JPH1077319A - Polymer-dispersing polyol and polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer-dispersing polyol capable of providing a polyurethane resin excellent in flame resistance, hardness and rebounding elasticity by dispersing polymer fine particles obtained by polymerizing a specific ethylenically unsaturated monomer. SOLUTION: The objective polymer-dispersing polyol has fine particles of a polymer obtained by polymerizing (B) an ethylenically unsaturated monomer dispersed in (A) a polyol, and the component B comprises at least (i) 60.0-99.9wt.% aromatic ethylenically unsaturated monomer and (ii) 0.1-40wt.% ethylenically unsaturated monomer having an active hydrogen. Preferably, the component (i) is at least one kind selected from the group consisting of styrene, α-methylstyrene, a chloromethylstyrene and a vinylpyridine and the component (ii) is at least one kind selected from the group consisting of 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, (meth)acrylic acid, maleic acid, fumaric acid and itaconic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer-dispersed polyol and a polyurethane resin using the same.

[0002]

2. Description of the Related Art A polyol in which polymer particles are obtained by polymerizing an ethylenically unsaturated monomer such as styrene or acrylonitrile in a polyol is conventionally called a polymer polyol or a polymer-dispersed polyol. Used as a raw material. In particular, when a polymer-dispersed polyol is used for a flexible polyurethane foam, effects such as promotion of cell communication and improvement of foam hardness are obtained.

However, when a polymer-dispersed polyol in which polymer particles of acrylonitrile and styrene are dispersed is used, the hardness of the polyurethane foam is improved, but physical properties such as rebound resilience are disadvantageously reduced. Therefore, in the case of a polyurethane resin using a known polymer-dispersed polyol, there is a problem that when the hardness is increased, the rebound resilience is reduced.

[0004] JP-A-61-268711, JP-A-62-104824, JP-A-62-104829
JP-A-62-149748 discloses a method of polymerizing a glycol ester of an ethylenically unsaturated carboxylic acid, an unsaturated aliphatic alcohol and / or an ester thereof, together with an unsaturated nitrile and other monomers in a polyol. It teaches that the rigidity and impact resistance of polyurethane can be improved by using the obtained pendant type hydroxyl group-containing polymer polyol.

JP-A-62-195011 discloses that a pendant hydroxyl-containing polymer polyol obtained by polymerizing a monomer containing furfuryl alcohol in a polyol in the presence of an acid catalyst is used to form a polyurethane. It teaches that rigidity, heat resistance, and impact resistance can be improved.

However, polymer-dispersed polyols obtained by these methods are used for RIM applications such as rigid or impact-resistant urethane elastomers having no foaming or low foaming (density of 0.8 to 1.4 g / cm ³ ). The present invention differs from the present invention in the molding method and the desired physical properties.

[0007] Further, improvement of the flame retardancy of polyurethane resins has been a major issue in recent years. In general, a method of adding an organic halogenated phosphorus compound, melamine, or the like is known, but an improvement has been demanded because the physical properties of the polyurethane resin are significantly impaired.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a polymer-dispersed polyol having a novel composition for use in the production of a polyurethane resin, whereby a polyurethane resin having excellent properties in flame retardancy, hardness and rebound resilience is provided. The purpose is to provide.

[0009]

Means for Solving the Problems The first invention of the present application is:
In a polymer-dispersed polyol in which polymer fine particles obtained by polymerizing an ethylenically unsaturated monomer are dispersed in a polyol, the ethylenically unsaturated monomer is at least (a component) an aromatic ethylenically unsaturated monomer.
A polymer-dispersed polyol characterized by being an ethylenically unsaturated monomer comprising 0 to 99.9% by weight and (b component) 0.1 to 40.0% by weight of an ethylenically unsaturated monomer having active hydrogen. .

In a second aspect of the present invention, in the first aspect, the aromatic ethylenically unsaturated monomer (a) is selected from the group consisting of styrene, α-methylstyrene, chloromethylstyrene and vinylpyridine. At least one polymer-dispersed polyol.

The third invention of the present application is the first invention, wherein the (b) ethylenically unsaturated monomer having active hydrogen is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, The present invention relates to a polymer-dispersed polyol comprising at least one selected from the group consisting of hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

In a fourth aspect of the present invention, in the first aspect, the ethylenically unsaturated monomer is (a) an aromatic ethylenically unsaturated monomer of 60.0 to 99.
An ethylenically unsaturated monomer containing 0.1 to 5% by weight of ethylenically unsaturated nitriles, in addition to 0.1 to 40.0% by weight of 9% by weight and (b component) ethylenically unsaturated monomer having active hydrogen. A certain polymer-dispersed polyol.

