JP5019011B2 - Polyurethane resin composition and molded product thereof - Google Patents

Abstract

Provided is a polyurethane resin composition which can be molded by a one-shot method or a prepolymer method using a silicone polyol highly miscible with a polyol to be used as a starting material of a polyurethane resin, and achieves excellent blooming resistance, Si atom aggregability, various physical properties, and low frictional properties when formed into a polyurethane molded article, and also provided is a molded article thereof. The polyurethane resin composition comprises (A) a polyisocyanate and (B) a polyol, and is characterized in that the polyol (B) comprises 0.01 to 5% by mass of a silicone polyol having one end modified with lactone (B1) obtained by the ring-opening addition polymerization of 5 to 10 moles of a lactone monomer at each primary hydroxyl group of an organopolysiloxane having two primary hydroxyl groups at one end and 95 to 99.99% by mass of another polyol (B2).

Description

The present invention relates to a polyurethane resin composition from which a polyurethane cured product having excellent bleeding resistance, Si atom aggregation, physical properties and low friction properties can be obtained, and a molded product obtained by using the polyurethane resin composition.

In recent years, organopolysiloxane compounds have excellent interfacial properties such as low friction, thermal stability, water repellency, antifoaming, and releasability, so that the performance of synthetic resins such as paints and molded products can be improved. , for example, dimethyl polysiloxane, methylphenyl polysiloxane, reactive group-containing dimethyl polysiloxane, modifiers and polyether-modified organopolysiloxane is used added.

However, these have insufficient compatibility with the resin, and their heat resistance is insufficient, so the range of use has been limited. Therefore, a lactone-modified organopolysiloxane compound in which a lactone is added to an addition reaction product of polysiloxane and glycerin monoallyl ether has been proposed for the purpose of improving these disadvantages (see, for example, Patent Document 1).
However, in this product, the lactone reacts with a plurality of hydroxyl groups of glycerin monoallyl ether to have a plurality of polylactone chains, so that a cross-linked structure increases, and a primary hydroxyl group and a secondary hydroxyl group are mixed during the urethanization reaction. Therefore, it has been difficult to use as a raw material for polyurethane resin because the reactivity varies and the compatibility with polyol is poor.

Moreover, if the polyurethane resin composition containing polyisocyanate and polyol as essential components was merely used for molding, the resulting molded product was inferior in friction resistance. In order to improve this problem, it has been proposed to introduce organopolysiloxane into the urethane polymer (see, for example, Patent Document 2).
However, although the technique of Patent Document 2 certainly has some improvement in friction resistance, it is inferior in the compatibility between the organopolysiloxane and the polyol, so that the resulting molded product tends to bleed , particularly by the one-shot method. Such defects were prominent in molding.

  As described above, the compatibility with polyol is improved, and a polysiloxane chain-containing polyol (hereinafter referred to as silicone polyol) that can be used well as a raw material for polyurethane resin in any one of the one-shot method, the prepolymer method, and the molding method. ) Was desired.

Japanese Patent Laid-Open No. 03-6230 JP 2003-186366 A

The purpose of the present invention is to use a silicone polyol having excellent compatibility with a polyol that is a polyurethane resin raw material and excellent reactivity with an isocyanate group, and can be molded by any one of the one-shot method and the prepolymer method, An object of the present invention is to provide a polyurethane resin composition excellent in bleed resistance, Si atom aggregation, various physical properties, and low friction when it becomes a polyurethane molded product, and a molded product thereof.

As a result of diligent research on silicone polyols for polyurethane resins, the present inventors found that silicone polyols obtained by adding a specific amount of lactone monomers to specific polysiloxanes are excellent in compatibility with polyols, and when used as polyurethane resin raw materials, bleeding resistance, The present inventors have found that a polyurethane cured product excellent in Si atom aggregation, various physical properties, and low friction properties can be obtained, and completed the present invention.

That is, the present invention relates to a polyurethane resin composition containing (A) polyisocyanate and (B) polyol, wherein the polyol (B) has two primary hydroxyl groups at one end and at the other end. Lactone-modified one-end type silicone polyol (B1) of 0.01 to 5% by mass obtained by ring-opening addition polymerization of lactone monomer to the hydroxyl group of organopolysiloxane having no reactive group and other polyol (B2 And 95 to 99.99% by mass. A polyurethane resin composition is provided.

