TWI454527B - Polyurethane resin composition and molded article thereof - Google Patents

Description

Polyurethane resin composition and formed product thereof

The present invention relates to a polyurethane resin composition capable of obtaining a cured product of a polyurethane having excellent resistance to fussing, helium atom cohesiveness, various physical properties and low friction properties, and the use thereof Things.

In recent years, the organopolysiloxane compound has excellent interfacial properties such as low friction, thermal stability, water repellency, defoaming property, and mold release property, and is added to improve the performance of synthetic resins such as paints and molded articles. A modifier such as dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, a dimethylpolysiloxane containing a reactive group, or a polyether-modified organopolyoxyalkylene is used.

However, such miscibility with the resin is not sufficient and heat resistance is insufficient to make the use range limited. Therefore, a lactone-modified organopolyoxane compound in which a lactone is added to an addition reaction of polyoxyalkylene and glycerol monoallyl has been proposed for the purpose of improving these disadvantages (for example, see Patent Document 1). .

However, since the lactone of this compound has a plurality of polylactone chains due to reaction with a plurality of hydroxyl groups of glycerol monoallyl ether, there are many cross-linking structures, and the urethane reaction is due to the primary hydroxyl group and the secondary hydroxyl group. The mixture is miscible, and the miscibility with the polyol is poor, and it is difficult to use it as a raw material for the polyurethane resin.

Further, when the polyurethane resin composition containing a polyisocyanate and a polyol as an essential component is used only for molding, the obtained molded article is inferior in abrasion resistance. In order to improve this problem, it is proposed to introduce an organopolysiloxane to a urethane polymer. (for example, refer to Patent Document 2).

However, the technique of Patent Document 2 does provide a slight improvement in the rubbing resistance, but since the miscibility of the organopolysiloxane and the polyol is inferior, the resulting molded article is liable to cause halation, especially when formed by a one-stage method. This kind of bad situation is very significant.

As described above, it has been desired to develop a miscibility with a polyol, and it can be used as a raw material for a polyurethane resin in any of a one-stage or pre-polymer method. A polyol containing a polyoxyalkylene chain (hereinafter referred to as polyoxyl polyol) is used.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 03-6230

Patent Document 2 Japanese Patent Laid-Open Publication No. 2003-186366

An object of the present invention is to provide a polyoxyl polyol which is excellent in miscibility with a polyol which is a raw material of a polyurethane resin and which is excellent in reactivity with an isocyanate group, and can be used in a one-stage method and prepolymerization. A polyurethane resin composition which is excellent in resistance to fusting, helium atom cohesiveness, various physical properties, and low friction property when forming a polyurethane molded article by any one of the methods And its shape.

The present inventors have conducted research on a polyurethane resin using a polyoxyl polyol, and found that a polyoxyl polyol having a specific amount of a lactone monomer added to a specific polysiloxane has a polyhydric alcohol. Excellent miscibility, when When it is used as a raw material of a polyurethane resin, a cured polyurethane having excellent resistance to halo, cesium atom cohesiveness, various physical properties, and low friction can be obtained, and the present invention has been completed.

That is, the present invention provides a polyurethane resin composition comprising a polyisocyanate (A) polyisocyanate and (B) a polyol, which is characterized in that the polyol (B) contains : 0.01 to 5% by mass of lactone-modified one-side terminal polyoxyl polyol (B1), and 95 to 99.99% by mass of other polyol (B2), wherein lactone-modified one-side terminal polyoxyl The polyol (B1) has the first primary hydroxyl group of the organopolyoxyalkylene having two primary hydroxyl groups at one end and the other terminal having no reactive group, and each of the mole-opening addition polymerization 5 to 10 moles of lactone is used. body.

The present invention uses a specific amount of a polyoxyl polyol to which a lactone monomer is added in a specific amount in a specific polyoxyalkylene which is excellent in miscibility with a polyol which is a raw material of a polyurethane resin, and other plural The specific amount of the alcohol can be subjected to one-stage forming, and one of a one-stage forming method and a pre-polymer forming method can be used, and the fuzzing resistance and the cesium atom condensation can be produced at the time of forming the polyurethane molding. A cured polyurethane resin having excellent properties, various physical properties, and low friction properties provides a polyurethane resin composition useful as a raw material of a polyurethane resin.

