dioxide at a high pressure. In order to perform foaming smoothly, the production conditions are limited and the production cost also increases. Therefore, a method has been proposed in which a hydrate of an inorganic compound such as dihydrate gypsum is used as a foam raw material, and the reaction temperature is lowered by utilizing the latent heat of vaporization of water generated by heating.

In addition, the polyurethane foam for frame laminate is required to have high adhesive strength such as peel strength to the skin material. In order to satisfy such a requirement, a method of improving initial adhesiveness using a cross-linking agent made of a specific polyol is known (see, for example, Patent Document 1).
JP 2003-252946 A (pages 2 and 3)

  As described above, the polyurethane foam for frame laminate is required to have high adhesion strength with the skin material and at the same time, less discoloration due to scorch. However, the technique described in Patent Document 1 is excellent in initial adhesiveness, but the foam raw material contains a hydrate of an inorganic compound as a heat-absorbing agent and is not consumed in the foaming process. When the hydrate remains, the melting temperature of the polyurethane foam rises. Therefore, there is a problem that the polyurethane foam is hardly melted by the frame, and as a result, the adhesive strength is lowered.

  Accordingly, an object of the present invention is to provide a polyurethane foam for a frame laminate that can exhibit excellent adhesive strength and can suppress discoloration.

  In order to achieve the above object, the polyurethane foam for a frame laminate of the invention according to claim 1 is obtained by reacting a raw material of a polyurethane foam containing polyols, polyisocyanates, a foaming agent and a catalyst, A polyurethane foam for a frame laminate formed by curing, wherein the polyurethane foam material contains at least one organic compound selected from a benzothiazole compound and a dithiocarbamate compound and an endothermic agent. It is characterized by.

  The polyurethane foam for frame laminate of the invention described in claim 2 is characterized in that, in the invention of claim 1, the organic compound is a compound having a decomposition temperature of 170 to 220 ° C.

  The polyurethane foam for a frame laminate according to a third aspect of the present invention is the invention according to the first or second aspect, wherein the organic compound is blended in an amount of 0.1 to 2.0 mass per 100 parts by mass of polyols. Part.

  The polyurethane foam for a frame laminate according to a fourth aspect of the present invention is the invention according to any one of the first to third aspects, wherein the endothermic agent is a sulfate hydrate. It is.

  The polyurethane foam for frame laminate of the invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the endothermic agent is blended in an amount of 3.0 to 20 per 100 parts by mass of polyols. 0.0 part by mass.

According to the present invention, the following effects can be exhibited.
In the polyurethane foam for frame laminate according to the first aspect of the present invention, at least one organic compound selected from a benzothiazole compound and a dithiocarbamate compound is blended in the raw material. This organic compound is considered to exhibit an action of lowering the melting start temperature of the polyurethane foam. As a result, the polyurethane foam is easily melted by the frame, and the melted portion is increased to improve the adhesiveness. Accordingly, the polyurethane foam can exhibit excellent adhesive strength such as peel strength.

  Moreover, since the endothermic agent is blended in the raw material of the polyurethane foam, the endothermic agent develops an endothermic action during the foaming process, so the temperature during the reaction is lowered. Therefore, scorch is suppressed and discoloration of the polyurethane foam can be suppressed.

  In the polyurethane foam for frame laminate of the invention according to claim 2, when the decomposition temperature of the organic compound is 170 to 220 ° C., the effect of lowering the melting start temperature of the polyurethane foam is effectively expressed. It is estimated that Therefore, the effect of the invention according to claim 1 can be improved.

  In the polyurethane foam for frame laminate of the invention described in claim 3, the compounding amount of the organic compound is 0.1 to 2.0 parts by mass per 100 parts by mass of polyols. The effect of the invention which concerns on claim | item 2 can fully be exhibited.

  In the polyurethane foam of the invention described in claim 4, the endothermic agent is a sulfate hydrate. For this reason, in addition to the effect of the invention according to any one of claims 1 to 3, the sulfate hydrate is decomposed along the foaming process of the raw material of the polyurethane foam to produce water. The endothermic effect can be satisfactorily exhibited by the latent heat of vaporization.