The present invention uses a specific amount of a silicone polyol obtained by adding a specific amount of a lactone monomer to a specific polysiloxane excellent in compatibility with a polyol, which is a polyurethane resin raw material, and a specific amount of another polyol, thereby allowing one-shot molding. The polyurethane resin cured product excellent in bleed resistance, Si atom aggregation, various physical properties, and low friction when it becomes a polyurethane molded product can be produced by either the one-shot molding method or the prepolymer molding method. A polyurethane resin composition useful as a polyurethane resin raw material can be provided.

In the polyol (B), 5 to 10 moles of ring-opening addition of lactone monomer is added to the hydroxyl group of the organopolysiloxane having two primary hydroxyl groups at one end and no reactive group at the other end. It contains 0.01 to 5% by mass of polymerized lactone-modified one-end type silicone polyol (B1) and 95 to 99.99% by mass of other polyols (B2). If it is less than 0.01% by mass, low friction cannot be imparted to the polyurethane resin, and if it exceeds 5% by mass, it tends to be separated, which is not preferable.

The organopolysiloxane used in the present invention is an organopolysiloxane having two primary hydroxyl groups at one end and no reactive group at the other end . The organopolysiloxane preferably has a molecular weight of 1000 to 4000, and particularly preferably has a molecular weight of 2000 to 4000. The hydroxyl value is preferably 20 to 60 mgKOH / g, and the acid value is preferably 0.5 mgKOH / g or less.

If the molecular weight of the organopolysiloxane is 1000 or more, it is preferable because excellent effects such as low friction are easily imparted to the urethane resin composition of the present invention. Moreover, if the molecular weight is 4000 or less, the reaction between the lactone monomer and the organopolysiloxane proceeds smoothly and unreacted primary hydroxyl groups are reduced, which is preferable.
However, when the molecular weight of the organopolysiloxane is greater than 4000, the reaction between the lactone monomer and the organopolysiloxane does not proceed well, resulting in two peaks and a tendency to increase the number of unreacted primary hydroxyl groups. It is not preferable. Moreover, when molecular weight is smaller than 1000, there exists a tendency for it to become difficult to provide effects, such as the low friction property which is the effect of organopolysiloxane, to a urethane resin composition, and is not preferable.

However, the molecular weight referred to in the present invention refers to a value determined by the following calculation formula.
Molecular weight = (56100 × 2) / (hydroxyl value + acid value)

Examples of the lactone monomer used in the present invention include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ-crotonolactone, and preferably ε-caprolactone. Wherein upon reaction with the organopolysiloxane, it ring-opening addition polymerization of primary hydroxyl group per 5-10 moles in the organopolysiloxane lactone monomer. Furthermore, it is preferable to carry out addition polymerization of the lactone monomer by two moles to two primary hydroxyl groups on one side of the organopolysiloxane. When the lactone monomer is less than 5 moles per primary hydroxyl group of the organopolysiloxane, unreacted primary hydroxyl groups increase, which is not preferable as a urethane raw material. On the other hand, when the amount is more than 10 mol, the viscosity of the obtained polyurethane resin becomes high and the handling property is inferior.

The lactone-modified one-end type silicone polyol (B1) is produced by carrying out in the system at a temperature of 80 to 140 ° C. in the presence of a catalyst. More preferably, it is 80-120 degreeC. When the temperature in the system is lower than 80 ° C., the reaction rate becomes slow and a long-time synthesis is required. When the temperature in the system is higher than 140 ° C., an organopolysiloxane having two primary hydroxyl groups at one end and no reactive group at the other end is decomposed to produce a desired lactone-modified piece. A terminal type silicone polyol cannot be obtained.

  The catalyst is preferably a tin-based catalyst, and particularly preferably butyltin tris-2-ethylhexanoate. At that time, the concentration of the catalyst in the system is preferably 100 to 500 ppm with respect to the total mass of the synthesis raw material of the lactone-modified one-end type silicone polyol (B1).

In order to produce a lactone-modified one-end type silicone polyol (B1), an organoorganism having a molecular weight of 1000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end in the reaction vessel. A polysiloxane and a catalyst are added, the temperature in the system is set to 80 to 140 ° C., and a lactone monomer is charged in a nitrogen gas atmosphere so as to be 5 to 10 mol per hydroxyl group of the organopolysiloxane, preferably 6 to 24 The reaction is performed for a period of time, more preferably 8 to 15 hours, and the reaction is terminated when the nonvolatile content reaches 99.5% by mass or more. Thereafter, the silicone polyol may be taken out.