The polyol (B) contains 0.01 to 5% by mass of a lactone-modified one-side terminal polyoxyl polyol (B1), and 95 to 99.99% by mass of another polyol (B2), wherein the lactone is modified. The unilateral terminal polyoxyl polyol (B1) has two primary hydroxyl groups at one end and no opposite at the other end. The aforementioned primary hydroxyl group of the organopolyoxyalkylene group is a 5 to 10 mole lactone monomer per mole open-loop addition polymerization. When the amount is less than 0.01% by mass, the polyurethane resin cannot be imparted with low friction properties, and if it is more than 5% by mass, the tendency to separate is not preferable.

The organopolyoxane used in the present invention is an organopolyoxane having two primary hydroxyl groups at one terminal end and no reactive group at the other end. The organic polysiloxane is preferably a molecular weight of 1,000 to 4,000, and particularly preferably a molecular weight of 2,000 to 4,000. Further, the valence of the hydroxyl group is preferably 20 to 60 mgKOH/g, and the acid value is preferably 0.5 mgKOH/g or less.

When the molecular weight of the above-mentioned organopolyoxane is 1000 or more, it is preferable because it is easy to impart excellent effects such as low friction property to the urethane resin composition of the present invention. Further, when the molecular weight is 4,000 or less, the reaction between the lactone monomer and the organopolyoxane can be smoothly carried out, and the unreacted primary hydroxyl group is preferably reduced.

However, when the molecular weight of the aforementioned organopolyoxane is more than 4,000, the reaction between the lactone monomer and the aforementioned organopolyoxane cannot proceed smoothly to form two peaks, and there is a tendency that the unreacted primary hydroxyl group increases without good. Further, when the molecular weight is less than 1,000, there is a tendency that it is difficult to impart an effect such as low friction property which is an effect of the urethane resin composition as an organic polysiloxane.

However, the molecular weight as used in the present invention means a value obtained by the following formula.

Molecular weight = (56100 × 2) / (hydroxyl price + acid value)

The lactone monosystem used in the present invention means, for example, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ-crotonolactone. Etc., preferably ε-caprolactone. In the reaction with the above-mentioned organopolyoxane, it is preferred to carry out ring-opening addition polymerization of 5 to 10 moles of lactone monomer per mole of primary hydroxyl group in the above organopolyoxane. More preferably, each of the 8 moles of lactone monomer is subjected to addition polymerization with two primary hydroxyl groups on one side of the organopolyoxyalkylene. According to the primary hydroxyl group possessed by each mole organic polyoxane, when the lactone monomer is less than 5 moles, it is less preferred as a urethane raw material due to an increase in the unreacted primary hydroxyl group. On the other hand, when it is more than 10 mol, the viscosity of the obtained polyurethane resin is increased, and the handleability is deteriorated.

The lactone-modified one-side terminal polyoxyl polyol (B1) is produced by performing the system at a temperature of 80 to 140 ° C and a catalyst. More preferably 80~120 °C. If the temperature in the system is lower than 80 ° C, the reaction rate is slowed down and a long time of synthesis is required. When the temperature in the system is higher than 140 ° C, the organopolysiloxane having two primary hydroxyl groups at one end and having no reactive group at the other end will be decomposed, and the desired lactone modified one side cannot be obtained. Terminal type polyoxyl polyol.

The above-mentioned catalyst means that it is preferably a tin-based catalyst, and particularly preferably a butyltin tris-2-ethylhexanoate. At this time, the concentration of the catalyst in the system is preferably from 100 to 500 ppm with respect to the total mass of the synthetic raw material of the lactone-modified one-side terminal polyoxyl polyol (B1).

In order to produce a lactone-modified one-side terminal polyoxyl polyol (B1), the following steps may be carried out: an organopolyoxane having two primary hydroxyl groups at one end and no reactive group at the other end. And the catalyst is added to the reaction vessel, the temperature in the system is 80-140 ° C, and the lactone monomer is added under a nitrogen gas atmosphere so as to be in front of each mole of organopolyoxane The hydroxyl group of the first stage is 5 to 10 moles, and the reaction is preferably carried out for 6 to 24 hours, more preferably 8 to 15 hours. When the nonvolatile content is 99.5% by mass or more, the reaction is considered to be completed. Thereafter, the polyoxyl polyol was taken out.

In the case of the above lactone-modified one-side terminal polyoxyl polyol (B1), it is preferred that the molecular weight determined by the above formula is 2500 to 6000 using a hydroxyl value and an acid value. The lactone-modified one-side terminal polyoxyn polyol ((B1) has a molecular weight as long as it is in a relevant range, and it is excellent in low friction, and the handleability is not deteriorated.

Specific examples of the lactone-modified one-side terminal polyoxyl polyol (B1) include the compounds represented by the following formula (1).

Further, in the following formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents a methyl group or a phenyl group, m represents 1 to 4, and n represents a repeating unit number of 20 to 40.

