JP2007231071A - Alkyl (meth)acrylate-grafted polyether, its production method, polyether composition, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent polyether which is useful as a raw material for a cured polyurethane resin excellent in weathering resistance and bleeding resistance and scarcely undergoing a change with time such as thickening even when mixed with a compound having a hydroxyl-reactive functional group and to provide a polyether polyol composition containing the polyether. <P>SOLUTION: The polyether is an alkyl ester-grafted polyether wherein OH-blocked terminals account for not less than 70 mol% of its entire terminal groups, and hydroxyl groups account for less than 30 mol% of its entire terminal groups and is obtained by, for example, blocking not less than 70 mol% of the entire hydroxyl groups of an alkyl (meth)acrylate grafted-polyether polyol with a blocking agent, and leaving less than 30 mol% of them unblocked with hydroxyl groups. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a (meth) acrylic acid alkyl ester graft polyether, a method for producing the same, and a polyether composition, and further relates to a plasticizer and a resin composition containing the polyether. More specifically, a graft polyether obtained by sealing a part or all of the hydroxyl groups of a graft polyether polyol obtained by grafting (meth) acrylic acid alkyl ester to a polyoxyalkylene polyol, and the graft polyether are contained. It relates to a polyether composition. Furthermore, the present invention relates to a plasticizer containing the graft polyether and a resin composition containing the plasticizer.

  Polyether polyols are widely used as raw materials for polyurethane resins. In addition, this polyether polyol is liquid at room temperature, remains liquid even at low temperatures, has a viscosity that is easy to handle, and has good compatibility with resins such as polyurethane, and solvents such as water and organic solvents. It has been used as a plasticizer, lubricant, solvent and surfactant. In particular, in the field of plasticizers, this polyether polyol is a high molecular weight plasticizer as a plasticizer that replaces the low molecular weight plasticizers that have been pointed out as problems such as bleed out from resins and paint contamination and the possibility of environmental pollution. (For example, Patent Document 1 (Japanese Patent Laid-Open No. 55-31874)).

  However, since this polyether polyol has a hydroxyl group at the ether chain end, it is a plasticizer of a compound having a group capable of reacting with a hydroxyl group such as an isocyanate group, an alkoxysilyl group, a disulfide group, an epoxy group, a carboxylic acid group, or an ester group. When used as a solvent, when these are mixed and stored, there is a problem that thickening or gelation occurs and storage stability is lowered.

  In order to solve such problems, various polyether high molecular weight plasticizers in which the hydroxyl group at the end of the ether chain is inactivated have been proposed. For example, those obtained by reacting a hydroxyl group at the end of the ether chain with an isocyanate group and urethanized (for example, Patent Document 2 (Japanese Patent Laid-Open No. 2001-64505)) and those obtained by reacting with a carboxylic acid (for example, Patent Document 2) 3 (Japanese Patent Laid-Open No. 2003-119280), etherified by reacting with an alkyl halide by the Williamson etherification method or adding an olefin (for example, Japanese Patent Laid-Open No. 2000-345137). )).

  However, polyether-based high molecular weight plasticizers in which the terminal hydroxyl group is urethanated have a problem that viscosity increases because hydrogen bonds are formed. In addition, in a polyether high molecular weight plasticizer in which a terminal hydroxyl group is esterified, a transesterification reaction may occur when a compound having a hydroxyl group or a carboxylic acid group is mixed, and a hydrolysis reaction may occur when water is mixed. When these reactions occur, there is a problem that the viscosity, the curing characteristics of the resin, the physical properties of the resin, and the like change over time. Furthermore, when a composition added with a polyether high molecular weight plasticizer in which a terminal hydroxyl group is esterified or a cured product thereof absorbs moisture, a hydrolysis reaction occurs, and physical properties such as viscosity, curing characteristics, and cured product characteristics of the composition change. There was a problem. Polyether type high molecular weight plasticizers with etherified terminal hydroxyl groups have a problem that a large amount of alkali metal catalyst is used in Williamson synthesis and that alkyl halides are relatively expensive. However, since ethylene and propylene are gases, handling is complicated, terminal inactivation efficiency is poor, and there is a problem that polyolefin is by-produced and mixed during the olefin addition reaction.

In addition, an acrylic resin is often added to the polyurethane resin composition in order to increase its weather resistance. However, the acrylic resin has a low compatibility with a polyurethane resin, particularly a polyurethane resin using a polyether polyol, and there is a problem that the acrylic resin tends to bleed out.
JP 55-31874 A JP 2001-64505 A JP 2003-119280 A JP 2000-345137 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is useful as a raw material for a polyurethane resin cured product having excellent weather resistance and bleed resistance, and is an isocyanate group or an alkoxysilyl group. Even when mixed with a compound having a functional group capable of reacting with a hydroxyl group, such as thickening, a transparent polyether and a polyether composition containing this polyether, It aims at providing the manufacturing method of the said polyether. In particular, an object of the present invention is to provide a plasticizer containing the polyether, which is useful as a high molecular weight plasticizer in a resin composition such as polyurethane.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has a graft polyether obtained by inactivating the hydroxyl group of a polyether polyol grafted with a (meth) acrylic acid alkyl ester, and has good compatibility with a polyurethane resin. As a result, the cured polyurethane resin containing the graft polyether is excellent in weather resistance and bleed resistance. Further, even when the graft polyether is mixed with a compound having a functional group capable of reacting with a hydroxyl group, As a result, it was found that thickening and gelation hardly occur in the present invention, and the present invention has been completed.

  That is, the (meth) acrylic acid alkyl ester graft polyether according to the present invention has 70 mol% of terminal groups in which hydroxyl groups are sealed with a sealing agent among all terminals of the (meth) acrylic acid alkyl ester graft polyether. As described above, the hydroxyl group is less than 30 mol%.

