JPS642129B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel elastic polyurethane resin composition. More specifically, the present invention relates to an elastic polyurethane resin composition that exhibits a good elongation at tensile break, which is an important property for an elastic composition, without impairing the inherent properties of the polyurethane resin. Generally, what is called elastic urethane resin is a polyisocyanate compound R(-NCO)n having two or more isocyanate groups (-NCO) and a -OH group, _-NH2 group, -NH having two or more active hydrogens.
It is an elastic resin formed by mixing and reacting with a curing agent component having a group, -SH group, etc. Conventionally, the method for producing elastic urethane resins is to form a prepolymer by heating a polyisocyanate compound and a polyether-type active hydrogen compound at room temperature or by heating, and then harden this prepolymer through a chain lengthening reaction and a crosslinking reaction at room temperature or by heating to produce urethane. A prepolymer method for making resin is common. The elastic urethane resin thus obtained can be adjusted to have an elastic hardness suitable for the application by appropriately combining the structures of the polyisocyanate compound and curing agent, or by changing the ratio of isocyanate groups to active hydrogen groups. It is used in construction sealants, waterproofing agents such as paint film waterproofing agents, and elastic paving agents for seamless floors and tennis courts. However, polyisocyanate compounds and curing agents are generally expensive, and therefore there has been a desire to develop a substance that does not reduce the inherent properties of urethane resins and contributes to lower prices. Furthermore, additives such as viscosity modifiers and reaction extenders are required due to operational problems during the production of urethane resins. Therefore, as additives for elastic urethane resin compositions, esters such as phthalate esters, sebate esters, and adipic esters, fats and oils such as castor oil and tall oil, mineral oils and their derivatives, or coal tar pitch, etc. is widely used. In addition to these, calcium carbonate, silica, magnesium carbonate, aluminum hydroxide, calcium sulfate, calcium sulfite, talc, clay, titanium oxide, zinc oxide, metal powder, glass powder,
It is known that inorganic materials such as carbon black are sometimes used as fillers. However, none of these known additives was fully satisfactory in terms of performance and price. In particular, the above-mentioned additives reduce the strength, elongation, and other physical properties of the elastic polyurethane composition, making it difficult to obtain desired physical properties. It is an object of the present invention to provide an elastic polyurethane resin composition that eliminates the drawbacks of the conventional additives mentioned above and has a good elongation at break. In order to achieve the above object, the present inventors have conducted extensive research and have arrived at the present invention.
That is, the present invention is directed to (1) polyisocyanate compounds having two or more isocyanate groups in the molecule, (2) compounds having two or more active hydrogens in the molecule, and (3) by-produced by decomposition of petroleum. Carbonization obtained by adding a Friedel-Crafts type catalyst to a system in which 7 to 25 parts by weight of phenols are added to 100 parts by weight of a hydrocarbon oil fraction with a boiling point range of 140 to 280°C containing unsaturated hydrocarbons and polymerizing it. It consists of an elastic polyurethane resin composition characterized by containing a hydrogen resin as an essential component. In addition, (1) polyisocyanate compounds having two or more isocyanate groups in the molecule, (2) compounds having two or more active hydrogens in the molecule, and (3) unsaturated hydrocarbons that are by-produced by decomposition of petroleum. A hydrocarbon resin and (4 ) The elastic polyurethane resin composition is characterized by containing a hydrocarbon solvent or a plasticizer. 2 isocyanate groups used in the present invention in the molecule
The polyisocyanate compound having more than 100% polyisocyanate may be any ordinary polyisocyanate compound used in the production of polyurethane resins, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, etc. These polyisocyanates can be used alone or in mixtures. However, in general, a prepolymer having a reactive isocyanate group at the end, which is produced by a reaction between the above-mentioned polyisocyanate compound and a mixture of one or more polyether type polyols, is used. Commercially available prepolymers include Polyflex (Daiichi Kogyo Seiyaku), Takenate (Takeda Pharmaceutical Co., Ltd.), Adekal Resin UP (Asahi Denka Kogyo), Samprene (Sanyo Chemical), and Hypren (Mitsui Nisso Urethane). The compound having two or more active hydrogens in the molecule used in the present invention has two or more OH groups or NH ₂ groups in the molecule and is used as a curing agent. For example, castor oil or castor oil derivatives, polyols and derivatives thereof such as polyoxypropylene diol, polyoxypropylene triol, polyols such as low molecular weight diols, triols, polyoxyethylene diol, polyoxyethylene triol, polyester glycol, polyester triol, etc. , 4'-methylenebisorthochloroaniline, p-phenylenediamine, and triylenediamine. Typical commercially available curing agents such as polyhardener (Daiichi Kogyo Seiyaku), Iharakyuamine (Ihara Chemical), and bisamine (Wakayama Seika Kogyo) can be used. The hydrocarbon resin used as an additive in the present invention is produced by thermal decomposition such as steam cracking of petroleum such as naphtha, kerosene, and light oil to produce ethylene, propylene, etc.
