KR100525352B1 - Manutacturing method of non-yellowing flexible polyurethane foam - Google Patents

Abstract

The present invention is a method for producing a flexible polyurethane foam by the catalytic reaction of isocyanate and polyol, octylic acid in a polyether polyol having 0 to 30% by weight of ethylene oxide, 70 to 100% by weight of propylene oxide and 400 to 7,000 molecular weight Resin premixes using a mixed catalyst of tin and dibutyltin dilaurate, carboxylic acid metal salt catalyst, and diazabicycloalkene catalyst at the same time as the isocyanate index range of 90 to 130 to have a stable foam structure and excellent yellowing resistance A method for producing a polyurethane foam.

Soft urethane foam produced by the method of the present invention has a stable foam structure and does not cause yellowing even when exposed to light for a long time there is an effect that can maintain a good commercial quality for a long time.

Description

Manufacturing method of yolk yellow flexible polyurethane foam {Manutacturing method of non-yellowing flexible polyurethane foam}

The present invention relates to a manufacturing method of yolk yellow soft polyurethane foam used in clothing, hygiene products, packaging materials, medical use and the like. More specifically, in the method for producing a flexible polyurethane foam by catalytic reaction of isocyanate and polyol, the content of ethylene oxide (hereinafter referred to as EO) is 0-30% by weight and the content of propylene oxide (hereinafter referred to as PO) is 70-100% by weight. Resin premix using a mixed catalyst of octylic acid tin and dilauric dibutyltin, a carboxylic acid metal salt catalyst, and a diazabicycloalkene catalyst in a polyether polyol having a molecular weight of 400 to 7,000 and a molecular weight of 400 to 7,000 isocyanate index 90 to It relates to a method for producing a flexible polyurethane foam having a stable foam structure by reacting with isocyanate in the range of 130 and excellent in yellowing resistance.

Flexible polyurethane foams are widely used in cushioning materials, clothing products, especially bra cups, sneakers, swimwear pads, etc. due to their inherent elasticity, hardness and light weight.

However, general polyurethane foam is toluene, an aromatic compound.

Since diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are used, azo-compound structure and quinoneimide structure are formed by light, and yellowing tends to occur. This is a different dimension from the cleavage of polymer chains, and discoloration does not directly cause a decrease in physical properties. This yellowing phenomenon is known to be minimized by using an aliphatic or alicyclic isocyanate as an isocyanate component rather than an aromatic isocyanate.

Techniques for producing egg yolk polyurethane foams are not widely known, and in particular, very few are known as techniques for low density foams having a density of 50 kg / m ₃ or less. Representative prior arts of yolk-urethane polyurethane foams including high density foam manufacturing methods having a density of 50 kg / m ₃ or more include Japanese Patent Publication No. 52-30437, Japanese Patent Publication No. 54-15599, and Japanese Patent Publication No. 54-162795 Japanese Patent Application Laid-Open No. 4-239016, Japanese Patent Application Laid-Open No. 2000-226429, Japanese Patent Application Laid-Open No. 2000-273136, Japanese Patent Application Laid-Open 2001-72738, Japanese Patent Application Publication No. 2001-278942, US Patent 4, 067, 832, US Pat. No. 6, 031, 013, US Pat. No. 6, 191, 179 B1, US Pat. No. 2002/0035165 A1, and the like. Japanese Patent Publication No. 52-30437 describes a technique for improving weather resistance while maintaining physical properties of a polyurethane foam by using a catalyst specific to aliphatic or alicyclic isocyanates, and Japanese Patent Publication No. 54-15599 describes as isocyanate. A method of obtaining the color stability of polyurethanes using polyisocyanates in which NCO groups are not directly bonded to aromatic rings and certain catalysts is described. Japanese Patent Application Laid-Open No. 54-162795 discloses at least one compound selected from the group consisting of hydroxides, alcoholates or phenolates of alkali metals, alkali metal salts of weak acids or hexahydrotriazine-S-derivatives with respect to aliphatic or alicyclic polyisocyanates. A polyurethane having improved light stability, that is, improved yellowing due to light, is disclosed by using at least one compound selected from organic compounds such as zinc or iron. Japanese Patent Application Laid-Open No. 2001-72738 discloses a yellowing solution having a swelling ratio of 15% or less in an aqueous solution containing 0.5% by weight of an alkaline detergent by reacting and curing a polyol having an oxyethylene content of 18% by weight or less and an aliphatic polyisocyanate in the presence of a specific catalyst. A method for producing a polyurethane foam is described. U.S. Patent No. 4,025,466 describes diethylene glycol / adipate polyester polyols or polyether polyols, isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate, diazabicycloalkenes and the like. A method of making a low density soft foam having a density of 27 to 37 kg / m ³ using a catalyst in combination with a metal carboxylic acid salt is disclosed. US Pat. No. 6, 031, 013 discloses isocyanates with biuret or isocyanurate structures, which include catalysts of polyol mixtures of 400 to 8,000 molecular weight, blowing agents, metal salts and amine mixtures comprising polyols having a primary hydroxyl group of at least 50%; The reaction was carried out at 40 ° C. or higher to form a yolk yellow furniture foam having a density of 50 to 80 g / l. U. S. Patent No. 6, 191, 179 B1 discloses a mixture of polyols having a molecular weight of 400 to 8,000 containing at least one isocyanate of biuret or isocyanurate structure and at least one polyol having a primary hydroxyl group of at least 50%, a compound having a primary amine group, eg For example, diethanol amine was reacted with N, N-dimethylpropylene diamine, blowing agent, tin, and tertiary amine catalyst at 25 to 35 ° C. to form a foam having a density of 30 to 78 g / l. U.S. Patent No. 2002/0035165 A1 discloses a technique in which an acrylate polyol is added to compensate for the poor physical properties of aliphatic or cycloaliphatic isocyanate foams.