  The (meth) acrylic acid alkyl ester graft polyether is composed of 70 mol% or more of hydroxyl groups sealed with a sealing agent among all hydroxyl groups of the (meth) acrylic acid alkyl ester graft polyether polyol, and less than 30 mol%. It is preferable that the hydroxyl groups remain without being sealed.

  The (meth) acrylic acid alkyl ester graft polyether polyol is a hydroxyl group-containing (meth) acrylate graft polyether polyol having an ester group represented by the following formula (1) in the molecule and / or the following formula in the molecule: A (meth) acrylate graft polyether polyol having an ester group represented by (3) is preferred.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 18 carbon atoms.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
The (meth) acrylic acid alkyl ester graft polyether polyol is preferably a polyol obtained by reacting a polyoxyalkylene polyol with a vinyl monomer containing at least a (meth) acrylic acid alkyl ester.

  The (meth) acrylic acid alkyl ester is preferably a hydroxyl group-containing (meth) acrylate represented by the following formula (2) and / or a (meth) acrylate represented by the following formula (4).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 18 carbon atoms.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
The hydroxyl group is preferably sealed through at least one bond selected from an ester bond, an ether bond and a urethane bond.

The sealing agent is preferably at least one compound selected from monocarboxylic acid, monocarboxylic acid anhydride, and monocarboxylic acid halide.
The (meth) acrylic acid alkyl ester grafted polyether preferably has a light transmittance measured by a spectrophotometer of 30% or less at a light wavelength of 300 nm and 90% or more at a light wavelength of 500 nm.

  The polyether composition according to the present invention is a polyether composition containing the above (meth) acrylic acid alkyl ester graft polyether, and is a terminal group in which hydroxyl groups are sealed among all terminals in the composition. Is 70 mol% or more, and the hydroxyl group is less than 30 mol%.

The plasticizer which concerns on this invention contains the said (meth) acrylic-acid alkylester graft polyether.
The resin composition according to the present invention is a two-component curable polyurethane resin composition containing the plasticizer as a main agent and / or a curing agent, or a one-component curable polyurethane resin composition containing the plasticizer. It is characterized by.

  The method for producing the (meth) acrylic acid alkyl ester graft polyether comprises reacting a hydroxyl group with a sealing agent and sealing the hydroxyl group through at least one bond selected from an ester bond, an ether bond and a urethane bond. It is characterized by doing.

  The sealing agent is preferably at least one compound selected from monocarboxylic acid, monocarboxylic acid anhydride, and monocarboxylic acid halide.

  According to the present invention, by deactivating the terminal hydroxyl group of the (meth) acrylic acid alkyl ester graft polyether polyol, it is useful as a raw material for a polyurethane resin cured product having excellent weather resistance and bleed resistance. And a polyether composition containing the graft polyether which is less likely to change with time such as thickening even when mixed with a compound having a functional group capable of reacting with a hydroxyl group such as an alkoxysilyl group. In particular, a plasticizer containing the graft polyether useful as a high molecular weight plasticizer in a resin composition such as polyurethane can be obtained.

[Graft polyether]
The (meth) acrylic acid alkyl ester graft polyether according to the present invention (hereinafter, also referred to as “graft polyether”) has 70 mol% or more of terminal groups having hydroxyl groups sealed with a sealing agent among all terminals. And the hydroxyl group is less than 30 mol%. Such a graft polyether seals 70 mol% or more of hydroxyl groups with a sealing agent among all hydroxyl groups of (meth) acrylic acid alkyl ester graft polyether polyol, and does not seal less than 30 mol% of hydroxyl groups. It is obtained by remaining in

<Graft polyether polyol>
The (meth) acrylic acid alkyl ester graft polyether polyol (hereinafter also referred to as “graft polyether polyol”) used in the present invention contains a hydroxyl group having an ester group represented by the above formula (1) in the molecule ( It is preferably a (meth) acrylate graft polyether polyol and / or a (meth) acrylate graft polyether polyol having an ester group represented by the above formula (3) in the molecule.

  Such a graft polyether polyol includes, for example, a polyoxyalkylene polyol and at least a hydroxyl group-containing (meth) acrylate represented by the above formula (2) and / or a (meth) acrylate represented by the above formula (4). It can be obtained by graft reaction with the vinyl monomer contained. The graft reaction preferably uses an alkyl peroxide as a radical reaction initiator.

  The ester group represented by the above formula (1) is usually a group derived from a hydroxyl group-containing (meth) acrylate represented by the above formula (2). It preferably has a structure grafted to the alkylene group of the oxyalkylene polyol.

  The ester group represented by the above formula (3) is usually a group derived from a (meth) acrylate represented by the above formula (4), and the graft polyether polyol has a polyoxyalkylene ester group. It preferably has a structure grafted to the alkylene group of the polyol.

(Polyoxyalkylene polyol)
The polyoxyalkylene polyol used in the present invention can be produced by a conventionally known method, for example, an alkali metal catalyst such as potassium hydroxide or cesium hydroxide, a composite metal catalyst which is a cyano complex of zinc and cobalt, or It can be produced by subjecting a hydroxyl group-containing compound to ring-opening polymerization of an alkylene oxide in the presence of a known catalyst such as a phosphazenium catalyst such as phosphazene or phosphazenium having a nitrogen-phosphorus double bond. In the present invention, it is preferable to remove the used catalyst after completion of the ring-opening polymerization.

  The hydroxyl group-containing compound is not particularly limited as long as it is a hydroxyl group-containing compound usually used in the production of polyoxyalkylene polyols. For example, alkylene glycol such as ethylene glycol and propylene glycol; triol such as glycerol and trimethylolpropane; pentaerythritol And tetraols such as diglycerin; hexaols such as sorbitol; and sucrose. These may be used alone or in combination of two.