Styrene and alkylstyrenes, indenes and alkylindenes, which have 8 to 10 carbon atoms, are produced as by-products when producing butenes and butadienes.
A large amount of aromatic olefin, e.g. 35-65% by weight
Contains phenols such as phenol,
The raw material is a polymerized product of cresol, xylenol, t-butylphenol, nonylphenol, etc. alone or a mixture of two or more of them in an amount of 7 to 25 parts by weight, and boron trifluoride, aluminum chloride, trifluoride, etc. By adding 0.05 to 5% by weight of a Friedel-Crafts type catalyst such as a boron phenol complex compound or a boron trifluoride dialkyl ether complex compound, -
After polymerizing at a temperature in the range of 10° to +80°C for a time in the range of 10 minutes to 15 hours, the catalyst is decomposed and removed with an alkali such as caustic soda or soda carbonate.
It is obtained by washing with water if necessary and further decomposing unreacted substances and low molecular weight polymers by evaporation or distillation. The resin is pale to yellow, has a Gardner color number of 10 or less, and a softening point of 50 to 120°C (JIS K-
2531-60), and has a number average molecular weight of 500 to 1500. It is also possible to divide the cracked oil fraction within the boiling point range of 140 to 220°C and use it by distillation.
When fraction B is divided into fractions with a boiling point of 220°C and each fraction is used as a raw material for an aromatic resin in the composition of the present invention, when fraction A is used as a raw material, the softening point is 50°C.
When fraction B is used as a raw material, the softening point is as high as 90 to 120°C, and a yellow resin is obtained. The amount of the phenols used is within the range of 7 to 25 parts by weight per 100 parts by weight of the cracked oil fraction, which is the main raw material, and the resin obtained using 7 parts by weight or less is not compatible with the urethane resin. Unfortunately, the polyurethane resin composition obtained therefrom has a reduced elongation at tensile break. Further, resins obtained using 25 parts by weight or more cannot obtain the above-mentioned performance. Hydrocarbon solvents or plasticizers used as additives in the present invention include mineral spirits equivalent to industrial gasoline No. 4, kerosene, light oil, white oil, paraffinic or naphthenic process oils, phthalate esters, sebacilate esters, and Esters such as adipic acid ester, chlorinated paraffin, polybutene with a molecular weight of 300 to 5000,
Examples include diallylalkane, triallylalkane, tetraalkylalkane, alkylnaphthalenes such as mono-, di-, and triisopropylnaphthalene, and alkylbiphenyl alkyls such as diethyldiphenyl and triethyldiphenyl. The aforementioned diallylalkane, triallylalkane, and tetraalkylalkane are styrene, toluene, xylene, and other alkylbenzenes that are oxidized with Lewis acids such as sulfuric acid and phosphoric acid, liquid or solid oxidation catalysts such as cation exchange resins, or aluminum chloride, It is a compound obtained by reaction in the presence of a Friedel-Crafts catalyst such as boron oxide, and has 2 to 4 aromatic rings, or a mixture thereof, and has the structure shown below. In the present invention, in order to obtain an elastic polyurethane resin composition, a method of reacting a polyisocyanate compound and a polyol or amines, or a method of reacting a polyisocyanate compound and a polyol, is generally used to obtain an elastic polyurethane resin composition with an NCO/OH molar ratio of 1.5 to 15.0. An isocyanate prepolymer having a reactive isocyanate group at the terminal end of the isocyanate prepolymer is formed, and the prepolymer is usually given an NCO/OH molar ratio or an NCO/OH molar ratio.