  In the polyurethane foam of invention of Claim 5, since the compounding quantity of the said endothermic agent is 3.0-20.0 mass parts per 100 mass parts of polyols, any of Claims 1-4 In addition to the effects of the invention, the endothermic effect of the endothermic agent can be sufficiently exhibited.

In the following, embodiments that are considered to be the best of the present invention will be described in detail.
The polyurethane foam for frame lamination in the present embodiment (hereinafter, also referred to as polyurethane foam or simply foam) is obtained as follows. That is, it is obtained by reacting, foaming and curing a raw material of polyurethane foam containing polyols, polyisocyanates, a foaming agent and a catalyst. At that time, at least one organic compound selected from a benzothiazole-based compound and a dithiocarbamate-based compound and an endothermic agent are blended in the raw material of the polyurethane foam.

  And the said organic compound is considered that the melting start temperature of a polyurethane foam is lowered | hung and the surface of a foam is melted at a lower temperature and the function which improves adhesiveness is exhibited. On the other hand, the endothermic agent is considered to exhibit an endothermic effect when heated in the process of reaction and foaming of the raw material of the polyurethane foam.

Next, the raw materials for the polyurethane foam will be described in order.
As the polyols, polyether polyols or polyester polyols are used. Of these, polyether polyols are preferred because they are excellent in reactivity with polyisocyanates and do not hydrolyze like polyester polyols. Examples of the polyether polyol include polypropylene glycol, polytetramethylene glycol, polyether polyol made of a polymer obtained by addition polymerization of propylene oxide and ethylene oxide to a polyhydric alcohol, and modified products thereof. Examples of the polyhydric alcohol include glycerin and dipropylene glycol.

  Specific examples of polyether polyols include triols obtained by addition polymerization of propylene oxide to glycerin and addition polymerization of ethylene oxide, and diols obtained by addition polymerization of propylene oxide to dipropylene glycol and addition polymerization of ethylene oxide. . The polyethylene oxide unit in the polyether polyol is about 10 to 30 mol%. When the content of the polyethylene oxide unit is high, the hydrophilicity is higher than when the content is low, and the miscibility with highly polar molecules, polyisocyanates and the like is improved. As a result, the reactivity increases.

  As polyester polyols, in addition to condensation polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, diethylene glycol, propylene glycol and glycerin, lactone polyester polyols and polycarbonate systems A polyol is used. These polyols can change the number of functional groups and the hydroxyl value of the hydroxyl group by adjusting the kind of raw material component, the molecular weight, the degree of condensation, and the like.

  The polyisocyanates to be reacted with the polyols are compounds having a plurality of isocyanate groups, specifically, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI). ), Triphenylmethane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and modified products thereof. The isocyanate index (isocyanate index) of the polyisocyanates may be 100 or less or exceed 100, but is usually about 90 to 130, and preferably about 100 to 120. Here, the isocyanate index represents the equivalent ratio of the isocyanate groups of the polyisocyanates to the active hydrogen groups such as polyols and water as a foaming agent in percentage. Therefore, an isocyanate index exceeding 100 means that polyisocyanates are in excess of polyols and the like.

The foaming agent is for foaming a polyurethane resin to form a polyurethane foam. For example, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide gas, etc. are used in addition to water. As the foaming agent, water that is highly reactive in the foaming reaction and easy to handle is preferable. When the foaming agent is water, the blending amount is preferably 3 to 9 parts by mass with respect to 100 parts by mass of polyols in order to make the apparent density of the polyurethane foam 20 to 25 kg / m ³ . When the amount of water is less than 3 parts by mass, the amount of foaming is small, and the apparent density of the polyurethane foam tends to exceed 25 kg / m ³ , and when it exceeds 9 parts by mass, the temperature tends to rise during foaming and curing. It becomes difficult to lower

  The catalyst is for accelerating the urethanation reaction between polyols and polyisocyanates, the foaming reaction between water as a blowing agent and polyisocyanates, specifically, triethylenediamine, dimethylethanolamine, N , N ′, N′-trimethylaminoethylpiperazine, etc., tertiary amines, tin octylate (tin octoate), organometallic compounds (metal catalysts) such as dibutyltin dilaurate, acetates, alkali metal alcoholates and the like.