[0013] In a fifth aspect of the present invention, in the first aspect, the polymer MDI and the polymer-dispersed polyol are formed such that NCO / OH = 1.00 (molar ratio) with respect to the hydroxyl group of the polyol of the polymer-dispersed polyol. The present invention relates to a polymer-dispersed polyol which gives a polyurethane resin having a hardness of 65 or more, a rebound resilience of 79% or more, and an oxygen index of 21% or more when reacted at a certain ratio.

Further, the sixth invention of the present application relates to a polyurethane resin produced by reacting any of the above-mentioned polymer-dispersed polyols with an organic polyisocyanate.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The polyol used in the present invention is a polymer which is liquid at ordinary temperature and has two or more hydroxyl groups in a molecule, and includes polyether polyols, polyester polyols and the like usually used as a raw material for polyurethane. Known ones can be used.

The polyether polyol has 2 to 8 hydroxyl groups in the molecule, and has a molecular weight per hydroxyl group of 200 to 4000, preferably 600 to 3000.

For example, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and 1,4-butylene glycol; trihydric or higher such as glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc. Polyhydric alcohols; bisphenol A, bisphenol F, dihydroxybiphenyl,
Hydroquinone, resorcin, phloroglucin, naphthalene diol, aminophenol, aminonaphthol,
Phenolic compounds such as phenol formaldehyde condensate; alkanolamines such as methyldiethanolamine, ethyldiisopropanolamine, monoethanolamine, diethanolamine and triethanolamine; ethylenediamine, hexamethylenediamine, diethylenetriamine, bis (p-aminocyclohexyl)
Initiator is a compound arbitrarily selected from amines such as methane, aniline, toluidine, tolylenediamine, diphenylmethanediamine, naphthalenediamine and the like, and is usually a catalyst such as an alkali metal compound and / or an amine or a complex metal cyanide complex. And polyoxyalkylene polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide.

Furthermore, a mixture of two or more arbitrarily selected from these polyoxyalkylene polyols can also be used.

Further, as the polyester polyol,
Polyester polyols obtained by ring-opening addition of ε-caprolactone, γ-butyrolactone, etc. using a polyhydric alcohol such as glycerin as an initiator; diols such as ethylene glycol, propylene glycol, pentanediol and terephthalic acid, phthalic anhydride, etc. And polyester polyols obtained by condensation with dicarboxylic acids or dicarboxylic esters such as dimethyl terephthalate.

The ethylenically unsaturated monomer used in the present invention is a monomer having an ethylenically unsaturated double bond in the molecule and capable of being easily polymerized by a polymerization initiator. Saturated monomer and (b component)
An ethylenically unsaturated monomer having active hydrogen is contained as an essential component, and if necessary (component (c)), (a
Component) and an ethylenically unsaturated monomer other than Component (b).

Examples of the aromatic ethylenically unsaturated monomer used in the present invention include styrene, α-methylstyrene, chloromethylstyrene, vinylpyridine and the like, and styrene is particularly preferred.

The ethylenically unsaturated monomer having an active hydrogen used in the present invention has an ethylenically unsaturated double bond and an active hydrogen group such as a hydroxyl group, a carboxyl group, a mercapto group and an amino group in the molecule. The active hydrogen group is preferably a hydroxyl group or a carboxyl group.

Specifically, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 1,9-nonanediol methacrylate Methacrylic acid or acrylates having at least one hydroxyl group, such as 1,9-nonanediol acrylate, tripropylene glycol methacrylate, tripropylene glycol acrylate, tetraethylene glycol methacrylate, tetraethylene glycol acrylate, and acrylic acid, methacrylic Carboxylic acids such as acid, maleic acid, fumaric acid, and itaconic acid; 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid is preferred.

The amount of the (a) aromatic ethylenically unsaturated monomer in the total amount of the ethylenically unsaturated monomer is 6%.
0.0 to 99.9% by weight. On the other hand, the amount of the (b component) ethylenically unsaturated monomer having active hydrogen in the total amount of the ethylenically unsaturated monomer is 0.1 to 40.0% by weight. Polyurethane resins using polymer-dispersed polyols obtained from amounts other than these amounts do not exhibit an effect that sufficiently satisfies all of flame retardancy, hardness, and rebound resilience. Further preferably, the amount of the (a component) aromatic ethylenically unsaturated monomer is from 60.0 to 90.0% by weight,
(Component b) The amount of the ethylenically unsaturated monomer having active hydrogen is from 5.0 to 30.0% by weight.