The polyol (B) is obtained by mixing the lactone-modified one-side terminal polyoxyl polyol (B1) and other polyol (B2) to form a polyol (B), and then reacting with the polyisocyanate (A). A cured polyurethane resin is prepared. As a production method at this time, the polyol (B) and the polyisocyanate (A) may be previously prepared as a urethane prepolymer, and a hardener containing a compound containing an active hydrogen may be added to be hardened to carry out prepolymerization. The molding may be carried out by mixing a polyisocyanate (A), a polyol (B), or a chain extender as needed.

The above polyisocyanate (A) means, for example, 2,4-toluene diiso a mixture of cyanate ester, 2,6-toluene diisocyanate or the like; m-phenylene diisocyanate or p-phenylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, six Methylene-1,6-diisocyanate, 4,4'-diphenylmethane-diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4-biphenyldiisocyanate, 3,3 -bicyclo-4,4-biphenyldiisocyanate, 4,4-biphenyldiisocyanate or 1,5-naphthalene diisocyanate, tolidinediisocyanate, isophorone diisocyanate And cyclohexane diisocyanate, toluidine diisocyanate, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate, triphenylmethane triisocyanate, and various derivatives thereof. Further, a urethane prepolymer having an isocyanate group at the end of the reaction of the following polyol with any of the above polyisocyanates may be mentioned.

The aforementioned other polyols (B2) refer to various polyether polyols, polycarbonate polyols, polylactone polyester polyols or general polyester polyols, that is, also include the presence of a polyol and a polycarboxylic acid in a catalyst. The condensation reaction is carried out to have an ester bond. The molecular weight determined by the hydroxyl value and the acid value of the above other polyol is preferably from 600 to 6,000, particularly preferably from 600 to 3,000.

The molecular weight of the aforementioned other polyol (B2) is in a relevant range, and when the lactone-modified one-side terminal polyoxyl polyol (B1) is mixed with the aforementioned other polyol (B2), separation does not occur. A molded article having excellent tensile strength is preferred.

However, if the molecular weight of the other polyol (B2) is less than 600, the tendency of separation occurs when the lactone-modified one-side terminal polyoxyl polyol (B1) and the other polyol (B2) are mixed. Not good. When the molecular weight of the other polyol (B2) is more than 6000, there is It is difficult to obtain a molded article which exhibits excellent tensile strength, which is not preferable.

The polyester polyol is any one which has an ester bond by performing a condensation reaction between a polyhydric alcohol and a polycarboxylic acid in the presence of a catalyst, and also includes a polyether ester polyol and a polycarbonate polyester polyol. Wait. The polyester polyol has a molecular weight determined by a hydroxyl value and an acid value of preferably 600 to 6,000, particularly preferably 600 to 3,000.

The above polyol is preferably a linear diol having a main chain carbon number of 2 to 15, specifically ethylene glycol, 1,3-propanediol, diethylene glycol, 1,4-butanediol, 1,5- A hydrocarbon such as a diol such as pentanediol, 1,6-hexanediol, dihydroxyethoxybenzene or p-xylenediol is used as a main chain. The total number of carbon atoms is preferably from 3 to 34, more preferably from 3 to 17, such as 1,2-propanediol, 2-methyl-1,3-propanediol, di-1,2-propanediol, 1,2- Butylene glycol, 1,3-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl Base-1,3,5-pentanetriol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl 3-hydroxypropyl-2,2-dimethyl-3-hydroxypropyl ester, neopentyl glycol, 2-n-butyl-2-ethyl-1,3-propanediol, 3-ethyl-1, 5-pentanediol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 2-ethyl -1,3-hexanediol, 3-tetradecyl-1,5-pentanediol, 3-stearylpurine-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 3-(4-mercaptophenyl)-1,5-pentanediol, 3,3-bis(4-mercaptophenyl)-1,5-pentanediol, 1,2-bis(hydroxymethyl) Cyclopropane, 1,3-bis(hydroxyethyl)cyclobutane, 1,3-bis(hydroxymethyl)cyclopentane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4- Bis(hydroxyethyl)cyclohexane, 1,4-bis(hydroxypropyl)cyclohexane, 1,4-bis(hydroxyethyl)cycloheptane, 1,4-bis(hydroxymethoxy) ring Hexane, 1,4-bis(hydroxyethoxy)cyclohexane, 2,2-bis(4'-hydroxymethoxy Cyclohexyl)propane, 2,2-bis(4'-hydroxyethoxycyclohexyl)propane, hydroxymethyl Propane or the like, these may be used alone or in combination of two or more.