  As this catalyst, it is preferable to use a combination of an amine catalyst and a metal catalyst in order to enhance the effect. In particular, when the blending amount of the endothermic agent such as a hydrate of an inorganic compound is a large amount blending of 20 to 30 parts by mass per 100 parts by mass of the polyol, the strain characteristics of the foam tends to be inferior. It is desirable to employ a catalyst system in combination with a metal catalyst.

  It is preferable that the compounding quantity of an amine catalyst is 0.01-0.5 mass part per 100 mass parts of polyols, and it is more preferable that it is 0.1-0.5 mass part. When the compounding amount of the amine catalyst is less than 0.01 parts by mass, the resinification reaction and the foaming reaction cannot be promoted sufficiently and in a well-balanced manner. On the other hand, if it exceeds 0.5 parts by mass, the resinification reaction and the foaming reaction may be excessively promoted, or the balance between the two reactions may be impaired. Moreover, it is preferable that the compounding quantity of a metal catalyst is 0.1-0.5 mass part per 100 mass parts of polyols. When the blending amount of the metal catalyst is less than 0.1 parts by mass, the balance between the resinification reaction and the foaming reaction is lost and foaming cannot be performed satisfactorily. On the other hand, when it exceeds 0.5 parts by mass, the resinification reaction and the foaming reaction are excessively promoted, the balance between the two reactions is deteriorated, and the strain characteristic of the foam is deteriorated.

  Next, the organic compound will be described. Such an organic compound is a material that functions to increase the adhesiveness by melting the foam surface at a lower temperature by lowering the melting start temperature of the foam. As such an organic compound, at least one compound selected from benzothiazole compounds and dithiocarbamate compounds is used. Examples of the benzothiazole compound include 2-mercaptobenzothiazole or a salt thereof, di-2-benzothiazolyl disulfide, and the like. Dithiocarbamate compounds include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibutyldithiocarbamate, dimethyldithiocarbamate Examples thereof include copper acid and ferric dimethyldithiocarbamate.

  It is preferable that the compounding quantity of this organic compound is 0.1-3.0 mass parts per 100 mass parts of polyols. When this compounding quantity is less than 0.1 mass part, the effect | action of an organic compound is not fully exhibited but the adhesive strength of the polyurethane foam obtained tends to be insufficient. On the other hand, when the blending amount exceeds 3.0 parts by mass, the action of the organic compound is not further improved, and the physical properties of the polyurethane foam may be lowered due to the excessive organic compound.

Next, the endothermic agent will be described. This endothermic agent is a substance that can exhibit an endothermic effect when heated in the process of producing a polyurethane foam, and an inorganic compound hydrate or the like is used. Hydrates of inorganic compounds are materials that decompose by heating and generate water by decomposition. Specifically as a hydrate of an inorganic compound, calcium sulfate dihydrate (CaSO ₄ .2H ₂ O, dihydrate gypsum, specific gravity 2.32, decomposition temperature 128 to 163 ° C.), magnesium sulfate monohydration To 7 hydrate (MgSO ₄ .H ₂ O to MgSO ₄ .7H ₂ O, specific gravity 2.57 to 1.68, decomposition temperature 150 ° C.), iron sulfate monohydrate to pentahydrate (FeSO ₄ · H ₂ O to FeSO ₄ · 5H ₂ O, specific gravity 2.97, decomposition temperature 100 to 130 ° C.) or a mixture thereof, and other monohydrate to trihydrate (Al ₂ O ₃ · H) ₂ O to Al ₂ O ₃ .3H ₂ O, specific gravity 2.4 to 3.4, decomposition temperature 150 to 360 ° C., copper sulfate pentahydrate (CuSO ₄ .5H ₂ O, specific gravity 2.29), etc. Is used. The water of hydration contained in the hydrate of the inorganic compound is water that is stably present at room temperature as a solid crystal and is crystal water. The inorganic compound hydrate is preferably a sulfate hydrate such as calcium sulfate hydrate, magnesium sulfate hydrate, or iron sulfate hydrate. This is because the sulfate hydrate can gradually decompose at a temperature of, for example, 100 ° C. or higher along the foaming process of the raw material of the polyurethane foam to produce water, thereby exhibiting an endothermic effect.