The reaction may be carried out by a prepolymer method in which polyols or amines are reacted at an NH ₂ molar ratio of 0.5 to 2.0, preferably 0.8 to 1.2. The reaction temperature is in the range of room temperature to 120°C. In the present invention, when producing an elastic polyurethane resin composition, in the first invention, the polyisocyanate compound or isocyanate prepolymer is used, although it varies depending on the type of urethane resin.
The hydrocarbon resin is added in an amount of 0.5 to 30, preferably 1 to 20 parts by weight per 100 parts by weight. Further, in the second invention, the amount of hydrocarbon resin is 0.5 to 30, preferably 1 to 30 parts by weight, depending on the type of urethane resin, based on 100 parts by weight of the polyisocyanate compound or isocyanate prepolymer.
20 parts by weight, at least one selected from hydrocarbon solvents and plasticizers from 1 to 60, preferably from 2 to
By adding 50 parts by weight, an elastic polyurethane resin composition with good elongation at tensile breakage can be obtained without impairing the inherent properties of the polyurethane resin. In the present invention, there is usually no need for a catalyst, but
In particular, when curing is accelerated, known catalysts for polyurethane resins can be used. Examples of this catalyst include lead octylate, lead naphthenate, stannath octoate, dibutyltin dilaurate, triethylamine, and triethylenediamine. The additives may be mixed at the time of mixing the isocyanate prepolymer and the polyol or amine, or may be added to the prepolymer, polyol, and amine individually or individually in advance. In addition, in the present invention, calcium carbonate, silica,
Talc, clay, titanium oxide, zinc oxide, magnesium carbonate, aluminum hydroxide, calcium sulfate, calcium sulfite, metal powder, glass powder, sand,
5 to 100 parts by weight of an inorganic filler such as carbon black may be added to 100 parts by weight of the urethane resin composition. The composition of the present invention exhibits the following good properties. (1) Increase in elongation at break It is known that when additives such as solvents and diluents are added to urethane resin compositions, the elongation at break increases. However, as the elongation rate increases, the tensile strength significantly decreases.The additive of the present invention has the feature of significantly increasing the elongation rate at tensile break and hardly decreasing the tensile strength. (2) Improving the compatibility of urethane resins, polyols, and amines and reducing the bleeding of additives from elastic polyurethane compositions The additives of the present invention can be used to improve the compatibility of urethane resins, polyols, and amines with curing agents that have poor compatibility. By adding it to the system, it is possible to increase the compatibility between the two and easily make them uniform. In particular, it shows good compatibility with systems using polyols. Furthermore, the additive of the present invention has the characteristic that it is difficult to bleed out from the polyurethane resin composition. Next, the present invention will be explained by examples, but the present invention is not limited to these examples. Example 1 Phenol was added to 100 parts by weight of the cracked fraction obtained by steam cracking of naphtha, which had a boiling point range of 140 to 210°C and contained 40% by weight of unsaturated components.