  The lactone-modified one-end type silicone polyol (B1) preferably has a molecular weight of 2500 to 6000 determined by the above formula using a hydroxyl value and an acid value. When the molecular weight of the lactone-modified one-end type silicone polyol ((B1) is within such a range, excellent low friction properties can be imparted and handling properties are not inferior.

Specific examples of the lactone-modified one-terminal silicone polyol (B1) include compounds represented by the following general formula (1).
In the following general 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 the number of repeating units of 20 to 40. .

  The polyol (B) is a polyurethane resin cured by mixing the lactone-modified one-end silicone polyol (B1) and another polyol (B2) to form a polyol (B) and reacting with the polyisocyanate (A). It is assumed to be a thing. As a manufacturing method at that time, the polyol (B) and the polyisocyanate (A) may be cured in advance by adding a curing agent containing an active hydrogen-containing compound as a urethane prepolymer, and may be prepolymer molded. A), polyol (B), and, if necessary, a chain extender may be mixed for one-shot molding.

  Examples of the polyisocyanate (A) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, tetramethylene- 1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 4,4'-diphenylmethane-diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4-biphenylene diisocyanate, 3,3-dichloro-4,4- Biphenylene diisocyanate, 4,4-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, tolidine diisocyanate, ifosolone diisocyanate, cyclohexane diisocyanate, toluidine Isocyanates, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate are triphenylmethane triisocyanate and their various derivatives. Moreover, the urethane prepolymer whose terminal which made the following polyol and one of the said polyisocyanates react is an isocyanate group is also mentioned.

  The other polyols (B2) are various polyether polyols, polycarbonate polyols, polylactone polyester polyols or ordinary polyester polyols, that is, polycondensation alcohols and polycarboxylic acids are subjected to a condensation reaction in the presence of a catalyst. Those having an ester bond are also included. The other polyols preferably have a molecular weight of 600 to 6000, particularly preferably 600 to 3000, determined from the hydroxyl value and the acid value.

If the molecular weight of the other polyol (B2) is within such a range, when the lactone-modified one-end type silicone polyol (B1) and the other polyol (B2) are mixed, separation does not occur, and excellent high elongation A molded product having the following is obtained, which is preferable.
However, when the molecular weight of the other polyol (B2) is smaller than 600, separation tends to occur when the lactone-modified one-end silicone polyol (B1) and the other polyol (B2) are mixed. Absent. On the other hand, when the molecular weight of the other polyol (B2) is larger than 6000, it tends to be difficult to obtain a molded product that can exhibit excellent strength and elongation.

  The polyester polyol may be any one as long as it has an ester bond by condensation reaction of polyhydric alcohol and polyvalent carboxylic acid in the presence of a catalyst, such as polyether ester polyol, polycarbonate polyester polyol, etc. Is also included. The polyester polyol preferably has a molecular weight determined by a hydroxyl value and an acid value of 600 to 6000, particularly preferably 600 to 3000.

  The polyhydric alcohol is preferably a linear glycol having 2 to 15 main chain carbon atoms, specifically ethylene glycol, 1,3-propylene glycol, diethylene glycol, 1,4-butylene glycol, 1,5-pentamethyl. The main chain is a hydrocarbon such as glycol, 1,6-hexamethylene glycol, bishydroxyethoxybenzene or p-xylene glycol. The total number of carbon atoms is preferably 3 to 34, more preferably 3 to 17, such as 1,2-propylene glycol, 2-methyl-1,3-propanediol, di-1,2-propylene glycol, 1, 2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl-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 -Hydroxypropanate, neopentyl glycol, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pen Diol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 3- Myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 3- (4-nonylphenyl) -1,5-pentanediol, 3,3 -Bis (4-nonylphenyl) -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) cyclohebutane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4′-hydroxymethoxycyclohexyl) ) Propane, 2,2-bis (4′-hydroxyedoxycyclohexyl) propane, trimethylolpropane and the like, and these may be used alone or in combination of two or more.

  As the polyhydric alcohol component, a compound having 3 or more hydroxyl groups can be used in combination. The compound that can be used in combination may be any compound that is generally used for polyester polyols, and examples thereof include polyfunctional polyhydroxy compounds such as glycerin, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine.