The component (c) may be used together with the components (a) and (b) to improve the physical properties of the polyurethane resin using the polymer-dispersed polyol and to improve the dispersion stability of the polymer-dispersed polyol. it can. The content is 39.9% by weight or less, preferably 5% by weight in the total amount of the ethylenically unsaturated monomers used in the present invention.
It is as follows.

Examples of the monomer used as the component (c) include ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, methacrylic esters such as methyl methacrylate and butyl methacrylate, and acrylic acid such as methyl acrylate and butyl acrylate. Examples thereof include halogen-containing ethylenically unsaturated monomers such as esters, vinyl chloride, and vinylidene chloride.

Among these, ethylenically unsaturated nitriles such as acrylonitrile are preferred from the viewpoint of improving the stability of the polymer-dispersed polyol, and 39.9% by weight or less, preferably 59.9% by weight of all the ethylenically unsaturated monomers used. An amount of less than or equal to 0.1% by weight can be used, for example.

The amount of the ethylenically unsaturated monomer used in the present invention is not particularly limited, but is preferably 0.5% by weight or more and less than 70% by weight based on the total amount of the ethylenically unsaturated monomer and the polyol. Is 0.5% by weight or more 5
It is less than 0% by weight, more preferably 0.5% by weight or more and less than 30% by weight.

In polymerizing these ethylenically unsaturated monomers, a radical initiator which generates a radical and starts polymerization is usually used as a polymerization initiator. Specific examples include azo compounds such as 2,2-azobisisobutyronitrile, peroxides such as benzoyl peroxide, and persulfates.

The amount of the polymerization initiator to be used is generally 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight, based on the ethylenically unsaturated monomer.

To produce a polymer-dispersed polyol,
There are two ways. One method is to polymerize the monomer in the polyol to disperse the polymer particles, and the other is to polymerize the monomer in a solvent other than the polyol to disperse the polymer particles in the polyol. Is the way. In the present invention, either method can be used.

The method of polymerizing the monomer in the polyol can be carried out by a batch method or a continuous method, and can be carried out under normal pressure or under pressure. The polymerization temperature is usually 70
To 150 ° C, preferably 80 to 130 ° C.

In the present invention, a chain transfer agent can be used if necessary. Specific examples include alcohols such as isopropanol, mercaptans, halogenated hydrocarbons, and aliphatic tertiary amines.

The amount of the chain transfer agent to be used is from 0.1 to 10.3 based on the total amount of the polyol and the ethylenically unsaturated monomer.
0% by weight, and preferably 0.5 to 5.0% by weight.

For the purpose of stably dispersing the polymer fine particles, a dispersion stabilizer such as a polyoxypropylene polyol having a molecular weight of 15,000 or more or a polyoxypropylene polyol having a double bond in the molecule may be used. it can.

As the dispersion stabilizer, after reacting an unsaturated carboxylic anhydride such as maleic anhydride or itaconic anhydride with the polyol, propylene oxide, if necessary,
High molecular weight polyols obtained by adding an alkylene oxide such as ethylene oxide are exemplified. These dispersion stabilizers are not included in the ethylenically unsaturated monomers.

The above polymerization reaction can be carried out without a solvent, but can also be carried out in the presence of an organic solvent. Examples of the organic solvent include toluene, xylene, acetonitrile, hexane, heptane, dioxane, ethylene glycol dimethyl ether, N, N-dimethylformamide, butanol, isopropanol and the like.

After the completion of the polymerization reaction, the obtained polymer-dispersed polyol can be used as a raw material for polyurethane or the like as it is, but is used after distilling off unreacted monomers, decomposition products of the catalyst, chain transfer agents, solvents and the like under reduced pressure. Is preferred.

When the monomer is polymerized in a solvent other than the polyol, polymer fine particles can be produced using the above-mentioned ordinary organic solvent or water as a solvent.

The amount of the fine polymer particles contained in the polymer-dispersed polyol of the present invention is determined based on the polymer-dispersed polyol 10
It is from 0.5% by weight to less than 70% by weight, preferably from 0.5% by weight to less than 50% by weight, more preferably from 0.5% by weight to less than 30% by weight per 0 part by weight.