A compound having a hydroxyl group number of 3 or more can be used in combination with the above polyol component. The compound which can be used in combination is generally used as a polyester polyol, and examples thereof include polyfunctional polyhydroxy compounds such as glycerin, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine.

The polycarboxylic acid refers to, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, Tridecanedioic acid, tetradecanedioic acid, dodecanedioic acid, and aromatic diacids such as phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, hexahydrogen An acid anhydride such as isophthalic acid or the like, an ester derivative such as a methyl ester, or the like may be used alone or in combination of two or more. Adipic acid is mainly used from an industrial point of view. A dimer acid obtained by polymerizing a talloil fatty acid or the like can also be used. The pine oil fatty acid is a mixture of an unsaturated acid such as oleic acid or linoleic acid with palmitic acid, stearic acid or the like.

The polyether polyol refers to an alkylene oxide such as an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, and a compound having two or more, preferably 2 to 6 active hydrogen atoms. For example, the aforementioned polyol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, mannitol, di-trimethylolpropane, dipentaerythritol or the like may be added singly or in combination of two or more, preferably 2 to 9 moles. The resulting polyol is polymerized. The molecular weight determined from the hydroxyl value is preferably from 300 to 6,000, particularly preferably from 600 to 3,000. Further, the hydroxyl value is preferably from 20 to 750.

For the polylactone polyester polyol, for example, a lactone-based polyester diol obtained by subjecting a lactone such as ε-caprolactone to ring-opening polymerization can be used. Inside The ester polyester diol may be obtained by addition polymerization of one or more of ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, and the like with the above polyol. By.

The polycarbonate polyol is obtained, for example, by a condensation reaction between a low molecular polyol and a dialkyl carbonate. The low molecular polyol may, for example, be 1,6-hexanediol or 1,5-pentanediol. Further, the dialkyl carbonate may, for example, be dimethyl carbonate, diethyl carbonate or ethylene carbonate.

Further, the polycarbonate polyol may, for example, be a lactone-modified polycarbonate polyol obtained by subjecting a lactone to a ring-opening addition polymerization with a polycarbonate polyol, or by making other polyester polyols or polyethers plural. A cocondensed polycarbonate polyol obtained by co-condensation of an alcohol or the like with a polycarbonate polyol.

As the chain extender, a low molecular weight linear diol or a diamine compound having 2 to 10 carbon atoms is preferably used. Representative examples thereof include ethylene glycol alone, 1,2-propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 2,2'-dimethyl-1. , 3-propanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane 1,4-diol, cyclohexane-1,4 glycol, cyclohexane- 1,4 dimethanol or the like; ethylenediamine, 1,6-hexanediamine, piperazine 2,5-Dimethyl pipe , isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine , 1,2-propanediamine, diethylenetriamine, triethylenetetramine, amine compounds such as 3,3'-dichloro-4,4'-diaminodiphenylmethane, and hydrazine, hydrazine Equivalent amines. Particularly preferred are 1,4-butanediol and trimethylolpropane.

The polyurethane resin composition of the present invention can be made not only into an urethane elastomer but also an aqueous polyurethane resin or an aqueous polyurethane resin. The polyurethane resin composition One or more types selected from the group consisting of an anionic group, a cationic group, and a nonionic group are introduced as a hydrophilic group to carry out water dispersion. In this case, a chain extender having a hydrophilic group may be used for the polyester polyol produced by the catalyst, and a hydrophilic group-containing alcohol and/or a hydrophilic group-containing diprotic acid may be partially used as the polyester polyol. The hydrophilized polyester polyol is produced by using a raw material of a polyester polyol produced by a catalyst, and a water-based or aqueous polyurethane resin composition is produced by a conventional method.

The manufacturing method may be, for example, (i) using a group containing at least one hydroxyl group, an amine group in one molecule and containing one group selected from the group consisting of an anionic group, a cationic group, and a nonionic group in one molecule. A method for producing an aqueous or aqueous polyurethane resin by using a compound of the above hydrophilic group, wherein the hydroxyl group and the amine group can be reacted with an isocyanate group using a polyester polyol which does not contain a hydrophilic group produced by using a catalyst And (ii) using a polyol having a hydrophilic group represented by an anionic group, a cationic group, and a nonionic group or a neutralizing salt thereof, and/or containing the aforementioned hydrophilicity A polycarboxylic acid or a dicarboxylic acid whose main component is a polycarboxylic acid or an ester derivative thereof, and a hydrophilic polyol-containing polyester polyol is produced by using a catalyst to produce a water-based or aqueous polyamine group using the same. A method of a formate resin.