  Examples of the alkylene oxide include ethylene oxide and propylene oxide. These may be used alone or in combination of two. Among these, it is preferable to use propylene oxide alone or in combination of ethylene oxide and propylene oxide. That is, the polyoxyalkylene polyol preferably contains at least an oxypropylene unit.

The hydroxyl value of the polyoxyalkylene polyol is preferably 1 to 224 mgKOH
/ G, more preferably 2 to 112 mgKOH / g, most preferably 5 to 56 mgKOH / g. When the hydroxyl value of the polyoxyalkylene polyol is in the above range, a graft polyether having excellent weather resistance and bleed resistance can be obtained.

  The number average molecular weight of the polyoxyalkylene polyol is preferably 500 to 100,000, more preferably 1000 to 50000, and most preferably 2000 to 20000. When the number average molecular weight of the polyoxyalkylene polyol is in the above range, a graft polyether having excellent weather resistance and bleed resistance can be obtained. The hydroxyl value and number average molecular weight of the polyoxyalkylene polyol can be adjusted by controlling the degree of ring-opening polymerization of the alkylene oxide.

  In the present invention, the polyoxyalkylene polyol is usually 40 to 95 parts by weight, preferably 50 to 90 parts by weight, more preferably 60 to 85 parts by weight with respect to 100 parts by weight of the total of the polyoxyalkylene polyol and the vinyl monomer. It is desirable to use it. When the amount of the polyoxyalkylene polyol is in the above range, a graft polyether is obtained that is useful as a raw material for a polyurethane resin cured product having more excellent weather resistance and bleed resistance, and excellent in transparency and compatibility. be able to.

(Vinyl monomer)
The vinyl monomer used in the present invention contains at least a (meth) acrylic acid alkyl ester. Among them, it is preferable to contain a hydroxyl group-containing (meth) acrylate represented by the above formula (2) and / or a (meth) acrylate represented by the above formula (4). This alkyl (meth) acrylate is preferably contained in an amount of 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more based on 100% by weight of the total vinyl monomers. By grafting a vinyl monomer containing the above (meth) acrylic acid alkyl ester in the above range, a graft polyether excellent in transparency and compatibility can be obtained, and a cured polyurethane resin using this graft polyether is excellent. Excellent weather resistance and bleed resistance.

In the above formulas (2) and (4), R ¹ is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of weather resistance and handling properties. R ² is an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, and particularly preferably an alkyl group having 4 to 18 carbon atoms. R ³ is an alkylene group having 1 to 18 carbon atoms, preferably an alkylene group having 2 to 18 carbon atoms.

  Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, cyclohexyl group, dicyclopentanyl group, isobornyl group, lauryl group, tridecyl group and stearyl group. Can be mentioned. Of these, a butyl group and a 2-ethylhexyl group are preferable.

Examples of the aralkyl group having 7 to 18 carbon atoms include a phenylene group and a benzyl group.
Examples of the alkylene group having 1 to 18 carbon atoms include a methylene group, an ethylene group, a 1-methylethylene group, a propylene group, and a butylene group. Among these, an ethylene group and a propylene group are preferable.

  Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and the like. It is done. These (meth) acrylic acid alkyl esters improve the weather resistance as the carbon number of the alkyl group increases.

  Examples of other vinyl monomers that may be used in combination with the (meth) acrylic acid alkyl ester include vinyl esters such as acrylonitrile, styrene, acrylamide, and vinyl acetate, and vinyl ethers such as ethyl vinyl ether. These other vinyl monomers may be used alone or in combination of two or more.

  In the present invention, the vinyl monomer containing the (meth) acrylic acid alkyl ester is usually 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polyol and the vinyl monomer. It is desirable to use parts by weight, more preferably 15 to 40 parts by weight. When the amount of the vinyl monomer used is within the above range, it is useful as a raw material for a polyurethane resin cured product having more excellent weather resistance and bleed resistance, and obtains a graft polyether having excellent transparency and compatibility. Can do.

In the present invention, it is preferable to use an alkyl peroxide as a radical reaction initiator when performing the graft reaction. Examples of the alkyl peroxide used in the present invention include di-tert-butyl peroxide, di-tert-hexyl peroxide, α, α′-bis (te
tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, dialkyl peroxides such as tert-butylcumyl peroxide; tert-butyl Peroxyneodecanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxybenzoate, tert-butylperoxyacetate Peroxyesters such as 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylper And peroxyketals such as oxycyclohexyl) propane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, and the like.

  These alkyl peroxides may be used alone or in combination of two or more. In the present invention, the alkyl peroxide is usually preferably used in an amount of 0.1 to 5 mol per mol of the hydroxyl group of the polyoxyalkylene polyol. When the amount of the alkyl peroxide used is within the above range, the graft reaction of the polyoxyalkylene polyol and the vinyl monomer can be suitably performed.

(Graft reaction)
When carrying out the grafting reaction, it is preferable to add a vinyl monomer to the polyoxyalkylene polyol for reaction. The reaction temperature is preferably 100 to 200 ° C, more preferably 110 to 180 ° C, and most preferably 120 to 160 ° C.

  The addition method of the vinyl monomer may be either a batch addition method or a sequential addition method. However, in the case of the batch addition, the temperature may be rapidly increased by the heat of reaction, so that the addition is preferably performed sequentially. The addition time (dropping time) of the vinyl monomer is preferably 5 to 600 minutes, more preferably 60 to 450 minutes, and most preferably 120 to 300 minutes. When the vinyl monomer is dropped over a time in the above range, a rapid temperature increase due to reaction heat can be prevented, and the graft reaction can be performed stably. The vinyl monomer is preferably mixed with a part of the polyoxyalkylene polyol in advance and then added to the remaining polyoxyalkylene polyol. Thus, the graft reaction can be stably performed by adding the vinyl monomer.

