JPH09151234A - Urethane foam and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane foam being capable of flame lamination and having low resiliency. SOLUTION: A polyol component comprising 10-60wt.% polyetherpolyesterpolyol having an average functionality of 2-4 and a hydroxyl value of 45-65mgKOH and 10-65wt.% polyol having an average functionality of 1.5-4.5 and a hydroxyl value of 200-300mgKOH is reacted with a polyisocyanate in the presence of a phosphorus compound and a blowing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane foam having a low impact resilience capable of frame lamination and a method for producing the same.

[0002]

2. Description of the Related Art A urethane foam having a low impact resilience has a glass transition point near room temperature and thus easily absorbs energy of vibration and shock, and is therefore used as a cushion material or a soundproof material. Since this urethane foam having low impact resilience has a peculiar moist feel, it can be used as a laminated material laminated with various films, sheets, cloths, etc., for example, automobile interior materials, footwear linings, furniture, clothing. Widely used in bags, etc.

[0003]

Generally, a method of laminating a urethane foam sheet with a film or another sheet includes a method of laminating with an adhesive and a method of applying a gas flame to one surface of the urethane foam sheet to melt the surface layer. It can be roughly classified into the frame lamination method, in which the film is made to be adhesive and the film or other sheet is quickly laminated and crimped. Although the method using an adhesive can be applied to almost all types of urethane foam sheets and films and other sheets, it takes a long time to apply, dry and cure the adhesive, and has the disadvantage of low work efficiency. is there. On the other hand, the frame lamination method enables high-speed bonding and has extremely high work efficiency, but the urethane foam sheet has a property suitable for frame lamination, for example, only the surface layer of the urethane foam sheet is appropriately melted by the flame, It must have the property that when it is bonded to the base material, it is instantly and firmly bonded to make the laminated material ready for winding at high speed. However, in the conventional low impact resilience urethane foam, even if the flame lamination method is applied, the melted part is not sufficiently cured after the bonding, and therefore the bonding still depends on a method with low workability using an adhesive. I had no choice.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted earnest research for producing a urethane foam having a low rebound resilience capable of flame lamination, and as a result, a polyether polyester polyol having a hydroxyl value of 45 to 65 mgKOH / g. And a specific amount of a polyol having a hydroxyl value of 200 to 300 mgKOH / g and, if necessary, a hydroxyl value of 20 to 80 mgKO
H / g polyol and hydroxyl value 80 ~ 150mgKOH
A soft polyurethane foam obtained by reacting a polyol (A) containing an appropriate amount of a polyol / g of a polyol with a polyisocyanate (B) in the presence of a phosphorus-containing compound (C) and a foaming agent (D) has a rebound resilience. The rate is 20% or less,
And it was discovered that frame lamination is possible,