The anionic group as the hydrophilic group is preferably a carboxyl group, a carboxylate group, a sulfonic acid group or a sulfonate group, and the cationic group is preferably a tertiary amino group, a part or all of which is a tertiary group. When the acid compound is neutralized or quaternized by a quaternizing agent, the nonionic group is preferably a polyoxyalkylene group structure, preferably For example, polyethylene glycol and copolymers thereof are exemplified.

Some or all of the anionic group and the cationic group may be neutralized by various basic compounds or acidic compounds, or a tertiary amine group as a cationic group may be further substituted by a quaternizing agent.

The polyester polyol containing the above anionic group may, for example, be a polyester polyol containing a carboxyl group or a polyester polyol containing a sulfonic acid group.

The urethane resin composition of the present invention can be produced by various methods for producing a polyurethane, such as a one-stage method, a prepolymer method or a quasi-prepolymer method, and further, a block polymerization or a solution can be used. Polymerization, emulsion polymerization, emulsion polymerization, and the like. The production method should also be a conventional method, which can be slab, double conveyor, hotcure, coldcure, RIM, open mold, Forming, in-situ construction, spray, casting, injection, coating, impregnation, etc. At the time of manufacture, the polyisocyanate and the polyol are preferably reacted at a molar ratio (NCO/OH+NH ₂ ) of 0.8 to 1.1, more preferably 1.0 to 1.05. Further, in the case of producing a urethane, a conventional urethane catalyst, a surfactant, another adjuvant, or the like can be used in an amount generally used.

Further, the urethane composition of the present invention may contain an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a filler, a colorant, a reinforcing agent, a mold release agent, a flame retardant, and the like as needed. Further, other thermoplastic polyurethane elastomers may be added, or other widely used thermoplastic resins, insofar as the effects of the urethane resin composition of the present invention are not impaired. For example, ABS resin, AS resin, vinyl chloride resin, polyamide or the like. The composition of the present invention may also contain a surfactant selected from a surfactant, a catalyst, Stabilizers, and various additives for pigments.

The invention can be used as a thermoplastic elastomer (TPU), a thermosetting elastomer (TSU), an aqueous polyurethane resin, a radical curable urethane resin, and can be used for a molding material, an adhesive, Adhesives, coatings, foams, sealants, photocurable resins and other areas of polyurethane products. The specific use can be used for three-dimensional forming of silk, film, sheet, belt, hose, roller, tire, anti-vibration material, liner, sole, etc., as well as artificial leather, synthetic leather, soft/hard foam, fiber material. , industrial materials, electrical and electronic materials, optical materials, medical materials, civil construction materials and many other fields.

[Examples]

The present invention will be specifically described below by way of examples, but is not limited thereto. Also, "parts" and "%" in the text are quality benchmarks.

Synthesis Example 1 (Synthesis of Modified 16-Meractone Modified Single-Ended Polyoxyl Polyol)

In a 1-liter four-necked flask equipped with a nitrogen gas introduction tube, a thermometer, a cooling tube, and a stirring device, the one-side terminal of the following structural formula (2) [n=33 in the formula] has two primary hydroxyl groups and the other end is not Organic polyoxyalkylene having a reactive group (hydroxyl price: 41.1 mgKOH/g, acid value: 0.05 mgKOH/g) 500 g, ε-caprolactone 335 g, butyltin tris-2-ethylhexanoate as a reaction catalyst 0.250 g was reacted at 100 ° C for 13 hours while introducing nitrogen gas. (The end point of the reaction is to measure the non-volatile content (NV) appropriately, and the end point is when the NV is 99.5% or more.)

After 13 hours of reaction, the NV has reached 99.7%, and the lactone-modified one-side terminal polyoxyl polyol (the addition of 8 moles per 1 mole of primary hydroxyl group) is also taken out from the flask. The Lc/Si polyol) was obtained by the reaction product having a hydroxyl group value of 24.4 mgKOH/g, an acid value of 0.55 mgKOH/g, a white solid at normal temperature (25 ° C), and a transparent liquid at 100 ° C. The molecular weight distribution measured by GPC showed a normal distribution, and the ratio of the unreacted primary hydroxyl group of the organopolyoxane measured by ¹³ C-NMR was 5% (that is, 95% of the primary hydroxyl group reacted with ε-caprolactone) .