  In the present invention, after a predetermined amount of vinyl monomer is added to the polyoxyalkylene polyol, the graft reaction is matured while maintaining the above reaction temperature. The reaction time at this time is preferably 5 to 600 minutes, more preferably 60 to 450 minutes, and most preferably 120 to 300 minutes. Thereafter, the graft polyether polyol can be obtained by removing unreacted monomers by a reduced pressure treatment or the like.

(Hydroxyl sealing)
In the graft polyether of the present invention, 70 mol% or more of the hydroxyl groups of the graft polyether polyol are sealed with a sealing agent (hereinafter, this group is also referred to as “end-capping group”). It is obtained by leaving less than 30 mol% of hydroxyl groups without sealing. Hereinafter, the ratio in which the hydroxyl groups are sealed is referred to as a terminal blocking ratio, and the ratio of the remaining hydroxyl groups is referred to as a hydroxyl group remaining ratio. The terminal blocking rate and the hydroxyl group remaining rate are determined by measuring the hydroxyl value of the graft polyether polyol before hydroxyl group sealing and the hydroxyl value of the graft polyether after sealing according to the method described in JIS K-1557. It can be calculated.

  As described above, the end-capping rate and the hydroxyl group residual rate of the graft polyether of the present invention are 70 mol% or more and less than 30 mol%, respectively, but a compound having a functional group capable of reacting with a hydroxyl group such as an isocyanate group. From the viewpoint of being able to more effectively suppress thickening and gelation when mixed with, and excellent in storage stability, the terminal blocking rate is preferably 75 mol% or more and the hydroxyl group residual rate is less than 25 mol%, More preferably, the terminal blocking ratio is 80 mol% or more and the hydroxyl group remaining ratio is less than 20 mol%. In addition, the upper limit of the terminal blocking rate is 100 mol%, and the lower limit of the hydroxyl group remaining rate is 0 mol%.

  In the graft polyether of the present invention, the hydroxyl group of the graft polyether polyol is reacted with a sealing agent, and the hydroxyl group is sealed through at least one bond selected from an ester bond, an ether bond and a urethane bond. Is preferred. Among the above bonds, it is preferable to seal via an ester bond. In the case of sealing via an ester bond, examples of the sealing agent used include monocarboxylic acid, monocarboxylic acid anhydride, and monocarboxylic acid halide. The sealant may be used alone or in combination of two or more.

Examples of the monocarboxylic acid include methanoic acid (= formic acid), ethanoic acid (= acetic acid), propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and pentanoic acid.
The monocarboxylic acid anhydride is a monocarboxylic acid bimolecular acid anhydride, and examples thereof include acetic anhydride, propanoic anhydride, and butanoic anhydride.

Examples of monocarboxylic acid halides include chlorides, bromides, and iodides of monocarboxylic acids such as chloroacetic acid and bromoacetic acid.
Among these sealants, acetic acid and acetic anhydride are preferable from the viewpoint of economy.

  The amount of the sealing agent used is preferably 1.0 to 2.0 mol, more preferably 1.1 to 1.9 mol, particularly preferably 1.3 to 1 mol of the hydroxyl group of the graft polyether polyol. -1.8 mol. When the amount of the sealing agent used is in the above range, the end-capping reaction (hydroxyl deactivation) can be carried out efficiently, and the residual carboxylic acid can be easily removed.

  The reaction temperature between the graft polyether polyol and the sealant is preferably 40 to 180 ° C, more preferably 70 to 160 ° C, and particularly preferably 100 to 140 ° C. When the reaction temperature is within the above range, the end-capping reaction can be carried out efficiently, and damage to the polyether can be suppressed.

  The graft polyether according to the present invention preferably has a light transmittance at a light wavelength of 300 nm measured by a spectrophotometer of 30% or less, more preferably 25% or less, and particularly preferably 20% or less. The light transmittance at a light wavelength of 500 nm is preferably 90% or more, more preferably 93% or more. A graft polyether having a light transmittance in the above range at a light wavelength of 300 nm has a sufficient amount of graft chains and is excellent in compatibility with an acrylic resin. Further, the graft polyether having a light transmittance at a light wavelength of 500 nm in the above range is excellent in transparency in the visible light region. The graft polyether polyol has a transparency of transmitted light turbidity of usually 50 degrees (kaolin) or less, preferably 40 degrees (kaolin) or less, more preferably 25 degrees (kaolin) or less. Yes.

[Polyether composition]
The polyether composition according to the present invention is a polyether composition containing the above graft polyether, and out of all the terminals in the polyol composition, the terminal groups with hydroxyl groups sealed are 70 mol% or more. A polyol composition having a hydroxyl group of less than 30 mol%.

  The ratio of the terminal blocking group and the ratio of the hydroxyl group to all the terminals are the ratio of the hydroxyl group sealed with a sealing agent among the hydroxyl groups of the raw material polyoxyalkylene polyol, as in the case of the graft polyether ( Hereinafter, it is also referred to as “terminal blocking rate”) and the ratio of the remaining hydroxyl group (hereinafter also referred to as “hydroxyl residual rate”), and the hydroxyl value of the polyoxyalkylene polyol before sealing and the poly value after sealing. The hydroxyl value of the ether composition is measured according to the method described in JIS K-1557, and can be calculated by the following formula.

  As described above, the polyether composition has a terminal blocking rate and a hydroxyl group residual rate of 70 mol% or more and less than 30 mol%, respectively, but a compound having a functional group capable of reacting with a hydroxyl group such as an isocyanate group. From the viewpoint of being able to more effectively suppress thickening and gelation when mixed with, and excellent in storage stability, the terminal blocking rate is preferably 75 mol% or more and the hydroxyl group residual rate is less than 25 mol%, More preferably, the terminal blocking ratio is 80 mol% or more and the hydroxyl group remaining ratio is less than 20 mol%. In addition, the upper limit of the terminal blocking rate is 100 mol%, and the lower limit of the hydroxyl group remaining rate is 0 mol%.