  Examples of the polyvalent carboxylic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonamethylene dicarboxylic acid, and 1,10-decamethylene dicarboxylic acid. 1,11-undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, dodecanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, hexahydro Isophthalic acid, their anhydrides, ester derivatives such as methyl ester, etc. can be used alone or in combination of two or more. From an industrial point of view, adipic acid is mainly used. Dimer acid obtained by polymerization of tall oil fatty acid can also be used. The tall oil fatty acid is a mixture of an unsaturated acid such as oleic acid or linoleic acid and palmitic acid or stearic acid.

  The polyether polyol is a compound having 2 or more, preferably 2-6 active hydrogens, for example, the polyhydric alcohol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, mannitol, ditrimethylolpropane, dipentaerythritol. For example, it is a polyol obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or the like alone or in combination of 2 to 9 moles with respect to alkylene oxide. The molecular weight determined by the hydroxyl value is preferably 300 to 6000, particularly preferably 600 to 3000. The hydroxyl value is preferably 20 to 750.

  As the polylactone polyester polyol, for example, lactone polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone can also be used. Examples of the lactone polyester diols include those obtained by addition polymerization of one or more of ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone and the like to the polyhydric alcohol described above. Can be used.

  As said polycarbonate polyol, for example, a low molecular polyol and a dialkyl carbonate can be obtained by a condensation reaction. Examples of the low molecular polyol include 1,6-hexanediol and 1,5-pentanediol. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and ethylene carbonate.

  Examples of the polycarbonate polyol include a lactone-modified polycarbonate polyol obtained by further ring-opening addition polymerization of a lactone to the polycarbonate polyol, and a co-condensed polycarbonate polyol obtained by co-condensing a polycarbonate polyol with another polyester polyol or polyether polyol. Is mentioned.

  As the chain extender, a low molecular weight linear diol or diamine compound having 2 to 10 carbon atoms is preferably used. Typical examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2,2′-dimethyl-1,3-propanediol. , Diethylene glycol, 1,5 pentamethylene glycol, 1,6-hexamethylene glycol, cyclohexane 1,4-diol, cyclohexane-1,4 diol, cyclohexane-1,4 dimethanol, or the like; ethylenediamine, 1, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1, - propanediamine, diethylenetriamine, triethylenetetramine, 3,3'-dichloro-amine compounds such as, and hydrazine, hydrazine such as acid hydrazide. In particular, 1,4-butanediol and trimethylolpropane are preferable.

  The polyurethane resin composition of the present invention can be not only a urethane elastomer but also an aqueous polyurethane resin or a water-based polyurethane resin. This polyurethane resin composition introduces at least one selected from the group consisting of an anionic group, a cationic group, and a nonionic group as a hydrophilic group in order to disperse in water. At this time, a chain extender having a hydrophilic group may be used for the polyester polyol produced using the catalyst, and a glycol and / or hydrophilic group containing a hydrophilic group as a raw material for the polyester polyol produced using the catalyst. A polyester polyol hydrophilized by partially using a dibasic acid containing a functional group can be produced and used, and a water-based or aqueous polyurethane resin composition can be obtained using a known technique.

  The production method includes, for example, (i) using a polyester polyol containing no hydrophilic group produced using a catalyst, and containing at least one hydroxyl group or amine group capable of reacting with an isocyanate group in one molecule. And a method for producing an aqueous or aqueous polyurethane resin using a compound containing one or more hydrophilic groups in one molecule selected from the group consisting of an anionic group, a cationic group, and a nonionic group,

(Ii) An anionic group, a cationic group, a nonionic group, a polyol containing a hydrophilic group represented by a neutralized salt thereof, and / or a polycarboxylic acid containing the hydrophilic group or an ester derivative thereof is essential. A method for producing a polyester polyol containing a hydrophilic group using a catalyst using a polyol and dicarboxylic acid as components and producing an aqueous or aqueous polyurethane resin using the polyester polyol can be employed.

  Preferred examples of the anionic group as the hydrophilic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. The cationic group is a tertiary amino group, part or all of which is an acidic compound. Preferred are those that are summed or quaternized with a quaternizing agent, and the nonionic group has a polyoxyalkylene structure. For example, polyethylene glycol and copolymers thereof are preferred.

  The anionic group and cationic group may be partially or wholly neutralized with various basic compounds or acidic compounds, or a tertiary amino group as a cationic group may be converted into a quaternizing agent. The quaternized product may be used.