Synthesis Examples 2 and 3 and Comparative Synthesis Example 1

In the same manner as in Synthesis Example 1, 12 moles of lactone, 20 moles, and 4 moles of the modified one-side terminal polyoxyl polyol were synthesized in the same manner as in Synthesis Example 1. These polyoxyl polyols are added to a primary hydroxyl group per 1 mole, an addition of 6 moles of addition product, addition of 10 moles of addition product and addition of 2 moles of addition product. The characteristics of the obtained Lc/Si polyol are shown in Table 1.

In addition, the assessment method is as follows:

<non-volatile content>

1 g of the sample was taken and 5 ml of toluene was placed in a metal dish, and dried at 107.5 ° C for 1 hour to obtain a residual amount.

Non-volatile content (%) = [(B-C) / (A-C)] × 100

However, A: metal dish + mass of sample before drying (g)

B: Quality of the metal dish + sample after drying (g)

C: the quality of the metal dish

<hydroxyvalency>

After adding an acetalization agent containing acetic anhydride and pyridine to the sample, the oximation reaction was carried out at 115 ° C for 1 hour. Next, water was added to decompose excess acetic anhydride into acetic acid, and after adding acetone and toluene, acetic acid was neutralized and titrated using a 0.5 N potassium hydroxide ethanol solution.

Hydroxyl price (mgKOH/g) = [(B-T) × F × 28.05 / S] + AN

However, B: the amount of 0.5N potassium hydroxide ethanol solution in the blank test (ml)

T: Instillation amount of 0.5N potassium hydroxide ethanol solution in the official test (ml)

F: the price of 0.5N potassium hydroxide ethanol solution

S: sample size (g)

N: mol / liter

AN: Acid value of the sample

<acid price>

After adding a neutral solvent (toluene/methanol) to the sample to dissolve it, neutralization titration was carried out with a 0.1 N potassium hydroxide ethanol solution.

Acid value (mgKOH/g)=V×F×5.611/S

However, the amount of V:0.1N potassium hydroxide ethanol solution (ml)

F: the price of 0.1N potassium hydroxide ethanol solution

S: sample size (g)

N: mol / liter

<molecular weight separation rate>

The separation rate was determined from the hydroxyl value of the uni-side terminal diol type organopolyoxane, the acid value, and the molar ratio of ε-caprolactone/unilateral terminal diol type organopolyoxane. The obtained target molecular weight, the hydroxyl value of the obtained resin, and the acid value of the obtained experimental molecular weight were calculated.

Molecular weight separation rate (%) = [(target molecular weight - experimental molecular weight) / target molecular weight] × 100

However, molecular weight = (56100 × 2) / (hydroxyl price + acid value)

<Proportion of unreacted primary hydroxyl group (ratio of primary hydroxyl group of organic polyoxyalkylene not reacted with lactone)>

The sample was dissolved in heavy chloroform, and ¹³ C-NMR was measured by a conventional method. The peak represented by 65.5 ppm (a carbon adjacent to a hydroxyl group which is not reacted with a lactone) is calculated from the peak represented by 62.0 ppm (a carbon adjacent to a hydroxyl group which reacts with a lactone).

Ratio (%) of unreacted primary hydroxyl group = [65.5 ppm peak area / (65.5 ppm peak area + 62.0 ppm peak area)] × 100

<Molecular weight distribution determined by GPC>

The sample was dissolved in tetrahydrofuran (THF) (0.4% solution) and subjected to gel permeation chromatography. The shape of the resulting chromatogram was evaluated.

[Measurement conditions]

Eluent: THF; column: TSKgel; flow rate: 1.0 ml/min

Column: TSKgelG5, 4, 3, 2; detector: RI

(mismixing test)

3% by mass of Synthesis Example 1, a lactone-modified one-side terminal polyoxyl polyol of Comparative Synthesis Example 1, and an organic polyoxyalkylene having two unmodified primary hydroxyl groups at one end thereof were added to various pluralities. The alcohol was allowed to stand at 70 ° C for 4 days, and visually observed and evaluated.

(assessment)

××: There are more than 3mm separation liquid in the upper layer

×: The upper layer contains a separation liquid of 1 mm or more and less than 3 mm.