Add 16 parts by weight and 0.6% by weight of boron trifluoride ethyl ether complex catalyst, polymerize at 50°C for 2 hours, decompose the catalyst with an aqueous solution of caustic soda, wash with water, and remove unreacted oil by distillation under reduced pressure. A resin (sample) was obtained. Resin yield was 41% by weight;
The softening point was 89°C, and the compatibility with polyols and polyisocyanate prepolymers was good as shown in Table 1. Further, Table 2 shows the results of testing the performance as a coating film waterproofing agent using the following formulation. [Blending prescription] Prepolymer: Polyflex WP-8
100 parts by weight [Daiichi Kogyo Seiyaku Co., Ltd. (NCO = 3.7wt%)] Hardening agent: Iharakyuamine ML-530
20 parts by weight [Ihara Chemical Co., Ltd. Amine value 210KOHmg/
g] Additives (Types and amounts added are shown in Table 2) Filler: White P-30 55〃 [Shiraishi Kogyo Co., Ltd.] Catalyst: Lead octylate (PB content: 38wt%) 0.8〃 Example 2 Approximately 65 parts by weight of the resin (sample) obtained in Example 1 and 35 parts by weight of mineral spirits (manufactured by Nippon Oil Co., Ltd.) were added.
The sample is heated to 100℃ and dissolved.
In the same manner as in Example 1, compatibility and performance as a coating film waterproofing agent were tested. Example 3 A liquid hydrocarbon compound (average molecular weight 314, A sample was prepared by mixing and dissolving 60 parts by weight (viscosity: 8,000 cp at 20°C), and the compatibility and performance as a coating film waterproofing agent were tested in the same manner as in Example 1. Comparative Example 1 When making the resin (sample) obtained in Example 1,
A resin was obtained in the same manner as in Example 1 except that 3.0 wt% of phenol was added. The resin yield was 38% by weight, and the softening point was 101°C. Using this resin as a sample,
Similar to Example 1, compatibility and performance as a coating film waterproofing agent were tested, and the results are shown in Tables 1 and 2, respectively. Comparative Example 2 A sample was prepared by mixing 80 parts by weight of the sample obtained in Comparative Example 1 and 20 parts by weight of mineral spirits in the same manner as in Example 2. Comparative Examples 3 and 4 Commercially available plasticizer dioctyl phthalate (DOP),
Chlorinated paraffin was blended according to the same formulation as in Example 1, and its performance as a coating film waterproofing agent was tested.

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Claims (1)

[Scope of Claims] 1 Polyisocyanate compounds having two or more isocyanate groups in the molecule, compounds having two or more active hydrogens in the molecule, and 140 to 140 containing unsaturated hydrocarbons by-produced by decomposition of petroleum, etc. Contains as an essential component a hydrocarbon resin obtained by polymerizing a system in which 7 to 25 parts by weight of phenols are added to 100 parts by weight of a hydrocarbon oil fraction within the boiling point range of 280℃ and a Friedel-Crafts type catalyst is added. An elastic polyurethane resin composition characterized by: 2 Polyisocyanate compounds having two or more isocyanate groups in the molecule, compounds having two or more active hydrogens in the molecule, compounds with a boiling point of 140 to 280°C, including unsaturated hydrocarbons by-produced by decomposition of petroleum, etc. A hydrocarbon resin obtained by polymerizing a system in which 7 to 25 parts by weight of phenols are added to 100 parts by weight of a hydrocarbon oil fraction and a Friedel-Crafts catalyst, and a hydrocarbon solvent or plasticizer. An elastic polyurethane resin composition comprising: 3 If the hydrocarbon solvent or plasticizer is mineral spirits, kerosene, light oil, white oil, paraffinic or naphthenic process oil, esters such as phthalates, sebates, and adipates, chlorinated paraffins, or The elastic polyurethane resin composition according to claim 2, which is one or a mixture of two or more selected from 300 to 5,000 polybutenes, diallylalkane, triallylalkane, tetraalkylalkane, alkylnaphthalene, and alkylbiphenylalkyl. thing.