  Examples of the polyester polyol containing an anionic group include a carboxyl group-containing polyester polyol and a sulfonic acid group-containing polyester polyol.

The polyurethane resin composition of the present invention can be used for various polyurethane production methods, for example, one-shot method, prepolymer method or quasi-prepolymer method, as well as bulk polymerization, solution polymerization, emulsion polymerization, emulsion polymerization, etc. it can. The production method may be a conventionally known method, such as a slab method, a double conveyor method, a hot cure method, a cold cure method, a RIM method, molding by an open mold, an integral molding with a composite material, an on-site construction method, a spray method, a casting method. Methods such as injection, coating, and impregnation can be used. In the production, 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. Moreover, a well-known urethanization catalyst, surfactant, another adjuvant, etc. can be used in the addition amount generally used when manufacturing a polyurethane resin.

  Furthermore, the polyurethane resin composition of the present invention may be added with an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a filler, a colorant, a reinforcing agent, a release agent, a flame retardant, etc., if necessary. Furthermore, other thermoplastic polyurethane elastomers and other general-purpose thermoplastic resins such as ABS resin, AS resin, vinyl chloride resin, polyamide and the like can be added within a range not impairing the effect of the urethane resin composition according to the present invention. . The composition of the present invention may contain various additives selected from surfactants, catalysts, stabilizers, and pigments.

  The polyurethane resin composition of the present invention can be used as a thermoplastic elastomer (TPU), a thermosetting elastomer (TSU), an aqueous polyurethane resin, or a radical curable urethane resin, and can be used as a molding material, an adhesive, an adhesive, a paint, and a foam. It can be used for polyurethane products in various fields such as sealing agents and photo-curing resins. Specific applications include three-dimensional molded products such as yarns, films, sheets, belts, hoses, rolls, tires, anti-vibration materials, packings, and shoe soles, as well as artificial leather, synthetic leather, soft / hard foams, and textile materials. It can be used in many fields such as industrial materials, electrical and electronic materials, optical materials, medical materials, and civil engineering materials.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, it is not limited to these. In addition, “part” and “%” in the sentence are based on mass.

Synthesis Example 1 (Synthesis of Lactone 16-Mole Addition-Modified Single-Terminal Silicone Polyol)
A 1-liter four-necked flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirring device has two primary hydroxyl groups at one end of the following structural formula (2) [n = 33 in the formula] Moreover, 500 g of organopolysiloxane having no reactive group at the other end (hydroxyl value: 41.1 mg KOH / g, acid value: 0.05 mg KOH / g), ε-caprolactone 335 g, tris-2-ethylhexanoic acid as a reaction catalyst 0.250 g of butyltin was charged and reacted at 100 ° C. for 13 hours while passing nitrogen. (The reaction end point was determined by appropriately measuring the nonvolatile content (NV), and the end point was determined when NV was 99.5% or more.)
After the reaction for 13 hours, NV reached 99.7%, and the lactone-modified one-end type silicone polyol (8 mol lactone adduct per primary hydroxyl group, also referred to as Lc / Si polyol) was taken out from the flask. The reaction product had a hydroxyl value of 24.4 mgKOH / g, an acid value of 0.55 mgKOH / g, and obtained a white solid at room temperature (25 ° C.) and a transparent liquid at 100 ° C. The molecular weight distribution by GPC measurement shows a normal distribution, and the proportion of unreacted primary hydroxyl groups of organopolysiloxane by ¹³ C-NMR measurement was 5% (that is, 95% of primary hydroxyl groups reacted with ε-caprolactone). ).

Synthesis Examples 2 and 3 and Comparative Synthesis Example 1
In the same manner as in Synthesis Example 1, lactone 12 mol, 20 mol, and 4 mol modified one-end silicone polyols were synthesized with the formulation shown in Table 1. These silicone polyols are 6 mol adduct, 10 mol adduct and 2 mol adduct per primary hydroxyl group. The properties of the obtained Lc / Si polyol are shown in Table 1.