However, because aliphatic or cycloaliphatic isocyanates are much less reactive than aromatic isocyanates, high reaction solution temperatures, sometimes highly reactive components, are required to produce stable foams in addition to certain catalysts that are not commonly used in aromatic isocyanates. In addition, it is much more difficult to balance porosity and resination reactions than aromatic isocyanates to make good foams. For this reason, even if the reactivity of the aliphatic or cycloaliphatic isocyanate is improved in the prior art, the problem is that the foam is unstable and collapses in the actual production process.

Therefore, in this field, it is desired to develop a flexible polyurethane foam having yellowing resistance while maintaining a stable foam structure.

An object of the present invention is to prepare a flexible polyurethane foam by catalytic reaction of an isocyanate with a polyol, wherein the catalyst comprises a composition of tin octylate and dilauric dibutyltin in a fixed ratio and a metal carboxylic acid catalyst and diazabi Cycloalkenes are used together to provide a method for producing a flexible polyurethane foam having a stable foam structure and excellent yellowing resistance.

MEANS TO SOLVE THE PROBLEM In the method of manufacturing flexible polyurethane foam by catalyzing an isocyanate and a polyol, the catalyst used is 0.5-5.0 weight part of octylic acid tin catalysts, and dibutyl tin catalyst of dilaurate 1.0- with respect to 100 weight part of polyols. When the polyurethane foam is prepared using 10 parts by weight and 0.5 to 5 parts by weight of a diazabicycloalkene catalyst, the present invention was completed by confirming that a flexible polyurethane foam having a stable foam structure and excellent yellowing resistance can be produced.

The present invention relates to a method for producing an egg yolk soft polyurethane foam obtained by reacting and curing an aliphatic or alicyclic isocyanate with a polyol in the presence of a catalyst.