The average particle size of the fine polymer particles contained in the polymer-dispersed polyol of the present invention is preferably from 0.1 to 10.0 μm from the viewpoint of the effect on the dispersion stability of the polymer-dispersed polyol and the physical properties of the polyurethane resin. . To achieve such a particle size, when polymerizing in a polyol, the type and amount of the dispersion stabilizer,
It can be carried out by appropriately adjusting the weight composition ratio of the monomers and the like. When the polymerization is carried out in a solvent other than the polyol, the polymerization can be carried out by appropriately adjusting the weight ratio of the solvent to the monomer used, the weight composition ratio of the monomer, and the like.

When the polymer-dispersed polyol of the present invention is used as a raw material for polyurethane, the polymer-dispersed polyol can be used either by mixing the polymer-dispersed polyols or by diluting with the polyol described above.

The polyurethane resin of the present invention is obtained by reacting the above-mentioned polymer-dispersed polyol or the polymer-dispersed polyol diluted with the above-mentioned polyol with an organic polyisocyanate, if necessary, in the presence of a catalyst and other auxiliaries. And a polyurethane foam obtained in the presence of a foaming agent such as water, a foam stabilizer such as an organosilicon-based surfactant, and other auxiliaries such as a crosslinking agent.

As the organic polyisocyanate, any known organic polyisocyanate usually used in the production of polyurethane can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), isomer mixture in 65/35 weight ratio (TDI-65 / 35), crude tolylene diisocyanate containing polyfunctional tar (polyfunctional tar is a by-product in the production of isocyanate). And two isocyanate groups in the molecule
It is a mixture of tar-like substances containing more than one. same as below. ), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate,
2,2′-diphenylmethane diisocyanate, a mixture of any isomers of diphenylmethane diisocyanate, 3
Crude diphenylmethane diisocyanate (polymeric MDI) containing core or higher polyfunctional tar, toluidine diisocyanate, xylylene diisocyanate,
Hexamethylene diisocyanate, carbodiimide-modified or buret-modified organic polyisocyanates, or prepolymers obtained by modifying these with polyols or monools alone or in combination. The above-mentioned organic polyisocyanates can be used in a mixture at an arbitrary ratio.

The equivalence ratio between the organic polyisocyanate and the polymer-dispersed polyol or the polymer-dispersed polyol diluted with the above polyol is not particularly limited, but NCO and the polymer-dispersed polyol in the organic polyisocyanate are not limited. NCO / H (active hydrogen) = 0.50 to 2.0 based on active hydrogen based on polyol of
Is preferable.

As the catalyst, all those usually used in the production of polyurethane can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine,
N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether,
Organometallic catalysts such as triethylenediamine and salts of triethylenediamine include tin acetate, tin octylate,
Tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride,
Examples include lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

These catalysts can be arbitrarily mixed and used in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the polymer-dispersed polyol or the polymer-dispersed polyol diluted with the above polyol. .0
Parts by weight. In addition, a flame retardant, a plasticizer, a stabilizer, a colorant, and the like can be added as needed.

[0048]

The present invention will be described below with reference to examples. The raw materials used in Examples and Comparative Examples are as follows. The numbers in the examples represent parts by weight in principle.

[Raw Materials Used for Production] Polyol A: A hydroxyl value of 3 obtained by adding propylene oxide to glycerin and then adding ethylene oxide.
3 mg KOH / g polyol (EO content 14%) Ethylenically unsaturated monomer: AN: acrylonitrile ST: styrene HEMA: 2-hydroxyethyl methacrylate AAC: acrylic acid Initiator: AIBN (azobisisobutyronitrile) organic polyisocyanate A: Polymeric MDI (NC
O% = 31.3%, manufactured by Mitsui Toatsu Chemicals Co., Ltd. Catalyst A: a 16.5% by weight diethylene glycol solution of triethylenediamine

[Examples 1 to 4, Comparative Examples 1 to 4, Reference Example 1] [Synthesis of Polymer-Dispersed Polyol] Monomers as described in the column of polymerization recipe in Tables 1 and 2 were mixed in polyol A for 120 minutes. Polymerization was carried out for 2 hours at C to synthesize polymer-dispersed polyols B to I.

[Production of Polyurethane Resin] A polyurethane resin was produced in the following manner using the synthesized polymer-dispersed polyols B to I or polyol A and polymeric MDI.

100 g of the polymer-dispersed polyol BI or polyol A is weighed into a 500 ml polycup, and polymeric MDI (NCO / OH = 1.00 based on the hydroxyl group based on the polyol) and 0.03 g of the catalyst A are added.
The mixture was stirred with a stirrer (300 rpm) for 3 minutes, and the mixture was defoamed under reduced pressure for 15 minutes. Aluminum mold (diameter 30mm
× For 6 cylindrical molded products with a depth of 12 mm, and 200 m
The mixture was poured into a sheet (m × 200 mm × 1 mm) and cured at 80 ° C. for 48 hours under a nitrogen atmosphere.