  If the polyether composition has an end-capping rate and a hydroxyl group residual rate in the above ranges, only a graft polyether in which a part of the end hydroxyl groups of the graft polyether polyol is sealed with a sealant is used. It may be constituted, or may be a mixture of a graft polyether and a graft polyether polyol in which a part or all of the terminal hydroxyl groups of the graft polyether polyol are sealed with a sealant. The graft polyether polyol contained in this mixture may be one in which the graft polyether polyol used in the preparation of the graft polyether remains in an unreacted state or may be newly added to the prepared graft polyether. .

  The content of the graft polyether contained in the mixture is preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more, and most preferably 80% by weight based on the entire polyether composition. % By weight or more. A polyether composition in which the content of the graft polyether is within the above range is excellent in storage stability.

  The number average molecular weight of the graft polyether polyol contained in the mixture is preferably 1000 to 30000, more preferably 5000 to 20000, and most preferably 8000 to 15000. The number average molecular weight of the graft polyether polyol is a standard polyethylene glycol and standard polypropylene glycol conversion value measured by gel permeation chromatography (GPC, column: TSKgel G1000H + G2000H + G3000H + GuardColumn). The content of this graft polyether polyol is preferably less than 50% by weight, more preferably less than 40% by weight, particularly preferably less than 30% by weight and most preferably less than 20% by weight, based on the total polyether composition. is there.

  In the polyether composition according to the present invention, the content of a low molecular weight compound having a number average molecular weight of less than 1000 as measured by GPC is preferably 30% by weight or less. If the polyether composition contains a large amount of a low molecular weight compound, bleeding of the low molecular weight compound may occur in a cured product using the composition.

  Furthermore, the polyether composition according to the present invention includes chlorinated paraffin, epoxy soybean oil, acrylic plasticizer, phthalic acid esters such as dioctyl terephthalate, known low molecular weight plasticizers such as dioctyl adipate, water and alcohols. A solvent such as ethers can be contained.

  Such a polyether composition is useful as a raw material for a cured polyurethane resin excellent in weather resistance and bleed resistance, and is thickened even when mixed with a compound having a functional group capable of reacting with a hydroxyl group. Such a polyurethane resin composition containing a high molecular weight plasticizer, a polyol and a polyisocyanate is cured in a cured product obtained by curing the polyurethane resin composition. It is excellent in that the bleeding of the plasticizer hardly occurs.

[Plasticizer]
The graft polyether of the present invention is excellent in compatibility with a resin, reduced viscosity, etc., and can be suitably used as a plasticizer. Since this graft polyether is obtained by grafting acrylic onto a graft polyether polyol, it has very little bleeding and can be used as a plasticizer without substantial bleeding. In addition, this graft polyether does not act as an environmental hormone and is safe to use in large quantities. Furthermore, since it is grafted with acrylic, it can be used as a plasticizer having excellent weather resistance.

  The graft polyether according to the present invention can be used as a plasticizer for various resins. Particularly, since it is excellent in compatibility with a polyurethane resin, it can be suitably used as a plasticizer for a polyurethane resin.

  Since the plasticizer according to the present invention has few bleeds and is excellent in weather resistance, it can be suitably used, for example, for urethane resins for building materials such as sealing agents. Moreover, this plasticizer can be used for both one-component and two-component curable urethane resin compositions. At this time, the addition amount of the plasticizer is usually 0.5 to 50% by weight, preferably 1 to 30% by weight, particularly preferably 5 to 10% by weight, based on the total amount of the urethane resin composition.

  In order to reduce bleed, the graft polyether of the present invention preferably has a number average molecular weight (Mn) of 3000 or more. Further, a graft polyether having an Mn of 15000 or less is desirable in terms of ensuring better workability.

[Polyurethane resin composition]
The graft polyether according to the present invention can be used by being added as a plasticizer to a conventionally known one-component or two-component curable polyurethane resin composition. When the graft polyether is used as a plasticizer for a two-component curable polyurethane resin composition, it may be added to the main agent or to the curing agent.

  The cured product of such a polyurethane resin composition has excellent weather resistance and bleed resistance, and is suitably used as a sealing agent, a waterproofing agent, an adhesive, a paint, a molding material, and the like. In addition, since the graft polyether is sealed at its end, even if the polyurethane resin composition contains a compound having a functional group capable of reacting with a hydroxyl group, it does not easily change over time such as thickening, and is stable in storage. Excellent in properties.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. First, the evaluation method will be described.

(Hydroxyl value)
It was measured in accordance with 6.4 “hydroxyl value” of JIS K1557 “Polyurethane Polyether Test Method”.

(Acid value)
It was measured according to Section 6.6 “Acid Value” of JIS K1557 “Polyurethane Polyether Test Method”.
(viscosity)
It was measured according to Section 6.3 “Viscosity” of JIS K1557.

(Polymer content in graft polyether polyol)
The polymer content in the (meth) acrylate graft polyether polyol is defined as the polymer amount derived from the vinyl monomer when the polyoxyalkylene polyol and the vinyl monomer are reacted, and gas chromatography is used under the following conditions. The amount of unreacted vinyl monomer was analyzed and calculated from the amount of vinyl monomer charged.
-Gas chromatography: Shimadzu GC-14A
Carrier gas: helium, 30 ml / min
Column: G-300 manufactured by Chemicals Inspection Association, inner diameter 1.2 mm, length 40 m, film thickness 1.0 μm Column temperature condition: held at 90 ° C. for 6 minutes, and then heated at 20 ° C./min. Hold at 200 ° C. for 8 minutes.