The polyol component used in the present invention is a polyether polyol having a molecular weight of 400 to 7,000 having an EO content of 0 to 30% by weight and a PO content of 70 to 100% by weight. Preferably polyether polyols containing 10 to 20% by weight of EO and having a molecular weight in the range of from 3,000 to 6,000 are suitable for this purpose. Aliphatic or cycloaliphatic isocyanates used in the present invention include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 4,4 'diamino diphenylmethane, Lysine diisocyanate, monomer or oligomer of 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane. Of these, monomers or oligomers of 1,6-hexamethylene diisocyanate and isophorone diisocyanate are suitable. Chain extenders and crosslinkers include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, diethyl toluene diamine, glycerin, diethanol amine, Triethanol amine, diol having a molecular weight of 2,000 or less, triol, tetraol, or a mixture selected from one or two or three may be used, preferably ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, diethyl toluene Diamine, glycerin, diethanol amine, triethanol amine, alone or in combination, are used in the range of 0.1 to 2% by weight. Amine catalysts include triethylene diamine, 33% triethylene diamine dissolved in dipropylene glycol, bis (N, N-dimethylaminoethyl) ether, and 70% bis (N, N-dimethylamino dissolved in dipropylene glycol. Ethyl) ether and formic acid block, N, N, N ', N'-tetramethyl-n-hexyl diamine, N, N, N', N ', N-pentamethyl-diethylene triamine. Tin octylate and dibutyl dilaurate tin catalysts can be used in combination rather than alone to significantly improve reactivity and foam stability. At this time, the content ratio of tin octylate to dibutyl tin dilaurate is used in the range of 1: 1 to 5% by weight based on the polyol weight. In addition, 1 to 5% by weight of a metal carboxylic acid catalyst and 0.5 to 5% by weight of a diazabicycloalkene catalyst are used. Representative of the catalyst of the metal carboxylic acid is potassium octoate (potassium octoate). Silicone foam stabilizers are commercially available products, specifically, L-580, L-600, L-620, L-2100, L-5309 from Cromphton or DABCO DC-198, DC-5160, DC from Air Products. Choose from -5188, DC-5388 or Degussa BF-2370, B-8021, B-4900, B-8002, B-8123, preferably L-580, DC-198, BF-2370 alone or Mix 0.5 to 3.0% by weight. As the blowing agent, water, methylene chloride, liquid carbon dioxide, n-pentane, hydrochlorofluorocarbon (hereinafter referred to as HCFC) may be used for the purpose, but preferably water, liquid carbon dioxide, and HCFC are used alone or in combination. do. Polyurethane foams using aliphatic or cycloaliphatic isocyanates are generally excellent in yellowing resistance, but are poor in heat resistance and UV stability, resulting in deterioration of physical properties. Therefore, it is preferable to add commercially available antioxidants, heat stabilizers, light stabilizers, and other additives. Do.

Hereinafter, an Example is given and this invention is demonstrated concretely.

However, the present invention is not limited only to the examples.

(Example 1)

Next, a resin premix composed of polyol, water, a crosslinking agent, a catalyst, a foam stabilizer, and a stabilizer shown in [Table 1] was used as the isophorone diisocyanate and an isocyanate index 105 having a monomer and trimer ratio of 7: 3. Mixing and stirring at 4,000 rpm for 7 seconds gave a flexible polyurethane foam.

The isocyanate index is an index indicating the input amount of isocyanate and resin premix when the polyurethane is prepared by reacting polyol and isocyanate. When the isocyanate is added in the same amount as stoichiometry input, this index is 100 and stoichiometric It is said that this index is greater than 100 when over-injected. The cream time and rise time of the polyurethane foam obtained here were measured, and the result is shown in following [Table 1].

delete

The detailed description about each component, such as a polyol used for the Example and the comparative example, is as follows.

Polyol: Polypropylene glycol with an average molecular weight of 3,000 (56 mgKOH / g hydroxyl value)

        (Examples 1, 2, 4, and Comparative Examples 1, 2 and 3, SKC having an EO content of 0 parts by weight

YUKOL 5603 was used. In Example 3, the EO content was 9

The brand name YUKOL 5613 which is a weight part% was used.)

Crosslinking agent 1: diethanol amine

Crosslinking agent 2: ethylene glycol

Catalyst 1: diazabicycloalkene

Catalyst 2: 70% bis (N, N-dimethylaminoethyl) ether dissolved in dipropylene glycol

Catalyst 3: 33% triethylene diamine dissolved in dipropylene glycol

Catalyst 4: N, N, N ', N', N-pentamethyl-diethylene triamine

Catalyst 5: potassium octylate

Catalyst 6: Octyl Acid Tin

Catalyst 7: dibutyl dilaurate

Anti-foaming agent: L-580

Stabilizer: Tinuvin B 75 from Ciba Specialty Chemicals

Aliphatic isocyanate: In Examples 1,2,3,4 and Comparative Example 1, isophorone diisocyanate (a ratio of monomer to trimer of 7 to 3) was used.