  The specific gravity of the inorganic compound hydrate is preferably 1.5 to 4.0. If this specific gravity is less than 1.5, a predetermined mass cannot be added unless a large amount of inorganic compound hydrate (powder) is added to the polyurethane foam raw material, for example, polyols. Mixing and stirring with a kind cannot be performed sufficiently. And the volume of the hydrate of the inorganic compound which occupies in a polyurethane foam becomes large, and the physical property as a polyurethane foam falls. On the other hand, if the specific gravity exceeds 4.0, water of an inorganic compound that tends to settle when stored for a long time in a polyurethane foam raw material, particularly in a polyol, disperses in the reaction mixture, and lowers the heat generation temperature. The function of Japanese products is reduced.

  The decomposition temperature of the inorganic compound hydrate is preferably 100 to 170 ° C. When the decomposition temperature is less than 100 ° C., water generated by decomposition is generated at the initial stage of foaming and curing by the polyurethane raw material, that is, at a stage where the exothermic temperature is low. May function as a foaming agent. By the way, calcium sulfate dihydrate (dihydrate gypsum) decomposes 1.5 mol water out of 2 mol water in the molecule at 128 ° C. into free water, resulting in 0.5 hydrate calcium sulfate. It becomes a thing (half water gypsum). In addition, magnesium sulfate heptahydrate is decomposed into 6 mol of water out of 7 mol of water in the molecule at 150 ° C. to become free water, and becomes magnesium sulfate monohydrate.

  The blending amount of the endothermic agent is preferably 3.0 to 20.0 parts by mass per 100 parts by mass of polyols. When the blending amount is less than 3.0 parts by mass, the amount of water generated by decomposition is small, and an increase in heat generation temperature based on reaction and foaming cannot be sufficiently suppressed. On the other hand, when the amount exceeds 20.0 parts by mass, excess water functions as a foaming agent, and the foaming reaction may proceed excessively to increase the heat generation temperature.

  A foam stabilizer, a crosslinking agent, a filler, a stabilizer, a colorant, a flame retardant, a plasticizer, and the like are blended in the polyurethane foam raw material according to a conventional method, if necessary. Examples of the foam stabilizer include silicone compounds, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate, polyether siloxane, and phenolic compounds.

  A polyurethane foam is produced by reacting a polyurethane raw material with foaming and curing, but the reaction at that time is complicated, and basically the following reaction is the main component. That is, addition polymerization reaction (polyurethanation reaction) between polyols and polyisocyanates, foaming (foaming) reaction between polyisocyanates and water as a blowing agent, and crosslinking between these reaction products and polyisocyanates ( Curing) reaction.

  When producing a polyurethane foam, a one-shot method in which a polyol and a polyisocyanate are directly reacted or a polyol and a polyisocyanate are reacted in advance to obtain a prepolymer having an isocyanate group at the terminal, Any of the prepolymer methods in which polyols are reacted therewith can be employed. Polyurethane foam is foamed and cured in the mold by injecting the polyurethane foam raw material (reaction mixture) into the slab foaming method and molding mold obtained by foaming and curing at room temperature and atmospheric pressure, and then clamping the mold. It may be produced by any method of the mold foaming method obtained. In this case, the slab foaming method is preferable because it is simple and can be continuously produced.