(appearance)
It observed visually at room temperature (20-25 degreeC).
(Light transmittance)
Using a UV-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), the spectral light transmittance was measured under the following conditions. The results showed transmittances with light wavelengths of 300 nm and 500 nm. The light transmittance at a wavelength of 300 nm in the ultraviolet region is attributed to the structure of the graft polyol, and the light transmittance at a wavelength of 500 nm in the visible light region is an index reflecting the visual transparency.
・ Measurement method: Transmission method ・ Measurement mode: Wavelength measurement ・ Data mode: Transmittance (0 to 100%)
・ Measurement standard: 300 nm / min
・ Slit: 6.00 nm (fixed)
・ Sampling interval: 1.00 nm
Detector: Integrating sphere / photomultiplier tube Cell: Quartz cell with a thickness of 10 mm in the optical path Reference: Hexane Measurement wavelength range: 900-200 nm
Baseline correction: After correcting the baseline in a state where hexane was put in the cell on the reference side and the sample side, the measurement sample was put in the cell on the sample side, and the light transmittance was measured.

(amount of water)
It measured according to JIS K0068-2001.
(Storage stability)
After preparing the polyurethane composition, the viscosity change rate VX _n % at a storage temperature of 50 ° C. was measured according to the storage stability test described in 7.4 of JIS K6833-1994, and the viscosity after preparation was set to V ₀ (mPa · S), the viscosity of the stored n-th day as _{V n (mPa · S),} VX n = (V n -V 0
) / V ₀ × 100.

(Bleedability)
The polyurethane resin composition was molded into a block shape of 40 mm × 40 mm × 10 mm and allowed to stand at room temperature for 7 days. Thereafter, this block was placed on a half paper, and left in a dryer at 60 ° C. for 3 days, then the state of the half paper was visually observed and evaluated according to the following criteria.
A: No evidence of plasticizer elution (no change).
B: Slight elution of the plasticizer was observed.
C: A trace of plasticizer elution was clearly observed.
D: The half paper was wet with a plasticizer.

(Weatherability)
The polyurethane resin composition was molded into a 40 mm × 40 mm × 2 mm sheet and left at room temperature for 7 days. Thereafter, the sheet was allowed to stand at 63 ° C. for 18 hours or 100 hours with no rain using a Fedometer (manufactured by Suga Test Instruments: Model FAL-5H-B), and the change in the shape of the sheet was observed and evaluated according to the following criteria. In addition, in order to accelerate | stimulate a test, when adjusting a polyurethane resin composition, it implemented without mix | blending an anti-aging agent.
A: No change in shape B: Partial melting C: Melting

[Preparation Example 1]
(Production of polyoxyalkylene polyol (1))
Dipropylene glycol and 6 mol% of potassium hydroxide with respect to the hydroxyl group of the dipropylene glycol were charged into the autoclave, and the pressure in the autoclave was reduced. To this, propylene oxide was sequentially charged such that the internal pressure of the autoclave did not exceed 0.4 MPaG, and the temperature was raised to 110 ° C. to carry out addition polymerization of propylene oxide to dipropylene glycol. The obtained crude polyol was neutralized with phosphoric acid and filtered to obtain a polyoxyalkylene polyol (1). This polyoxyalkylene polyol (1) is a polyoxypropylene polyol, the number of functional groups is 2, the hydroxyl value is 37.4 mgKOH / g, the viscosity is 600 mPa · s / 25 ° C., measured by GPC (column: TSKgel G1000H + G2000H + G3000H + GuardColumn). The number average molecular weight was 3000 in terms of standard polypropylene glycol.

[Preparation Example 2]
(Production of polyoxyalkylene polyol (2))
0.18 mol% phosphazenium hydroxide with respect to glycerin and the hydroxyl group of this glycerin was charged into the autoclave, and the inside of the autoclave was depressurized. To this, propylene oxide was sequentially charged such that the internal pressure of the autoclave did not exceed 0.4 MPaG, and the temperature was raised to 95 ° C. to carry out addition polymerization of propylene oxide on glycerin. The obtained crude polyol was subjected to an adsorption treatment with an alumina silicate adsorbent and filtered to obtain a polyoxyalkylene polyol (2). This polyoxyalkylene polyol (2) is a polyoxypropylene polyol, the number of functional groups is 3, the hydroxyl value is 18.7 mgKOH / g, the viscosity is 2400 mPa · s / 25 ° C., and the number average molecular weight measured by GPC is It was 9,000 in terms of standard polypropylene glycol.

[Preparation Example 3]
(Production of alkyl methacrylate grafted polyether (1))
Into a 1 L flask equipped with a stirrer, nitrogen inlet, monomer charging tube and water-cooled condenser, 568.8 parts by weight of the polyoxyalkylene polyol (1) was charged and heated to 120 ° C. with a mantle heater. Next, 189.6 parts by weight of the polyoxyalkylene polyol (1), 175.9 parts by weight of n-butyl methacrylate and 65.7 parts by weight of 2-hydroxyethyl methacrylate, and 1,1- A solution obtained by uniformly mixing 47.0 parts by weight of a radical reaction initiator (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhexa C) obtained by diluting bis (t-butylperoxy) cyclohexane with a hydrocarbon to a purity of 70% It was dripped at the said flask over 4 hours, and was further reacted for 4 hours. Thereafter, a reduced pressure treatment was performed for 2 hours under the conditions of 120 ° C. and 1.3 kPa or less to remove unreacted monomers to obtain a methacrylic acid alkyl ester graft polyether polyol (1). The graft polyether polyol (1) had a hydroxyl value of 54.5 mgKOH / g and a viscosity of 3100 mPa · s / 25 ° C. The appearance was colorless and transparent. Other physical properties are shown in Table 1.