The present invention was completed by further research. That is, in the present invention, (1) the average number of functional groups is 2 to 4, and the hydroxyl value is 45 to 6
5mgKOH / g polyether polyester polyol (A
-1) 10 to 60% by weight and an average number of functional groups of 1.5 to
A polyol (A) containing 10 to 65% by weight of a polyol (A-2) having a hydroxyl value of 200 to 300 mgKOH / g at 4.5, a polyisocyanate (B), a phosphorus compound (C) and a foaming agent (D). The urethane foam (2) obtained by reacting in the presence of (2) polyether polyester polyol (A-1) has an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 50 to 60 mgKOH / g. The urethane foam described in (1) and (3) polyol (A-2) have an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 230 to 270 mg.
The urethane foam described in (1) above which is KOH / g, and (4) the polyol (A) further has an average number of functional groups of 1.5 to 4.5 and a hydroxyl value of 20 to 80 mg KOH / g (A- 3) 1 to 50% by weight of the urethane foam according to (1) above, (5) polyol (A
-3) has an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 30.
The urethane foam (6) polyol (A) according to claim 4 having an average functionality of 1 to 3 and a hydroxyl value of 80 to 150 mg KOH / g (A-4) is 1 to 60 mg KOH / g. The urethane foam according to the above (1), which comprises ˜20% by weight. (7) Polyol (A
-4) has an average number of functional groups of 1.5 to 2.5 and a hydroxyl value of 90 to
115 mgKOH / g, the content of ethylene oxide unit is 50% by weight or more, the urethane foam according to the above (6), (8) the amount of the phosphorus compound (C) used is 1 to 30 with respect to the polyol (A). The urethane foam according to (1) above, which is a weight percent, (9) the foaming agent (D) is water, the urethane foam according to (1) above, and (10) the amount of water used is based on the polyol (A). The urethane foam according to (9) above, which is 0.5 to 4.5% by weight, (11) the polyisocyanate (B) above is a urethane foam according to (1) above, and (12) polyol (A). Contains 30 to 50% by weight of the polyether polyester polyol (A-1) and the polyol (A-
The urethane foam according to the above (1), which contains 20 to 40% by weight of 2), and the urethane according to the above (12), wherein the polyol (A) further contains 20 to 40% by weight of the polyol (A-3). Form, (14)
Polyol (A) further contains polyol (A-4)
The urethane foam according to the above (12), which contains 10 to 10% by weight, (15) 10 to 60% by weight of a polyether polyester polyol (A-1) having an average number of functional groups of 2 to 4 and a hydroxyl value of 45 to 65 mgKOH / g, and The polyisocyanate (B) and the polyol (A) containing 10 to 65% by weight of the polyol (A-2) having an average number of functional groups of 1.5 to 4.5 and a hydroxyl value of 200 to 300 mgKOH / g, and a phosphorus-containing compound (C ) And a foaming agent (D), the method for producing a urethane foam, (16) the polyol (A) has an average number of functional groups of 1.5 to 4.5 and a hydroxyl value of 20 to 20. 80 mg KOH / g polyol (A-3) 1
The method for producing a urethane foam according to (15) above, wherein the polyol (A) further has an average number of functional groups of 1 to 3, and a hydroxyl value of 80 to 150 mg KO.
The method for producing a urethane foam according to the above (15), which contains 1 to 20% by weight of H / g of the polyol (A-4),
It is.