The evaluation method is as follows.
<Nonvolatile content>
1 g of a sample was taken in a metal petri dish, 5 ml of toluene was added, and the remaining amount after drying at 107.5 ° C. for 1 hour was determined.
Nonvolatile content (%) = [(BC) / (AC)] × 100
However, A: Metal Petri dish + Mass of the sample before drying (g)
B: Mass of the metal petri dish + sample after drying (g)
C: Mass of metal petri dish

<Hydroxyl value>
An acetylating agent consisting of acetic anhydride and pyridine was added to the sample, and then acetylated at 115 ° C. for 1 hour. Next, water was added to decompose excess acetic anhydride into acetic acid, acetone and toluene were added, and then neutralization titration was performed using N / 2 potassium hydroxide ethyl alcohol solution.
Hydroxyl value (mgKOH / g) = [(BT) × F × 28.05 / S] + AN
However, B: Drop amount of N / 2 potassium hydroxide ethyl alcohol solution in the blank test (ml)
T: Drop amount of N / 2 potassium hydroxide ethyl alcohol solution in this test (ml)
F: titer of N / 2 potassium hydroxide ethyl alcohol solution S: sampling amount (g)
N: mol / liter AN: acid value of the sample

<Acid value>
The sample was dissolved by adding a neutral solvent (toluene / methanol), and then neutralized with a 0.1N potassium hydroxide ethyl alcohol solution.
Acid value (mgKOH / g) = V × F × 5.661 / S
V: Drop amount of 0.1N potassium hydroxide ethyl alcohol solution (ml)
F: Potency of 0.1N potassium hydroxide ethyl alcohol solution S: Sampling amount (g)
N: mol / liter

<Molecular weight deviation rate>
Calculated from the hydroxyl value and acid value of one-end diol type organopolysiloxane and the target molecular weight calculated from the molar ratio of ε-caprolactone / one-end diol type organopolysiloxane, and the hydroxyl value and acid value of the resulting resin. The divergence rate was determined from the experimental molecular weight determined by the above.
Molecular weight deviation rate (%) = [(target molecular weight−experimental molecular weight) / target molecular weight] × 100
However, molecular weight = (56100 × 2) / (hydroxyl value + acid value)

<Ratio of unreacted primary hydroxyl group (ratio of primary hydroxyl group of organopolysiloxane not reacted with lactone)>
A sample was dissolved in deuterated chloroform, and ¹³ C-NMR was measured by a conventional method. It was calculated from a peak appearing at 65.5 ppm (carbon adjacent to the primary hydroxyl group that did not react with lactone ) and a peak appearing at 62.0 ppm (carbon adjacent to the primary hydroxyl group reacted with lactone).
Unreacted primary hydroxyl group ratio (%) = [65.5 ppm peak area / (65.5 ppm peak area + 62.0 ppm peak area)] × 100

<Molecular weight distribution by GPC measurement>
The sample was dissolved in tetrahydrofuran (THF) (0.4% solution) and subjected to gel permeation chromatography analysis. The shape of the obtained chart was evaluated.
[Measurement conditions] Eluent: THF, Column: TSKgel, Flow rate: 1.0 ml / min
Column: TSKgel G5, 4, 3, 2, Detector: RI

(Compatibility test)
3 mass% of lactone-modified one-end type silicone polyol of Synthesis Example 1 and Comparative Synthesis Example 1 and organopolysiloxane having two unmodified primary hydroxyl groups at one end are added to various polyols at 70 ° C. × 4 It was left for days and observed and evaluated visually.

(Evaluation)
XX: Separation liquid 3 mm or more in the upper layer X: Separation liquid 1 mm or more and less than 3 mm in the upper layer ○: No separation

PTMG: Polytetramethylene glycol polyether polyol BG / AA polyester polyol: Polyester polyol BG / HG / AA polyester polyol of 1,4-butanediol and adipic acid: 1,4-butanediol and 1,6-hexanediol Polyester polyol with adipic acid 3MPD / AA polyester polyol: Polyester polyol with 3-methyl-1,5-pentanediol and adipic acid Polycaprolactone polyol: ε-caprolactone-added polyester polyol polycarbonate polyol with ethylene glycol as initiator Polycarbonate polyol consisting of 1,6-hexanediol and dimethyl carbonate Unmodified: Organopolysiloxane having two primary hydroxyl groups at one end Sun

Example 1 (Prepolymer method)
(Synthesis of urethane prepolymer)
483.0 g of 4,4′-diphenylmethane diisocyanate was placed in a 2 liter flask, 1000 g of ε-caprolactone-added polyester polyol (molecular weight 2000) using ethylene glycol as an initiator, and 16.7 g of the lactone-modified one-end silicone polyol of Synthesis Example 1 Were mixed and reacted at 70 ° C. for about 5 hours under a nitrogen atmosphere. A small amount of 4,4′-diphenylmethane diisocyanate or ε-caprolactone-added polyester polyol was added (adjusted) so that the NCO equivalent was 525 to obtain a silicone-containing urethane prepolymer.