Aromatic isocyanate: Toluene diisocyanate-80 was used in the comparative examples 2 and 3. (Unit: g) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyol 100 100 100 100 100 100 100 water 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Crosslinking agent One 1.0 1.5 1.5 - 1.0 - - 2 - - - 2.5 - - - catalyst One 0.5 0.5 0.5 0.5 0.5 - - 2 0.2 - 0.2 0.2 0.2 0.05 0.05 3 - - - - - 0.15 0.15 4 - 5.0 - - - - - 5 1.5 1.5 1.5 1.5 1.5 - - 6 0.5 0.5 0.5 0.5 1.5 0.2 0.2 7 1.0 1.0 1.0 1.0 - - - Defoamer 1.5 1.5 1.5 1.5 0.8 0.8 stabilizator - - - - - 2.0 Isocyanate Index 105 105 105 105 105 115 115 Cream Time (sec) 17 48 15 50 25 10 10 Rise time (seconds) 88 205 84 94 Foam collapse 95 95

Examples 2-4 and Comparative Examples 1-3

In Example 2, the kind of amine catalyst was changed, and in Example 3, except that the kind of crosslinking agent was changed, the polyurethane foam was produced in the same manner as in Example 1, and the reactivity and various properties were evaluated. In Example 4, it carried out by the method similar to Example 1, without using a foam stabilizer and a stabilizer.

In Comparative Example 1, tin octylate and dibutyl dilaurate tin catalyst were not used in combination, but tin octylate alone was used. Comparative Example 2 is a foam made using toluene diisocyanate-80 aromatic instead of aliphatic isocyanate in order to compare egg yolk variability, Comparative Example 3 is a low-yellowing polyurethane foam in which yellowing is delayed by adding a light stabilizer to be.

<Reactivity and Foam Stability Test>

In urethane foaming, the reactivity was evaluated by measuring the cream time (second) and rise time (second) with a stopwatch, and the foam stability was determined by visually observing the degree of foam sinking after reaching the maximum height during foaming. The results are shown in [Table 2].

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Responsive Cream Time (sec) 17 48 15 50 25 10 10 Rise time (seconds) 88 205 84 94 - 95 95 Foam stability Good Good Good Good collapse Good Good

<Yellowing test>

The soft urethane foams obtained in Example 1 and Comparative Example 3 were placed in a light resistance tester (manufactured by Kyung-King Co., Ltd.), and yellowed according to the methods specified in ASTM E3 13-96 and ASTM D 1925 for 10 hours for 0 to 40 hours. (Yellowness Index) was measured. At this time, the light source of the light resistance tester is an OSRAM solar lamp of 300W. The results are shown in FIG.

1 is a graph showing the yellowing degree of the flexible polyurethane foam obtained in Example 1, Comparative Example 3 and the like of the present invention. In FIG. 1, YI represents a yellowness index, and a lower slope means less yellowing.

The flexible urethane foam produced by the method of the present invention has a stable foam structure and does not cause yellowing even when exposed to light for a long time, and thus has an effect of maintaining good quality for a long time.

 1 is a graph showing the yellowing degree of the flexible polyurethane foam obtained in Example 1, Comparative Example 3 and the like of the present invention.

Claims (4)

In the method of manufacturing the flexible polyurethane foam, Ethylene oxide content from 0 to 30% by weight and propylene oxide content from 70 to 100 parts by weight of polyether polyol having 100% by weight and molecular weight of 400 to 7,000 Crosslinking agent: 0.1-2.5 parts by weight -Octylic acid tin: 0.5 ~ 5.0 parts by weight Dibutyl dilaurate: 1.0 to 10 parts by weight Metal carboxylic acid catalyst: 1 to 5 parts by weight Diazabai cyclo alkenes: 0.5 to 5.0 parts by weight -Silicone foam stabilizer: 0.2 ~ 3 parts by weight Water: 0.2 to 5 parts by weight A method for producing a yolk modified soft polyurethane foam in which a resin premix and an aliphatic or cycloaliphatic polyisocyanate prepared in an isocyanate index range from 90 to 130. The monomer or oligomer of claim 1, wherein the aliphatic or cycloaliphatic polyisocyanate is selected from monomers and oligomers of 1.6-hexamethylene diisocyanate, isophorone diisocyanate, 2.5 (2.6) bis (isocyanatomethyl) bicyclo (2.2.1) heptane. Method for producing a yolk yellow soft polyurethane foam selected. The method of claim 1, Method for producing a yellowing soft polyurethane foam wherein the crosslinking agent is selected from ethylene glycol, diethylene glycol, propylene glycol, 1.4-butanediol, diethyl toluene diamine, glycerin, diethanol amine, triethanol amine The method for producing a yolk yellow soft polyurethane foam according to claim 1, wherein the metal carboxylic acid catalyst is potassium octoate.