The polyether polyester polyol (A-1) used in the present invention includes, for example, Japanese Patent Publication No. 48-
As described in Japanese Patent Publication No. 10078, a structure in which a polyester chain is blocked in a polyether polyol, that is, a portion which replaces a hydrogen atom of each hydroxyl group of a polyether polyol or its derivative having a hydroxyl group is generally used. Formula (I)

Embedded image (In the formula, R ₁ and R ₂ are each a divalent hydrocarbon residue, and n is a number larger than 1 on average.). In the general formula (I), the divalent hydrocarbon residue represented by R ₁ is, for example, a saturated aliphatic or aromatic polycarboxylic acid residue, and R ₂ is a residue obtained by cleavage of a compound having a cyclic ether group. And n is preferably a number from 1 to 20. This polyether polyester polyol is obtained by reacting a polyether polyol compound with a polycarboxylic acid anhydride and an alkylene oxide compound.

Examples of the above polyether polyols include compounds having a structure in which an active hydrogen-containing compound is added with an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO), or two or more of them are randomly or block-added. be able to. The active hydrogen-containing compound, water or methanol,
Monohydric and polyhydric alcohols such as ethanol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, fatty acid monoglyceride, trimethylolpropane, pentaerythritol, sorbit, sorbitan, sucrose, amines, polyhydric phenols , Polyvalent carboxylic acids and the like. Water and polyhydric alcohols are particularly preferable. The molecular weight of these polyether polyols is not particularly limited, but 200 to 5000 is suitable. As a specific example of the polyether polyol, polyethylene glycol (molecular weight 1000 to 2000) is industrially advantageously used. Examples of the polycarboxylic acid anhydride include anhydrides of succinic acid, glutaric acid and adipic acid, and examples of the aromatic trimellitic acid anhydride include anhydrides of phthalic acid trimellitic acid and pyromellitic acid. . The amount of these used is preferably at least equimolar to the hydroxyl group in order to impart the polyester property to the polyether polyol. As the alkylene oxide compound, for example, ethylene oxide, propylene oxide, or a mixture thereof can be used. The amount used is a necessary and sufficient amount for making the end of the target product a hydroxyl group. As the polyols (A-2), (A-3) and (A-4) used in the method of the present invention, those usually used in the production of polyurethane foams can be used, and examples thereof include polyether polyols. As this polyether polyol,
Examples thereof include alkylene oxide added to an initiator such as water, alcohols, amines, and ammonia. Examples of alcohols include monohydric alcohols such as methanol and ethanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as diglycerin. Hexahydric alcohols such as D-sorbitol and polyhydric alcohols such as octahydric alcohols can be mentioned. Examples of amines include monovalent amines such as dimethylamine and diethylamine, divalent amines such as methylamine and ethylamine, trivalent amines such as monoethanolamine, diethanolamine and triethanolamine,
Examples include polyvalent amines such as tetravalent amines. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-, 1,4- and 2,3-butylene oxide and a combination of two or more thereof. Of these, preferred is propylene oxide and / or ethylene oxide, and the addition form when used in combination may be either block or random.

These polyols can be suitably used in the present invention as a vinyl polymer-containing polyol obtained by polymerizing a vinyl monomer therein. This vinyl polymer-containing polyol can be obtained by, for example, radically polymerizing vinyl monomers such as acrylonitrile and styrene in the above-exemplified polyols and stably dispersing them. The content of the vinyl polymer in the vinyl polymer polyol is usually 10 to 50% by weight, preferably 15 to 50% by weight.
40% by weight. The average number of functional groups of the polyol (A-2) is usually 1.5 to 4.5, preferably 2.5 to 3.5, and the hydroxyl value is usually 200 to 300 mgKOH / g, preferably 230 to 270 mgKOH / g. Is. Hydroxyl value is 200mgK
If it is less than OH / g, the energy absorption of the urethane foam will be insufficient, and if it exceeds 300 mgKOH / g, the resin forming the urethane foam will be hard and the feel will be deteriorated.
The average number of functional groups of the polyol (A-3) is usually 1.5 to
It is 4.5, preferably 2.5 to 3.5, and the hydroxyl value is usually 20 to 80 mgKOH / g, preferably 30 to 60 mgKOH.
/ G. The average number of functional groups of the polyol (A-4) is
It is usually 1 to 3, preferably 1.5 to 2.5, and the hydroxyl value is usually 80 to 150 mgKOH / g, preferably 90 to 115 m.
gKOH / g. Further, it is desirable that the content of ethylene oxide is high, usually 50% by weight or more, preferably 70% by weight or more. Polyol (A-1), (A-2),
The mixing ratio of (A-3) and (A-4) is usually 10 to 10.
60% by weight: 10-65% by weight: 1-50% by weight: 1-
20% by weight, preferably 20-40% by weight: 5
0 to 60% by weight: 1 to 10% by weight: 5 to 15% by weight. The mixing ratio is preferably 30 to 50% by weight: 20 to 4 in order to produce a foam whose hardness is less dependent on temperature.
It is 0% by weight: 20 to 40% by weight: 1 to 10% by weight.
The polyisocyanate (B) used in the present invention is a known polyisocyanate conventionally used for the production of flexible urethane foam, for example, toluene diisocyanate (T
DI), diphenylmethane diisocyanate (MD
I), aromatic polyisocyanates such as phenylene diisocyanate (PDI) and naphthalene diisocyanate (NDI), modified TDI, crude MDI and modified M
DI and the like can be mentioned, and these can be used alone or in combination of two or more kinds. In the present invention, TDI alone is preferably used.