○: no separation

PTMG: poly(1,4-butanediol) polyether polyol

BG/AA polyester polyol: polyester polyol of 1,4-butanediol and adipic acid

BG, HG/AA polyester polyol: 1,4-butanediol and polyester polyol of 1,6-hexanediol and adipic acid

3MPD/AA polyester polyol: polyester polyol of 3-methyl-1,5-pentanediol and adipic acid

Polycaprolactone polyol: ε-caprolactone addition polyester polyol with ethylene glycol as initiator

Polycarbonate Polyol: Polycarbonate Polycarbonate Containing 1,6-Hexanediol and Dimethyl Carbonate

Unmodified: an organopolyoxane having two primary hydroxyl groups at one end

Example 1 (prepolymer method) (Synthesis of urethane prepolymer)

483.0 g of 4,4'-diphenylmethane diisocyanate was added to a 2 liter flask, and ε-caprolactone addition polyester polyol (molecular weight 2000) 1000 g with ethylene glycol as a starting agent was mixed and a synthesis example. 16.7 g of a lactone-modified one-side terminal polyoxyl polyol was reacted in a nitrogen atmosphere at 70 ° C for about 5 hours. Adding (modulating) a trace amount of 4,4'-diphenylmethane diisocyanate or ε-caprolactone addition polyester polyol to make the NCO equivalent of 525, that is, prepolymerizing a urethane containing polyfluorene oxide Things.

(Production of urethane elastomer)

Mixing 400 g of a polyoxonium urethane prepolymer having a temperature of 80 ° C and a temperature of 50 ° C to a temperature of 50 ° C of 1,4-butanediol / trimethylolpropane 70 / 30 (mass ratio) 32.6 g of the mixture was cast into a centrifugal molding machine, hardened at 140 ° C for 1 hour, and then subjected to secondary hardening at 110 ° C for 16 hours to obtain a 2 mm thick urethane. Elastomer sheet.

Example 2 (a method) (Modulation of Polyol Compounds)

The ε-caprolactone addition polyester polyol (molecular weight 2000) 1000 g was mixed and prepared in a 2-liter flask, and the lactone-modified one-side terminal polyoxyl polyol of Synthesis Example 1 was 16.7 g, 1,4-butyl A polyol compound of 122.1 g (70 ° C, 10 minutes) of a 70/30 (mass ratio) mixture of diol/trimethylolpropane.

(Production of urethane elastomer)

300 g of a polyol compound adjusted to 70 ° C and 127.2 g of 4,4'-diphenylmethane diisocyanate adjusted to 60 ° C were mixed and cast into a centrifugal molding machine, and then allowed to stand at 140 ° C for 1 hour. After hardening, secondary hardening was carried out at 110 ° C for 16 hours to obtain a 2 mm thick urethane elastomer sheet.

Examples 3, 5, 7, 9, 11 (prepolymer method) (Synthesis of urethane prepolymer)

The mixed amount of the urethane prepolymer shown in Table 3 was prepared in the same manner as in the prepolymer synthesis of Example 1.

MDI: 4,4'-diphenylmethane diisocyanate

(Production of urethane elastomer)

The mixed amount of a 2 mm thick urethane elastomer sheet shown in Table 4 was obtained in the same manner as in the urethane elastomer of Example 1. The results of the evaluation are shown in Table 7-8.

Examples 4, 6, 8, 10, 12 (a method) (Modulation of Polyol Compounds)

The compounding amount of the polyol compound shown in Table 5 was obtained in the same manner as in the preparation of the polyol compound of Example 2.

(Production of urethane elastomer)

The mixed amount of a 2 mm thick urethane elastomer sheet shown in Table 6 was obtained in the same manner as in the urethane elastomer of Example 2. The results of the evaluation are shown in Table 7-8.

MDI: 4,4'-diphenylmethane diisocyanate

(Evaluation Results)

In addition, the assessment method is as follows:

<Sheet appearance (scizziness)>

The state of the sheet immediately after forming and one month after forming was evaluated by visual inspection and finger touch.

○: No halo.

△: It was impossible to judge visually but the oil was felt with a finger touch.

×: Both the visual and the finger touch (oil) are clearly noticeable to the halo.

<tensile strength, M100, M300, ductility>

The centrifugally formed sheet was punched out in the form of a dumbbell No. 4 and measured based on Japanese Industrial Standard JIS K 7312.

Punch speed: 500mm/min

<tension strength (tearingstrength)>

The centrifugally formed sheet was punched out into a non-notched angular dumbbell shape, and was measured based on Japanese Industrial Standard JIS K 7312.

Punch speed: 500mm/min

<Static friction coefficient, dynamic friction coefficient>

The centrifugally formed sheet was stored in the room for 2 weeks after the completion of the secondary hardening. Thereafter, it was cut into 10 × 20 cm, and the surface of the sheet was sufficiently washed with acetone several times on the day before the measurement.

In the measurement, the static friction coefficient and the dynamic friction coefficient of the centrifugally formed sheet were measured by a surface tester.

Planar cylindrical indenter (with clamp for sheet test piece fixation): 30 × 30mm, 84g

Measurement object: OA plain paper (mounted on a jig) / centrifugally formed sheet

Weighting: 84g of flat cylindrical indenter (no forced weighting)

Surface testing machine: Type-HEIDON-14 (New East Science Co., Ltd.)