(Creation of urethane elastomer)
400 g of silicone-containing urethane prepolymer adjusted to 80 ° C. and 32.6 g of a 70/30 (mass ratio) mixture of 1,4-butanediol / trimethylolpropane adjusted to 50 ° C. were poured into a centrifugal molding machine. After being molded and cured under conditions of 140 ° C. × 1 hour, secondary curing was performed under the conditions of 110 ° C. × 16 hours to obtain a 2 mm thick urethane elastomer sheet.

Example 2 (one-shot method)
(Preparation of polyol compound)
1000 g of ε-caprolactone-added polyester polyol (molecular weight 2000), 16.7 g of the lactone-modified one-end silicone polyol of Synthesis Example 1, and 122.1 g of a 70/30 (mass ratio) mixture of 1,4-butanediol / trimethylolpropane A polyol compound mixed in a 2 liter flask (70 ° C. × 10 minutes) was prepared.
(Creation 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 in a centrifugal molding machine and cured under conditions of 140 ° C. × 1 hour. Thereafter, secondary curing was performed under conditions of 110 ° C. × 16 hours to obtain a urethane elastomer sheet having a thickness of 2 mm.

Examples 3, 5, 7, 9, 11 (Prepolymer method)
(Synthesis of urethane prepolymer)
A urethane prepolymer having the composition shown in Table 3 was obtained in the same manner as in the prepolymer synthesis of Example 1.

・ＭＤＩ：４，４’−ジフェニルメタンジイソシアネート
（ウレタンエラストマーの作成）
実施例１のウレタンエラストマーと同様な操作で表４に示す配合の２ｍｍ厚のウレタンエラストマーシートを得た。評価結果は、表７−８に示す。

MDI: 4,4'-diphenylmethane diisocyanate (preparation of urethane elastomer)
A 2 mm thick urethane elastomer sheet having the composition shown in Table 4 was obtained in the same manner as the urethane elastomer of Example 1. The evaluation results are shown in Table 7-8.

Examples 4, 6, 8, 10, 12 (one-shot method)
(Preparation of polyol compound)
A polyol compound having the composition shown in Table 5 was obtained in the same manner as in the preparation of the polyol compound of Example 2.

(Creation of urethane elastomer)
A 2 mm-thick urethane elastomer sheet having the composition shown in Table 6 was obtained in the same manner as the urethane elastomer of Example 2. The evaluation results are shown in Table 7-8.

（評価結果）

(Evaluation results)

尚、評価法は以下のとおり。 尚、評価法は以下のとおり。

The evaluation method is as follows. The evaluation method is as follows.

<Sheet appearance ( bleed )>
The sheet state immediately after molding and one month after molding was evaluated by visual observation and finger touch.
○: No bleed .
Δ: Not visually recognized, but feels oily with finger touch.
X: Bleed clearly both visually and by touch (oil).

<Tensile strength, M100, M300, elongation>
A centrifugal molded sheet was punched with a No. 3 dumbbell and measured according to JIS K 7312.
Head speed: 500mm / min

<Tear strength>
A centrifugal molded sheet was punched with an angle-type dumbbell without cutting, and measured according to JIS K 7312.
Head speed: 500mm / min

<Static friction coefficient, Dynamic friction coefficient>
The centrifugal molded sheet was stored indoors for 2 weeks after the completion of the secondary curing. Then 10x20
The surface of the sheet was well washed several times with acetone on the day before measurement.
The measurement was performed by measuring the static friction coefficient and the dynamic friction coefficient of the centrifugally formed sheet with a surface testing machine.
Flat indenter (with clamp for fixing the sheet-shaped test piece): 30 × 30mm, 84g
Object to be measured: OA plain paper (attached to the clamp) / centrifugal forming sheet Weight: Only 84 g of flat indenter (no forced load)
Surface testing machine: Type-HEIDON-14 type (Shinto Scientific Co., Ltd.)