As the phosphorus-containing compound (C) used in the present invention, a known phosphorus-containing compound which has been conventionally used as a flame retardant for urethane foam is preferably used. Examples thereof include trismonochloroethyl phosphate, trisdichloropropyl phosphate, and the like. Trishaloalkyl phosphates such as trisdibromopropyl phosphate, trishaloalkyl phosphites such as tris monochloroethyl phosphite, tris monobromoethyl phosphite, ammonium phosphites such as diammonium phosphite, triacyl such as tricresyl phosphate. Phosphoric acid esters, phosphite esters, phosphates, phosphites such as reel phosphate, and alkoxyphosphoric acids such as propoxylated phosphoric acid, And organic phosphorus compound having an active hydrogen in a mixture of phosphate and phosphorus pentoxide in the molecule, such as phosphorus-containing polyols obtained by adding an alkylene oxide such as propylene oxide.

Examples of the foaming agent (C) used in the present invention include water and halogen-substituted aliphatic hydrocarbon foaming agents such as trichlorofluoromethane, dichlorodifluoromethane, trichloroethane, trichloroethylene, tetrachloroethylene, methylene chloride and trichlorotrichloride. Examples thereof include fluoroethane, dibromotetrafluoroethane and carbon tetrachloride. Of these blowing agents, water is preferred. In the present invention, in addition to the above components, if necessary, a catalyst, a foam stabilizer, and other auxiliary agents are used. As the catalyst, known ones usually used in the production of polyurethane, for example, tertiary amines such as triethylamine, triethylenediamine and N-methylmorpholine,
Quaternary ammonium salts such as tetraethylhydroxylammonium, amine catalysts such as imidazoles such as imidazole and 2-ethyl-4-methylimidazole, tin compounds such as tin acetate, tin octylate, dibutyltin dilaurate and dibutyltin chloride, octyl acid Examples thereof include organolead compounds such as lead and lead naphthenate, and organometallic catalysts such as organonickel compounds such as nickel naphthenate. Of these, preferred is the combined use of a tertiary amine and an organic tin compound. As the foam stabilizer, for example, a silicon-based surfactant which is conventionally used in the production of polyurethane foam, such as a siloxane-oxyalkylene block copolymer, is used. For example, F-242T manufactured by Shin-Etsu Chemical Co., Ltd. is used. Etc.

Examples of other auxiliaries include known flame retardants, colorants, plasticizers and the like other than the phosphorus-containing compound used in the production of urethane foam. Polyisocyanate (B), phosphorus-containing compound (C), blowing agent (D), catalyst, based on 100 parts by weight of the polyol in the present invention,
The amount of the foam stabilizer used is as follows. The polyisocyanate (B) has an NCO index of usually 75 to 125, preferably 85 to 115. The phosphorus-containing compound (C) is generally 1 to 30 parts by weight, preferably 2 to 15 parts by weight. The foaming agent (D) is usually 0.5 to 5 parts by weight, preferably 1.0 to 4 parts by weight. When water is used as the foaming agent, it is usually 0.5 to 4.5 parts by weight, preferably 1.
5 to 3 parts by weight. If it exceeds 4.5 parts by weight, the density becomes low and it is difficult to obtain a moist feel. The catalyst is usually 0.01 to 5 parts by weight, preferably 0.1.
The amount of the foam stabilizer is usually 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight. The urethane foam of the present invention can be manufactured by a conventionally known slab method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION To produce the urethane foam of the present invention, first, components other than the catalyst, polyisocyanate, such as polyol, phosphorus-containing compound, foam stabilizer and water, are mixed and stirred. A catalyst is added to this, the polyisocyanate is mixed by stirring for a few seconds, and the mixture is put into a foam box and foamed and cured to obtain the intended soft urethane foam.