The polyurethane foam thus obtained has a sufficient adhesive strength of 0.6 to 2.4 N / 25 mm, for example, as the adhesive strength by a frame laminating method, and a color difference (ΔYI) indicating discoloration of 9 to 9 27. Further, the apparent density specified in JIS K 7222: 1999 is a low density of 20 to 25 kg / m ³ . Furthermore, the polyurethane foam has a hardness of 70 to 85 N, an air flow rate of 20 to 75 L / min, a tensile strength of 100 to 150 kPa, an elongation of 110 to 200%, a tear strength of 4 to 7 N / cm, and a compressive residual strain. Is 4 to 11% and the rebound resilience is 25 to 30%. Such a polyurethane foam is a soft polyurethane foam that has good cushioning properties and is lightweight. Here, the flexible polyurethane foam generally refers to a cell (bubble) having a communication structure, flexibility and resilience. Therefore, the flexible polyurethane foam can exhibit properties such as cushioning properties, impact absorption properties, and sound absorption properties. The polyurethane foam for frame lamination is suitably used when covering the skin by the frame laminating method in the manufacturing process of a cushion used for an automobile seat (seat) or the like. In addition, it is used when the skin of fabric, leather, etc. is pasted on the ceiling material of automobiles, the sofa ceiling material of furniture, and the ceiling material of bed.

  Now, the operation of the present embodiment will be described. A polyurethane foam raw material is blended with an endothermic agent such as a hydrate of at least one organic compound and inorganic compound selected from a benzothiazole compound and a dithiocarbamate compound. The And the polyurethane foam is obtained by the raw material being heated, reacting, foaming and hardening. In this process, an endothermic effect due to the latent heat of vaporization of water is expressed, temperature rise is suppressed, and a foam is produced at a temperature lower than 170 ° C. For this reason, generation | occurrence | production of scorch is suppressed and yellowing of a foam is suppressed.

  When the obtained foam is used, for example, in the production process of a cushion used in a car seat (seat), when the skin is laminated by the frame lamination method, the organic compound lowers the melting start temperature of the foam. The foamed part of the frame starts to melt at a low temperature. For example, a polyurethane foam without an organic compound has a melting start temperature of about 200 ° C., whereas an organic compound has a melting start temperature of about 190 ° C., and the melting start temperature is about 10 ° C. descend. Therefore, the amount of the melted portion of the resin melted by the frame is increased, and high adhesiveness is expressed in the melted portion.

The effects exhibited by the above embodiment will be described below.
In the polyurethane foam for frame laminate in the present embodiment, at least one organic compound selected from benzothiazole compounds and dithiocarbamate compounds is blended in the raw material. This organic compound is considered to lower the melting start temperature of the polyurethane foam, and since the surface of the foam is easily melted by the frame, the polyurethane foam for the frame laminate can exhibit excellent adhesive strength. it can.

  Moreover, since the endothermic agent is mix | blended with the raw material of a polyurethane foam and the endothermic agent exhibits the endothermic effect in a foaming process, scorch is suppressed and discoloration of a polyurethane foam can be suppressed.

-The decomposition temperature of the said organic compound is 170-220 degreeC, The effect which reduces the melting start temperature of a polyurethane foam can be exhibited effectively.
-The compounding quantity of an organic compound can fully exhibit said effect by being 0.1-2.0 mass parts per 100 mass parts of polyols.

  ・ Since the endothermic agent is a sulfate hydrate, the sulfate hydrate is decomposed along the foaming process of the polyurethane foam raw material to produce water, and the heat is absorbed by the latent heat of vaporization of the water. Good performance can be achieved.

-The endothermic effect by an endothermic agent can fully be exhibited because the compounding quantity of an endothermic agent is 3.0-20.0 mass parts per 100 mass parts of polyols.
Furthermore, it is considered that the organic compound and the hydrate of the inorganic compound act in cooperation to suppress excessive progress of the foaming reaction and promote the crosslinking reaction. Therefore, mechanical properties such as hardness, tensile strength, elongation, and compressive residual strain of the obtained polyurethane foam can be improved.

  In addition, the organic compound suppresses the formation of chromophores such as urea bonds, and also suppresses the generation of NOx gas, thereby suppressing the discoloration of the foam. In addition, it is uniform on a mass production scale, and a good foam can be obtained, and the productivity of the foam can be improved.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
(Examples 1-7)
First, the raw material of the polyurethane foam used in each Example is shown below.