<Coagulation of Helium Atoms>

The centrifugally formed sheet was stored in the room for 2 weeks after the completion of the secondary hardening. Thereafter, the surface of the sheet was sufficiently washed with acetone for several days before the measurement. The measurement was evaluated by atom mapping of the SEM of the surface of the sheet (one side of the contact with air).

The part where the concentration of germanium atoms is higher than the periphery is round. Judging by the diameter of the high concentration part.

○: no condensation or diameter less than 1 μm

△: diameter 1 μm or more and less than 5 μm

×: 5 μm or more in diameter

Comparative Examples 1, 3, 5, 7, and 9 (prepolymer method) (Synthesis of urethane prepolymer)

The mixed amount of the urethane prepolymer shown in Table 9 was obtained in the same manner as in the prepolymer synthesis of Example 1.

‧MDI: 4,4'-diphenylmethane diisocyanate

(Production of urethane elastomer)

The mixed amount of a 2 mm thick urethane elastomer sheet shown in Table 10 was obtained in the same manner as in the urethane elastomer of Example 1. The results of the evaluation are shown in Tables 13-14.

Comparative example 2, 4, 6, 8, 10 (a method) (Modulation of Polyol Compounds)

The compounding amount of the polyol compound shown in Table 11 was obtained in the same manner as in the preparation of the polyol compound of Example 2.

(Production of urethane elastomer)

The mixed amount of a 2 mm thick urethane elastomer sheet shown in Table 12 was obtained in the same manner as in the urethane elastomer of Example 2. The results of the evaluation are shown in Tables 13-14.

‧MDI: 4,4'-diphenylmethane diisocyanate

(Evaluation Results)

HEIDON: Surface testing machine

In Comparative Examples 1 and 2, since the decane component was not added, the frictional resistance was large and the low friction property could not be obtained. In Comparative Examples 3 and 4, since the polyoxyl polyol was not in an appropriate range, a halo was observed on the sheet, and a circular portion having a higher concentration of germanium atoms than the periphery was observed on the surface of the sheet, which was uneven. . In particular, when a roller or a cleaning blade of a printer is used, if the photoreceptor or the printed matter is contaminated or the concentration of germanium atoms is uneven due to blooming, the roller and the cleaning blade may peel off ( Chipping) is not good.

In Comparative Examples 5 to 10, since unmodified decane was used, the reason was the same as that of Comparative Examples 3 to 4, and it was not practical to use it in a part of molding.

[Industrial availability]

The polyurethane resin composition of the present invention can be made into a polyamine-based group having excellent properties such as fuzzing resistance, helium atom cohesiveness, various physical properties, and low friction property by a one-stage molding method and a prepolymer molding method. The acid ester cured product can be used for three-dimensional molded articles such as silk, film, sheet, belt, hose, roller, tire, vibration-proof material, liner, sole, and the like, as well as artificial leather, synthetic leather, soft/hard foaming. Body, fiber materials, industrial materials, electrical and electronic materials, optical materials, medical materials, civil construction materials and many other fields.

Claims (7)

A polyurethane resin composition comprising (A) a polyisocyanate and (B) a polyurethane resin composition of a polyol, characterized in that the polyol (B) contains: 0.01 to 5 mass % lactone modified one-side terminal polyoxyl polyol (B1), and 95 to 99.99% by mass of other polyol (B2), wherein lactone modified one-side terminal polyoxyl polyol (B1) The first-order hydroxyl group of the organopolyoxane having two primary hydroxyl groups at one end and having no reactive group at the other end is 5 to 10 moles of lactone monomer per 1 mole of ring-opening addition polymerization. The polyurethane resin composition according to the first aspect of the invention, wherein the other polyol (B2) is at least one selected from the group consisting of polyether polyols and polyester polyols. The polyurethane resin composition according to claim 1, wherein the molecular weight of the above (B2) is from 600 to 3,000. The polyurethane composition according to claim 1, wherein the molecular weight of the above (B1) is 2,500 to 6,000. The polyurethane resin composition of claim 1, wherein the lactone monomer is ε-caprolactone. The polyurethane composition according to claim 1, wherein the lactone-modified one-side terminal polyoxyl polyol (B1) has two primary hydroxyl groups at one end and another The primary hydroxyl group of the organopolyoxyalkylene having no reactive group at one end is added with a lactone monomer of 8 moles per mole. A molded article obtained by the polyurethane resin composition according to any one of claims 1 to 6.