[0012]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 4 and Comparative Examples 1 to 5 1) Raw materials used (a) Polyol (1) Polyether polyester polyol, average number of functional groups of about 3, hydroxyl value 56 mg KOH / g, (Takeda Pharmaceutical Co., Ltd.)
Manufactured by Actol 3P-56B) (2) Polyether polyol, average number of functional groups about 3, hydroxyl value 250 mgKOH / g (3) Polyether polyol, average number of functional groups about 3, hydroxyl value 34 mgKOH / g (4) Polyether polyol , Average functional group number about 3, hydroxyl value 56 mgKOH / g (5) polyether polyol, average functional group number about 2, hydroxyl value 105 mgKOH / g ethylene oxide content 100% (b) polyisocyanate toluene diisocyanate (2,4-isomer 80 Wt%, 2,6-
20% by weight mixture of isomers) (Takenate T-80, manufactured by Takeda Pharmaceutical Co., Ltd.) (C) Phosphorus-containing compound trischloroisopropyl phosphate (Phiroll PCF, manufactured by Akzo Kashima Co., Ltd.) (d) Foaming Agent water (ion-exchanged water) (e) Foam stabilizer (6) Siloxane-oxyalkylene block copolymer type foam stabilizer (F-242T manufactured by Shin-Etsu Chemical Co., Ltd.) (7) Siloxane-oxyalkylene block copolymer Systematic foam stabilizer (B-8017 manufactured by Gold Schmidt Co., Ltd.) (f) Catalyst (8) Stanna Octoate (Stannocto, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) (9) Bis (2-dimethylaminoethyl) ether / Dipropylene glycol (70% solution) (manufactured by Tosoh Corporation,
Toyocat ET)

2) Method for producing urethane foam [Table 1] shows the composition ratio of the foamable compositions of Examples 1 to 4 and Comparative Examples 1 to 5.

[Table 1] The proportions of the respective components in the foamable composition in [Table 1] are all expressed in parts by weight except for the isocyanate index, but in the actual production method, the numerical value obtained by multiplying the stated numerical value by 4 g Numbers were used. Of the components shown in [Table 1], each component other than the catalyst and the isocyanate was stirred with a hand mixer, the catalyst was added, and after stirring for 5 seconds, the mixture was mixed with polyisocyanate according to the isocyanate index of [Table 1] to foam the mixture. It was placed in a box and foamed and cured. The obtained foam was allowed to stand at room temperature for 1 day and then subjected to physical property measurement. Note that in Comparative Examples 2 and 4, the closed cell ratio was high and contracted after standing, and various physical properties could not be measured.

3) Method for measuring physical properties of each foam The foams obtained in each of the examples and comparative examples were subjected to a performance test by the following method. (I) Density, impact resilience, hardness (25% ILD), dry heat and wet heat permanent set were measured according to JIS K 6401. (Ii) Tensile strength, tear strength and elongation were measured according to JIS K6301. (Iii) The air flow rate was measured with a woven fabric air permeability tester manufactured by Toyo Seiki Seisakusho Co., Ltd. using a cylindrical sample having a thickness of 1 cm and a diameter of 10 cm. (Iv) The peel strength was measured after a sample piece having a width of 2.54 cm, a thickness of 0.5 cm and a length of 8 cm was flame-laminated on a nylon cloth of the same size using a gas burner and allowed to stand for one day.

4) Measurement Results Examples 1 and 2 have a low impact resilience and an excellent heat fusion property. However, in Comparative Example 1, the impact resilience was not low, and the foam did not fuse to the cloth, so the peel strength could not be measured. In Comparative Example 2 in which the polyether polyester polyol (1) in each example was replaced with the polyether polyol (4), the foam was not sufficiently opened, and the foam shrank. When Example 2 and Comparative Example 3 are compared with each other, since the polyol (2) is replaced with the polyol (4), the heat fusion property is slightly decreased, but the impact resilience is increased. Further, in Comparative Example 4 which was carried out without using the polyol (5) used in Example 2, the foam was not sufficiently opened, and it contracted. In order to see the effect of the phosphorus-containing compound, Example 2 and Comparative Example 5 were compared. As a result, Comparative Example 5 containing no phosphorus-containing compound did not exhibit heat fusion property.