Polyol L-50: Polyether polyester polyol, hydroxyl value 58 (mgKOH / g), manufactured by Mitsui Takeda Chemical Co., Ltd. Polyol GP3000: Polyether polyol obtained by addition polymerization of propylene oxide to glycerin, molecular weight 3000, the number of functional groups of hydroxyl groups 3. Hydroxyl value 56 (mgKOH / g), Sanyo Chemical Industries Co., Ltd. Water: Foaming agent Dimethylethanolamine: Amine catalyst Metal catalyst MRH-110: Dibutyltin dilaurate, Johoku Chemical Co., Ltd. Foam stabilizer F-650A : Silicone foam stabilizer, Shin-Etsu Chemical Co., Ltd. Phosphorus compound: Tris (dipropylene glycol) phosphite, GE Toshiba Silicone Co., Ltd., CS-22
Flame retardant: Chlorinated phosphate ester, manufactured by Daihachi Chemical Co., Ltd., CR-504L
Polyisocyanate T-80: manufactured by Nippon Polyurethane Industry Co., Ltd., Tolylene diisocyanate (a mixture of 80% by mass of 2,4-tolylene diisocyanate and 20% by mass of 2,6-tolylene diisocyanate)
Dihydrate gypsum: dihydrate gypsum with a specific gravity of 2.32 and an average particle size of 40 μm, manufactured by Noritake Company Limited, G-40
Organic compound powder 1: zinc dibenzyldithiocarbamate, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller ZTC
Organic compound powder 2: zinc N-pentamethylenedithiocarbamate, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller ZP
Organic compound powder 3: zinc diethyldithiocarbamate, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller EZ
Organic compound powder 4: zinc N-ethyl-N-phenyldithiocarbamate, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller PX
Organic compound powder 5: 2-mercaptobenzothiazole, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller M (or Noxeller MP)
Organic compound powder 6: N-oxydiethylene-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller MSA-G
And the raw material of the polyurethane foam in each example was prepared with the compounding ratio shown in Table 1.

These polyurethane foam raw materials are poured into foam containers of 500 mm in length, width, and depth, foamed at room temperature and atmospheric pressure, and then cured (crosslinked) by passing through a heating furnace to be softened. A slab foam was obtained. The obtained soft slab foam was cut out to produce a sheet-like polyurethane foam. With respect to this polyurethane foam, the apparent density, hardness, air flow rate, tensile strength, elongation, tear strength, compression residual strain, rebound resilience, peel strength and color difference (ΔYI) were measured according to the following measurement methods. The results are shown in Table 1. In Table 1, the values in parentheses in the peel strength and color difference represent the ratio (percentage) to the value of Comparative Example 1, respectively.
(Measuring method)
Apparent density (kg / m ³ ): Measured according to JIS K 7222: 1999.

Hardness (N): Measured according to JIS K 6400-2: 2004.
Aeration rate (L / min): Measured according to ASTM D3574.
Tensile strength (kPa), elongation (%) and tear strength (N / cm): Measured according to JIS K 6400-5: 2004.

Compression residual strain (%): Measured according to JIS K 6400-4: 2004.
Rebound resilience (%): Measured according to JIS K 6400-3: 2004.
Peel strength (N / 25 mm): Using a frame lamination device, the polyurethane foam was bonded to a cloth (cloth), and peeled after 70 seconds, 95 seconds and 120 seconds from the start of melting of the foam in the frame lamination device. The strength (180 degree peel strength) was measured according to JIS L 1066.

  Color difference (ΔYI): Color difference meter (SM color computer SM-4, manufactured by Suga Test Instruments Co., Ltd.) for the part (center part) and the part (surface part) having a low temperature during reaction and foaming. Were used to measure the yellowing degree (whiteness) and indicated by their color difference (ΔYI).