[Preparation Example 4]
(Production of methacrylic acid alkyl ester graft polyether (2))
Into a 1 L flask equipped with a stirrer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, 929.7 parts by weight of the polyoxyalkylene polyol (2) was charged and heated to 120 ° C. with a mantle heater. Next, 29.4 parts by weight of n-butyl methacrylate and 41.0 parts by weight of 2-ethylhexyl methacrylate and 1,1-bis (t-butylperoxy) cyclohexane as the vinyl monomer are hydrocarbons with a purity of 70%. A solution obtained by uniformly mixing 19.2 parts by weight of a radical reaction initiator (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhexa C) was added dropwise to the flask over 4 hours, followed by further reaction for 4 hours. . Thereafter, a reduced pressure treatment was performed for 2 hours under the conditions of 120 ° C. and 1.3 kPa or less to remove unreacted monomers to obtain a methacrylic acid alkyl ester graft polyether polyol (2). The graft polyether polyol (2) has a hydroxyl value of 17.5 mgKOH / g and a viscosity of 310
It was 0 mPa · s / 25 ° C. The appearance was colorless and transparent. Other physical properties are shown in Table 1.

(Production of terminal-blocked alkyl methacrylate grafted polyether (1))
Into a 1 L flask equipped with a stirrer, nitrogen inlet, monomer charging tube and water-cooled condenser, 960.8 parts by weight of the above methacrylic acid alkyl ester graft polyether polyol (1) was charged and heated to 80 ° C. with a mantle heater. . Next, 152.4 parts by weight of acetic anhydride (1.6 moles per mole of hydroxyl group of the graft polyether polyol) was added and reacted at 110 ° C. for 6 hours. Thereafter, the temperature was raised to 170 ° C., a pressure reduction treatment was performed for 2 hours under the condition of 1.3 kPa or less, unreacted acetic anhydride and generated acetic acid were removed, and an acetate ester of a methacrylic acid alkyl ester grafted polyether polyol (hereinafter, A polyether composition (1) containing “grafted polyether (1)” was obtained. The polyether composition (1) has a hydroxyl value of 0 mgKOH / g, a terminal blocking rate of 100%, a hydroxyl group residual rate of 0%, an acid value of 0.2 mgKOH / g, a viscosity of 2300 mPa · s / 25 ° C., moisture The amount was 150 ppm. The appearance was colorless and transparent. Other physical properties are shown in Table 2.

(Production of polyurethane resin composition (1))
A 1 L flask equipped with a stirrer, a nitrogen inlet, and a sample charging tube was charged with 20 parts by weight of the polyether composition (1) and heated to 50 ° C. with a mantle heater. Thereafter, 80 parts by weight of a urethane prepolymer (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Takenate L-1036, viscosity 25000 mPa · s / 25 ° C.) is added, mixed at 50 ° C. for 2 hours, and the graft polyether ( A polyurethane resin composition (1) containing 1) was obtained. The viscosity of this polyurethane resin composition (1) was 15600 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

(Production of terminal-blocked alkyl methacrylate grafted polyether (2))
Instead of the methacrylic acid alkyl ester graft polyether polyol (1), 987.1 parts by weight of the above methacrylic acid alkyl ester graft polyether polyol (2) was used, and the amount of acetic anhydride added was 50.3 parts by weight (the hydroxyl group of the polyol). Except that the molar amount of the sealing agent per mole was changed to 1.6), acetate ester of methacrylic acid alkyl ester graft polyether polyol (hereinafter referred to as “graft polyether (2)”) in the same manner as in Example 1. A polyether composition (2) containing The polyether composition (2) has a hydroxyl value of 0 mgKOH / g, a terminal blocking rate of 100%, a hydroxyl group residual rate of 0%, an acid value of 0.2 mgKOH / g, a viscosity of 2350 mPa · s / 25 ° C., and moisture content. The amount was 140 ppm. The appearance was colorless and transparent. Other physical properties are shown in Table 2.

(Production of polyurethane resin composition (2))
A polyurethane resin composition (2) containing the graft polyether (2) in the same manner as in Example 1 except that 20 parts by weight of the polyether composition (2) was used instead of the polyether composition (1). Got. The viscosity of the polyurethane resin composition (2) was 15700 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

(Production of terminal-blocked alkyl methacrylate grafted polyether (3))
Acetic ester of methacrylic acid alkyl ester grafted polyether polyol in the same manner as in Example 1 except that the amount of acetic anhydride added was changed to 123.9 parts by weight (1.3 mole per mole of hydroxyl group of graft polyether polyol). A polyether composition (3) containing (hereinafter referred to as “graft polyether (3)”) was obtained. This polyether composition (3) has a hydroxyl value of 11 mgKOH / g, an end-capping rate of 80%, a hydroxyl group residual rate of 20%, an acid value of 0.1 mgKOH / g, a viscosity of 2480 mPa · s / 25 ° C., moisture content The amount was 150 ppm. The appearance was colorless and transparent. Other physical properties are shown in Table 2.

(Production of polyurethane resin composition (3))
A polyurethane resin composition (3) containing the graft polyether (3) in the same manner as in Example 1 except that 20 parts by weight of the polyether composition (3) was used instead of the polyether composition (1). Got. The polyurethane resin composition (3) had a viscosity of 15900 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

[Comparative Example 1]
(Production of polyurethane resin composition (a))
A polyurethane resin composition (a) containing dioctyl phthalate in the same manner as in Example 1 except that 20 parts by weight of dioctyl phthalate having the physical properties shown in Table 2 was used instead of the polyether composition (1). Obtained. The viscosity of the polyurethane resin composition (a) was 12600 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

[Comparative Example 2]
(Production of end-capped polyether (b))
Instead of the methacrylic acid alkyl ester graft polyether polyol (1), 972.7 parts by weight of the above polyoxyalkylene polyol (1) having the physical properties shown in Table 2 was used, and the amount of acetic anhydride added was 105.9 parts by weight. A polyoxyalkylene polyol acetate (hereinafter referred to as “polyether (b)”) is included in the same manner as in Example 1 except that the polyoxyalkylene polyol is changed to 1.6 moles per mole of hydroxyl groups of the polyoxyalkylene polyol. A polyether composition (b) was obtained. The polyether composition (b) has a hydroxyl value of 0 mgKOH / g, a terminal blocking rate of 100%, a hydroxyl group residual rate of 0%, an acid value of 0.1 mgKOH / g, a viscosity of 450 mPa · s / 25 ° C., moisture The amount was 150 ppm. The appearance was colorless and transparent. Other physical properties are shown in Table 2.