[0016]

EFFECTS OF THE INVENTION The low impact resilience urethane foam of the present invention is capable of frame lamination and has a small permanent set value. Further, by optimizing the composition of the raw material polyol, it is possible to obtain a flame-laminatable low impact resilience urethane foam having various characteristics of small hardness temperature dependence.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 75:04

Claims (17)

[Claims] 1. An average number of functional groups of 2 to 4 and a hydroxyl value of 45 to 6
5mgKOH / g polyether polyester polyol (A
-1) 10 to 60% by weight and an average number of functional groups of 1.5 to
Polyol (A) containing 4.5 to 10% by weight of polyol (A-2) having a hydroxyl value of 200 to 300 mgKOH / g.
And polyisocyanate (B), phosphorus-containing compound (C)
And a urethane foam obtained by reacting in the presence of a foaming agent (D). 2. A polyether polyester polyol (A
-1) has an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 5
The urethane foam according to claim 1, which has a content of 0 to 60 mg KOH / g. 3. The urethane foam according to claim 1, wherein the polyol (A-2) has an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 230 to 270 mgKOH / g. 4. The polyol (A) further comprises 1 to 50% by weight of a polyol (A-3) having an average number of functional groups of 1.5 to 4.5 and a hydroxyl value of 20 to 80 mgKOH / g. Urethane foam. 5. The urethane foam according to claim 4, wherein the polyol (A-3) has an average number of functional groups of 2.5 to 3.5 and a hydroxyl value of 30 to 60 mg KOH / g. 6. The urethane foam according to claim 1, wherein the polyol (A) further contains 1 to 20% by weight of a polyol (A-4) having an average number of functional groups of 1 to 3 and a hydroxyl value of 80 to 150 mgKOH / g. 7. A polyol (A-4) having an average number of functional groups of 1.5 to 2.5, a hydroxyl value of 90 to 115 mg KOH / g and an ethylene oxide unit content of 50% by weight or more. Urethane foam. 8. The urethane foam according to claim 1, wherein the amount of the phosphorus-containing compound (C) used is 1 to 30% by weight based on the polyol (A). 9. The urethane foam according to claim 1, wherein the foaming agent (D) is water. 10. The urethane foam according to claim 9, wherein the amount of water used is 0.5 to 4.5% by weight based on the polyol (A). 11. The urethane foam according to claim 1, wherein the polyisocyanate (B) is toluene diisocyanate. 12. The urethane foam according to claim 1, wherein the polyol (A) contains 30 to 50% by weight of the polyether polyester polyol (A-1) and 20 to 40% by weight of the polyol (A-2). 13. The polyol (A) further contains 20 to 40% by weight of the polyol (A-3).
The urethane foam described in 2. 14. The polyol (A) further contains 1 to 10% by weight of the polyol (A-4).
Urethane foam described. 15. An average number of functional groups of 2 to 4, a hydroxyl value of 45 to
10 to 60% by weight of 65 mg KOH / g of polyether polyester polyol (A-1) and an average number of functional groups of 1.
A polyol (A) containing 10 to 65% by weight of a polyol (A-2) having a hydroxyl value of 5 to 4.5 and a hydroxyl value of 200 to 300 mgKOH / g, a polyisocyanate (B), a phosphorus-containing compound (C) and a foaming agent ( A method for producing a urethane foam, which comprises reacting in the presence of D). 16. The polyol (A) further comprises 1 to 50% by weight of a polyol (A-3) having an average number of functional groups of 1.5 to 4.5 and a hydroxyl value of 20 to 80 mgKOH / g. Method for manufacturing urethane foam. 17. The polyol (A) further contains 1 to 20% by weight of a polyol (A-4) having an average number of functional groups of 1 to 3 and a hydroxyl value of 80 to 150 mgKOH / g.
5. The method for producing a urethane foam according to 5.