<Agglomeration of Si atoms>
The centrifugally formed sheet was stored indoors for 2 weeks after the completion of the secondary curing. Thereafter, the sheet surface was washed well with acetone for several days on the day before the measurement. The measurement was performed by performing atomic mapping by SEM on the sheet surface (air contact side during molding).
The part where the concentration of Si atoms is higher than the surroundings appears in a circle. Judgment was made based on the diameter of the high concentration site.
○: None or less than 1 μm in diameter Δ: Diameter 1 μm or more and less than 5 μm ×: Diameter 5 μm or more

Comparative Examples 1, 3, 5, 7, 9 (Prepolymer method)
(Synthesis of urethane prepolymer)
The urethane prepolymer having the composition shown in Table 9 was obtained in the same manner as in the prepolymer synthesis of Example 1.

・ＭＤＩ：４，４’−ジフェニルメタンジイソシアネート

MDI: 4,4′-diphenylmethane diisocyanate

(Creation of urethane elastomer)
A 2 mm thick urethane elastomer sheet having the composition shown in Table 10 was obtained in the same manner as the urethane elastomer of Example 1. The evaluation results are shown in Table 13-14.

Comparative Examples 2, 4, 6, 8, 10 (one-shot method)
(Preparation of polyol compound)
A polyol compound having the composition shown in Table 11 was obtained in the same manner as the preparation of the polyol compound of Example 2.

（ウレタンエラストマーの作成）
実施例２のウレタンエラストマーと同様な操作で表１２に示す配合の２ｍｍ厚のウレタンエラストマーシートを得た。評価結果は表１３−１４に示す。

(Creation of urethane elastomer)
A 2 mm thick urethane elastomer sheet having the composition shown in Table 12 was obtained in the same manner as the urethane elastomer of Example 2. The evaluation results are shown in Table 13-14.

・ＭＤＩ：４，４’−ジフェニルメタンジイソシアネート
（評価結果）

MDI: 4,4'-diphenylmethane diisocyanate (evaluation result)

ＨＥＩＤＯＮ：表面試験機ＨＥＩＤＯＮ：表面試験機

HEIDON: Surface testing machine HEIDON: Surface testing machine

Since Comparative Examples 1 and 2 do not contain a silicone component, the frictional resistance is large and low frictional properties cannot be obtained. In Comparative Examples 3 and 4, since the silicone polyol is not in the proper range, bleeding is observed in the sheet, and a circular portion having a high Si atom concentration compared to the periphery is observed on the sheet surface. In particular, when used in printer rolls, cleaning blades, etc., it is not preferable that the photoreceptor or printed matter is contaminated by bleeding, or if the Si atom concentration is not uniform, the roll and cleaning blade cause chipping (a phenomenon of chipping).
In Comparative Examples 5 to 10, unmodified silicone was used, which is not preferable for the same reason as in Comparative Example 3-4. In particular, one-shot molding is not practical.

Since the polyurethane resin composition of the present invention is a polyurethane cured product excellent in performance such as bleed resistance, Si atom aggregation, various physical properties, and low friction, it can be produced by a one-shot molding method and a prepolymer molding method. Three-dimensional molded products such as yarns, films, sheets, belts, hoses, rolls, tires, anti-vibration materials, packings, and shoe soles, as well as artificial leather, synthetic leather, soft / hard foams, textile materials, industrial materials, and electrical machinery It can be used in many fields such as electronic materials, optical materials, medical materials, and civil engineering materials.

Claims (7)

In the polyurethane resin composition containing (A) polyisocyanate and (B) polyol, the polyol (B) has two primary hydroxyl groups at one end and a reactive group at the other end. no organo lactone monomer to the hydroxyl groups of the polysiloxane each 5-10 mole ring-opening addition polymerized lactone-modified one-terminal type silicone polyol (B1) 0.01 to 5 wt% and other polyols (B2) 95 to 99.99 A polyurethane resin composition comprising:% by mass. The polyurethane resin composition according to claim 1, wherein the other polyol (B2) is one or more selected from polyether polyol and polyester polyol. The polyurethane resin composition according to claim 1, wherein the molecular weight of (B2) is 600 to 3000. The polyurethane resin composition according to claim 1, wherein the molecular weight of (B1) is 2500 to 6000. The polyurethane resin composition according to claim 1, wherein the lactone monomer is ε-caprolactone. The polyurethane resin composition according to claim 1, wherein the lactone-modified one-end type silicone polyol (B1) is obtained by adding 8 mol of a lactone monomer per one primary hydroxyl group of an organopolysiloxane. A molded product obtained from the polyurethane resin composition according to any one of claims 1 to 6.