表１に示したように、実施例１〜７においては、剥離強度が比較例１における経時変化後の各々の剥離強度を基準として各実施例の値を比べると１２２〜３７８％という高い値を示し、接着強度（剥離強度）に優れていることが示された。これは、前記有機化合物の粉体がポリウレタン発泡体の溶融開始温度を下げて接着性の向上に寄与したためと考えられる。また、発泡体の色差も比較例１の各値に比べて２６〜７６％という低い値を示し、黄変度が少ないことが示された。これは、吸熱剤としての二水石膏が発泡体の製造過程で加熱され分解して水を生成し、蒸発潜熱を奪って温度上昇が抑制されたためと考えられる。さらに、得られたポリウレタン発泡体の硬さ、通気量、引張強さ、伸び、引裂強さ、圧縮残留歪及び反発弾性率が良好であった。これは、有機化合物の粉体と二水石膏とが相乗的に作用して泡化反応の過度の進行が抑えられるとともに、架橋反応が促進されたことによるものと推測される。
（実施例８〜１０及び比較例１〜３）
実施例１〜７と異なる点を以下に示し、その他は実施例１〜７と同様にしてポリウレタン発泡体を調製した。実施例１〜７と異なるポリウレタン発泡体の原料を以下に示す。

As shown in Table 1, in Examples 1 to 7, when the peel strength is compared with the values of the respective examples based on the peel strength after change with time in Comparative Example 1, a high value of 122 to 378% is obtained. It was shown that the adhesive strength (peel strength) is excellent. This is probably because the organic compound powder contributed to the improvement of adhesion by lowering the melting start temperature of the polyurethane foam. Further, the color difference of the foam also showed a low value of 26 to 76% as compared with the respective values of Comparative Example 1, indicating that the degree of yellowing was small. This is presumably because dihydrate gypsum as an endothermic agent was heated and decomposed in the process of producing the foam to produce water, taking away latent heat of evaporation and suppressing the temperature rise. Furthermore, the hardness, air flow rate, tensile strength, elongation, tear strength, compressive residual strain, and rebound resilience of the obtained polyurethane foam were good. This is presumably because the organic compound powder and dihydrate gypsum act synergistically to suppress excessive progress of the foaming reaction and promote the crosslinking reaction.
(Examples 8 to 10 and Comparative Examples 1 to 3)
Differences from Examples 1 to 7 are shown below, and the others were the same as in Examples 1 to 7, and polyurethane foams were prepared. The raw materials of the polyurethane foam different from Examples 1-7 are shown below.

Magnesium sulfate heptahydrate: Magnesium sulfate heptahydrate having a specific gravity of 1.68 and an average particle size of 50 μm In Example 8, magnesium sulfate heptahydrate was used as the hydrate of the inorganic compound. In Example 9, Noxeller ZTC and Noxeller MSA-G were used in combination as organic compounds. In Example 10, dihydrate gypsum as a hydrate of an inorganic compound and Noxeller ZP as an organic compound were used.

  In Comparative Example 1, dihydrate gypsum was blended as an inorganic compound hydrate, and the organic compound powder was not blended. In Comparative Example 2, an organic compound outside the scope of the present invention was blended as an organic compound. In Example 3 and Comparative Example 3, an example was shown in which the amount of dihydrate gypsum was increased to 20.0 parts by mass.

  Then, a polyurethane foam was produced in the same manner as in Examples 1 to 7, and the apparent density, tensile strength, elongation, tear strength, peel strength and color difference (ΔYI) of the obtained polyurethane foam were determined in Example 1. It measured according to the measuring method similar to ~ 7. The results are shown in Table 2. In Table 2, the values in parentheses in the peel strength and color difference represent the ratio (percentage) to the value of Comparative Example 1, respectively.