[Measurement of Physical Properties] The following physical properties of the produced polyurethane resin were measured. Hardness: The surface hardness of a cylindrical sample was measured using a type A durometer described in JIS K7215. Rebound resilience: The rebound resilience of a cylindrical sample was measured using a Lupke rebound resilience tester described in JIS K6301. Oxygen index: The oxygen index of the sheet sample was measured by the method described in JIS D1201. Polymer particle size: COULTE
The particle size of the polymer fine particles dispersed in methanol was measured using R LS130 (particle analyzer manufactured by COULTER).

[0054]

[Table 1]

[0055]

[Table 2] In Tables 1 and 2, 1) 2) is as follows: 1) monomer content A: weight% of aromatic ethylenically unsaturated monomer in ethylenically unsaturated monomer 2) monomer content B: in ethylenically unsaturated monomer % Of the ethylenically unsaturated monomer having active hydrogen.

From the comparison between the examples and the reference examples, the polyurethane resin using the polymer-dispersed polyol of the present invention is:
It can be seen that the hardness and the oxygen index are improved without reducing the rebound resilience. On the other hand, when comparing the comparative example and the reference example, the polyurethane resin using the polymer-dispersed polyol other than the present invention has a slightly improved oxygen index and hardness, but a reduced rebound resilience, as compared with those not used. I understand.

Also, as in Comparative Example 3, the amount of the monomer having active hydrogen such as HEMA exceeds 40% by weight of the ethylenically unsaturated monomer used, or as in Comparative Example 4, such as styrene. It can be seen that when the amount of the aromatic ethylenically unsaturated monomer is less than 60% by weight of the ethylenically unsaturated monomer used, the physical properties of the polyurethane resin are all deteriorated.

From Examples 1 to 4, Polymeric M
DI and the polymer-dispersed polyol of the present invention with respect to the hydroxyl groups of the polyol of the polymer-dispersed polyol.
The polyurethane resin obtained by reacting at a ratio of H = 1.00 (molar ratio) has a hardness of 65 or more and a rebound resilience of 79%.
As mentioned above, it turned out that it shows the outstanding characteristic which oxygen index is 21% or more.

[0059]

By using the polymer-dispersed polyol of the present invention and reacting it with an organic polyisocyanate, a polyurethane resin having excellent performance in hardness, rebound resilience and flame retardancy can be produced.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08F 220: 10) (72) Inventor Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A polymer-dispersed polyol in which polymer fine particles obtained by polymerizing an ethylenically unsaturated monomer are dispersed in a polyol, wherein the ethylenically unsaturated monomer contains at least (a) an aromatic ethylenically unsaturated monomer 60 0.09 to 99.9% by weight, and (b component) an ethylenically unsaturated monomer having an active hydrogen of 0.1 to 40.
A polymer-dispersed polyol characterized by being an ethylenically unsaturated monomer containing 0% by weight. 2. The polymer dispersion according to claim 1, wherein the (a) aromatic ethylenically unsaturated monomer comprises at least one selected from the group consisting of styrene, α-methylstyrene, chloromethylstyrene and vinylpyridine. Polyol. 3. The (b component) ethylenically unsaturated monomer having active hydrogen is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid. 2. The polymer-dispersed polyol according to claim 1, comprising at least one member selected from the group consisting of, maleic acid, fumaric acid and itaconic acid. 4. The method according to claim 1, wherein the ethylenically unsaturated monomer is (a)
Component) Aromatic ethylenically unsaturated monomer 60.0-9
Ethylenically unsaturated containing 0.1 to 5% by weight of ethylenically unsaturated nitriles in addition to 9.9% by weight and (b component) 0.1 to 40.0% by weight of ethylenically unsaturated monomer having active hydrogen The polymer-dispersed polyol according to claim 1, which is a monomer. 5. When polymer MDI and a polymer-dispersed polyol are reacted at a ratio of NCO / OH = 1.00 (molar ratio) to hydroxyl groups of the polyol of the polymer-dispersed polyol, the hardness is 65 or more and the rebound resilience is 79. The polymer-dispersed polyol according to claim 1, which gives a polyurethane resin having an oxygen index of 21% or more. 6. A polyurethane resin produced by reacting the polymer-dispersed polyol according to any one of claims 1 to 5 with an organic polyisocyanate.