(Production of polyurethane resin composition (b))
A polyurethane resin composition (b) containing the polyether (b) was obtained in the same manner as in Example 1 except that 20 parts by weight of the polyether composition (b) was used instead of the polyether composition (1). Obtained. The viscosity of the polyurethane resin composition (b) was 13500 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

[Comparative Example 3]
(Production of end-capped alkyl methacrylate grafted polyether (c))
Acetic ester of alkyl methacrylate ester grafted polyether polyol in the same manner as in Example 1 except that the amount of acetic anhydride added was changed to 66.7 parts by weight (0.7 mole per mole of hydroxyl group of graft polyether polyol). A polyether composition (c) containing (hereinafter referred to as “graft polyether (c)”) was obtained. The polyether composition (c) has a hydroxyl value of 16 mgKOH / g, a terminal blocking rate of 65%, a hydroxyl group residual rate of 35%, an acid value of 0.1 mgKOH / g, a viscosity of 2590 mPa · s / 25 ° C., moisture The amount was 130 ppm. The appearance was colorless and transparent. Other physical properties are shown in Table 2.

(Production of polyurethane resin composition (c))
A polyurethane resin composition (c) containing the graft polyether (3) in the same manner as in Example 1 except that 20 parts by weight of the polyether composition (c) was used in place of the polyether composition (1). Got. The viscosity of the polyurethane resin composition (c) was 14800 mPa · s / 25 ° C. Other physical properties are shown in Table 3.

  The polyether according to the present invention is less likely to change with time such as thickening even when mixed with a compound having a functional group capable of reacting with a hydroxyl group, and is a plasticizer used for polyurethane resin, polyvinyl chloride, etc. In particular, it can be used as a high molecular weight plasticizer, a lubricant, a solvent, a surfactant, and the like used for sealing agents, waterproofing agents, adhesives, paints, molding materials and the like.

Claims (16)

  Of all the terminals of the (meth) acrylic acid alkyl ester graft polyether, the terminal group whose hydroxyl group is sealed with a sealing agent is 70 mol% or more, and the hydroxyl group is less than 30 mol% ( (Meth) acrylic acid alkyl ester graft polyether.   Of all the hydroxyl groups of (meth) acrylic acid alkyl ester graft polyether polyol, 70 mol% or more of hydroxyl groups are sealed with a sealing agent, and less than 30 mol% of hydroxyl groups are left unsealed. The (meth) acrylic acid alkyl ester graft polyether according to claim 1. The (meth) acrylic acid alkyl ester graft polyether polyol is a hydroxyl group-containing (meth) acrylate graft polyether polyol having an ester group represented by the following formula (1) in the molecule: (Meth) acrylic acid alkyl ester graft polyether according to 2,

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 18 carbon atoms.) The (meth) acrylic acid alkyl ester graft polyether polyol is a (meth) acrylate graft polyether polyol having an ester group represented by the following formula (3) in the molecule: The (meth) acrylic acid alkyl ester graft polyether as described.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.) The (meth) acrylic acid alkyl ester graft polyether polyol is a polyol obtained by reacting a polyoxyalkylene polyol and a vinyl monomer containing at least a (meth) acrylic acid alkyl ester, The (meth) acrylic acid alkyl ester graft polyether according to claim 2. The (meth) acrylic acid alkyl ester graft polyether according to claim 5, wherein the (meth) acrylic acid alkyl ester is a hydroxyl group-containing (meth) acrylate represented by the following formula (2).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 18 carbon atoms.) The (meth) acrylic acid alkyl ester graft polyether according to claim 5, wherein the (meth) acrylic acid alkyl ester is a (meth) acrylate represented by the following formula (4).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)   The (meth) acryl according to any one of claims 1 to 7, wherein the hydroxyl group is sealed through at least one kind of bond selected from an ester bond, an ether bond and a urethane bond. Acid alkyl ester grafted polyether.   9. The (meta) according to claim 1, wherein the sealing agent is at least one compound selected from a monocarboxylic acid, a monocarboxylic acid anhydride, and a monocarboxylic acid halide. ) Acrylic acid alkyl ester grafted polyether.   The light transmittance measured with a spectrophotometer is 30% or less at a light wavelength of 300 nm and 90% or more at a light wavelength of 500 nm. Ester graft polyether.   It is a polyether composition containing the (meth) acrylic acid alkyl ester graft polyether according to any one of claims 1 to 10, wherein a terminal group in which hydroxyl groups are sealed among all terminals in the composition. Is a polyether composition characterized in that it is 70 mol% or more and the hydroxyl group is less than 30 mol%.   A plasticizer comprising the (meth) acrylic acid alkyl ester graft polyether according to any one of claims 1 to 10.   A two-component curable polyurethane resin composition, wherein the plasticizer according to claim 12 is contained in a main agent and / or a curing agent.   A one-component curable polyurethane resin composition comprising the plasticizer according to claim 12.   The hydroxyl group is reacted with a sealing agent, and the hydroxyl group is sealed through at least one bond selected from an ester bond, an ether bond and a urethane bond. The manufacturing method of the (meth) acrylic-acid alkylester graft polyether of description.   The (meth) acrylic acid alkyl ester according to claim 15, wherein the sealing agent is at least one compound selected from a monocarboxylic acid, a monocarboxylic acid anhydride, and a monocarboxylic acid halide. A method for producing graft polyether.