表２に示したように、実施例８〜１０においては、剥離強度が比較例１に比べて１５８〜２８１％という高い値を示した。また、発泡体の色差も比較例１に比べて１４．２〜２３．１％という低い値を示した。その一方、比較例１では有機化合物の粉体を全く配合しなかったため、剥離強度が低い結果であった。比較例２では有機化合物の粉体として本発明の範囲外の化合物を使用したため、剥離強度を向上させることができなかった。比較例３では二水石膏を増量したが、かえって接着しない状態になると共に、変色も大きくなる結果であった。これは、増量した二水石膏が一部残存し、また有機化合物が含まれていないため、接着が阻害されると同時に、変色が促進されたものと推測される。

As shown in Table 2, in Examples 8 to 10, the peel strength was as high as 158 to 281% compared to Comparative Example 1. Further, the color difference of the foam also showed a low value of 14.2 to 23.1% as compared with Comparative Example 1. On the other hand, in Comparative Example 1, since no organic compound powder was blended, the peel strength was low. In Comparative Example 2, since a compound outside the range of the present invention was used as the organic compound powder, the peel strength could not be improved. In Comparative Example 3, the amount of dihydrate gypsum was increased. However, the result was that it did not adhere, and discoloration increased. This is presumed that discoloration was promoted at the same time that adhesion was inhibited because part of the increased amount of dihydrate gypsum remained and no organic compound was contained.

In addition, this embodiment can also be changed and embodied as follows.
-In addition to inorganic hydrates, sodium phosphate, metal hydroxide, xylitol, etc. can be used as the endothermic agent.

  As the hydrate of the inorganic compound, a plurality of types of hydrates, for example, calcium sulfate hydrate and magnesium sulfate hydrate can be combined and blended. In that case, the function of the hydrate of the inorganic compound can be exhibited in a wider temperature range, and the exothermic temperature at the time of reaction and foaming can be effectively reduced.

Further, as the organic compound, two or more kinds of benzothiazole compounds and dithiocarbamate compounds can be used in combination.
-In addition to the said organic compound, vulcanization | cure acceleration | stimulation adjuvants, such as a stearic acid and a zinc stearate, can also be mix | blended.

The organic compound may be in the form of liquid in addition to powder.
Further, the technical idea that can be grasped from the embodiment will be described below.
The polyurethane foam for a frame laminate according to claim 4 or 5, wherein the sulfate hydrate is a calcium sulfate hydrate or a magnesium sulfate hydrate. In this case, in addition to the effect of the invention according to claim 4 or 5, the function of the hydrate of the inorganic compound can be effectively exhibited.

  The polyurethane for a frame laminate according to any one of claims 1 to 5, wherein the foaming agent is water, and a blending amount thereof is 3 to 9 parts by mass per 100 parts by mass of polyols. Foam. When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-5, a foaming reaction can fully be advanced.

  A process for producing a polyurethane foam by reacting, foaming and curing a polyurethane foam raw material containing polyols, polyisocyanates, a foaming agent and a catalyst, wherein the polyurethane foam raw material includes a benzothiazole-based material. A method for producing a polyurethane foam for a frame laminate, comprising blending at least one organic compound selected from a compound and a dithiocarbamate compound and an endothermic agent. According to this production method, a polyurethane foam for frame laminate that can exhibit excellent adhesive strength and can suppress discoloration can be easily produced only by adjusting raw material components.

Claims (5)

A polyurethane foam for a frame laminate obtained by reacting, foaming and curing a raw material of a polyurethane foam containing a polyol, a polyisocyanate, a foaming agent and a catalyst,
A polyurethane foam for a frame laminate, characterized in that at least one organic compound selected from a benzothiazole compound and a dithiocarbamate compound and an endothermic agent are blended as a raw material for the polyurethane foam. The polyurethane foam for a frame laminate according to claim 1, wherein the organic compound is a compound having a decomposition temperature of 170 to 220 ° C. The polyurethane foam for a frame laminate according to claim 1 or 2, wherein the compounding amount of the organic compound is 0.1 to 2.0 parts by mass per 100 parts by mass of polyols. The polyurethane foam for a frame laminate according to any one of claims 1 to 3, wherein the endothermic agent is a sulfate hydrate. 5. The polyurethane foam for a frame laminate according to claim 1, wherein the amount of the endothermic agent is 3.0 to 20.0 parts by mass per 100 parts by mass of polyols. body.